A filler, a method for preparing the filler, a resin composition comprising the filler, and articles thereof.

Abstract

This application discloses a filler comprising a first precursor and a second precursor. The first precursor is a hollow filler with a surface coated with a first silane coupling agent; the second precursor is a non-hollow filler with a surface coated with a second silane coupling agent; and the first and second precursors are connected by covalent bonds formed by a chemical reaction between the first and second silane coupling agents on their surfaces. This application also provides a method for preparing the filler and a resin composition including the filler. Prepreg, resin film, laminate, or printed circuit board products made from this resin composition possess excellent moisture absorption and heat resistance, low Df (hygrothermal change rate), low water absorption, and high copper foil tensile strength. Furthermore, the prepreg has a smooth appearance and uniform color, and the substrate has no streaks.

Description

Technical Field

[0001] This application relates to the field of high-frequency communication materials, and more particularly to a resin composition that can be used to prepare products such as prepregs, resin films, laminates or printed circuit boards, as well as a filler for the resin composition and a method for preparing the filler. Background Technology

[0002] With the advent of the 5G era, printed circuit boards (PCBs) for wireless communication are undergoing a new round of technological upgrades. This requires that the basic insulating materials in PCBs not only possess low dielectric properties but also high copper foil tensile strength, low water absorption, high moisture absorption and heat resistance, and excellent dielectric stability to meet the demands of PCBs in harsh environments. In existing technologies, to achieve good dielectric properties, polyphenylene ether or polyolefin is typically selected as the main material, triallyl isocyanurate (TAIC) as a crosslinking agent, and a large amount of spherical silica filler. The resulting substrate exhibits good dielectric properties, but these materials cannot simultaneously meet the increasingly demanding requirements for high copper foil tensile strength, low water absorption, high moisture absorption and heat resistance, and excellent dielectric stability. Therefore, there is an urgent need in this field to develop novel fillers that combine high copper foil tensile strength, low water absorption, high moisture absorption and heat resistance, and excellent dielectric stability. Summary of the Invention

[0003] To address the aforementioned problems, the first aspect of this application provides a filler comprising a first precursor and a second precursor. The first precursor is a hollow filler with a surface coated with a first silane coupling agent; the second precursor is a non-hollow filler with a surface coated with a second silane coupling agent; and the first precursor and the second precursor are connected by covalent bonds formed by a chemical reaction between the first silane coupling agent and the second silane coupling agent on their surfaces.

[0004] Optionally, the chemical composition of hollow fillers and non-hollow fillers can be independently organic, inorganic, or a combination thereof. Organic components include, but are not limited to, polytetrafluoroethylene, polyphenylene sulfide, polyetherimide, polyphenylene ether, polyethersulfone, silicone, or combinations thereof; inorganic components include, but are not limited to, glass, silicon dioxide, sodium oxide, calcium oxide, boron trioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, barium titanate, lead titanate, strontium titanate, calcium titanate, magnesium titanate, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanate, zinc molybdate, calcium molybdate, magnesium molybdate, zinc molybdate-modified talc, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, talc, silicon nitride, calcined kaolin, or combinations thereof.

[0005] Furthermore, the maximum particle size of hollow packing is less than or equal to 100 μm, and the maximum particle size of non-hollow packing is less than or equal to 15 μm.

[0006] Optionally, the first silane coupling agent and the second silane coupling agent are each independently a silane coupling agent containing carbon-carbon double bonds, epoxy groups, mercapto groups, amino groups, or combinations thereof.

[0007] Furthermore, the amount of the first silane coupling agent is 0.5% to 5% of the weight of the hollow filler, and the amount of the second silane coupling agent is 0.5% to 5% of the weight of the non-hollow filler.

[0008] Furthermore, the weight ratio of the first precursor to the second precursor is 3:97 to 30:70.

[0009] Secondly, this application provides a method for preparing the above-mentioned filler, comprising the following steps:

[0010] Preparation of the first precursor: Hollow packing is stirred in an alkaline solution to obtain surface-hydroxylated hollow packing; the surface-hydroxylated hollow packing is stirred with a first silane coupling agent in a first solvent to obtain the first precursor, wherein the first precursor is a hollow packing coated with the first silane coupling agent.

[0011] Preparation of the second precursor: The non-hollow filler is stirred in an alkaline solution to obtain a non-hollow filler with hydroxylated surface; the non-hollow filler with hydroxylated surface is stirred with a second silane coupling agent in a first solvent to obtain the second precursor, which is a non-hollow filler with a second silane coupling agent coated on its surface.

[0012] Chemical linking of the first and second precursors: The first and second precursors are mixed uniformly in a second solvent, and in the presence of a first curing accelerator, the first and second precursors are chemically linked by a covalent bond formed through a chemical reaction between the first and second silane coupling agents coated on their respective surfaces, thus obtaining the filler. Optionally, the first and second silane coupling agents are each independently a silane coupling agent containing carbon-carbon double bonds, epoxy groups, mercapto groups, or amino groups, or a combination thereof.

[0013] Optionally, the alkaline solution includes, but is not limited to, sodium hydroxide solution, potassium hydroxide solution, triethylamine or potassium tert-butoxide.

[0014] Optionally, the first solvent includes, but is not limited to, water, methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, methylpyrrolidone, or mixtures thereof.

[0015] Optionally, the second solvent includes, but is not limited to, methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and other solvents or mixtures thereof.

[0016] Optionally, the first hardening accelerator includes, but is not limited to, Lewis base, hardening initiator, or a combination thereof.

[0017] Furthermore, the temperatures for the preparation steps of the first precursor and the second precursor are controlled to be between 20°C and 60°C, respectively, and the stirring times are between 1 and 8 hours, respectively.

[0018] Furthermore, the temperature of the chemical linking step between the first precursor and the second precursor is controlled to be between 60°C and 120°C, and the time for the chemical reaction to occur is controlled to be between 1 and 6 hours.

[0019] Furthermore, in the step of chemically linking the first precursor and the second precursor, the weight ratio of the first precursor to the second precursor is controlled to be from 3:97 to 30:70.

[0020] Thirdly, this application also provides a resin composition comprising:

[0021] (A) Polyphenylene ether resin containing unsaturated carbon-carbon double bonds;

[0022] (B) Crosslinking agents containing unsaturated carbon-carbon double bonds; and,

[0023] (C) The packing material as described in the first aspect of this application.

[0024] Optionally, polyphenylene ether resins containing unsaturated carbon-carbon double bonds include, but are not limited to, vinyl benzyl polyphenylene ether resin, (meth)acryloyl polyphenylene ether resin, vinyl polyphenylene ether resin, or combinations thereof.

[0025] Optionally, crosslinking agents containing unsaturated carbon-carbon double bonds include, but are not limited to, bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, diallyl bisphenol A, styrene, butadiene, decanadiene, octadiene, vinylcarbazole, acrylates, or combinations thereof.

[0026] Further, based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition comprises 5 to 40 parts by weight of a crosslinking agent containing unsaturated carbon-carbon double bonds, and 50 to 130 parts by weight of the filler.

[0027] Further, based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition further includes 13 to 35 parts by weight of a polyolefin. The polyolefin includes, but is not limited to, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride-butadiene copolymer, polymethylstyrene, hydrogenated polybutadiene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-maleic anhydride terpolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, or combinations thereof.

[0028] Furthermore, the resin composition further includes maleimide resin, benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, styrene-maleic anhydride, amine curing agent, polyamide, polyimide, or a combination thereof.

[0029] Furthermore, the resin composition further includes a flame retardant, a second curing accelerator, a polymerization inhibitor, a third solvent, a third silane coupling agent, a surfactant, a dye, a toughening agent, or a combination thereof.

[0030] Fourthly, this application provides an article of manufacture made from the resin composition described in the third aspect of this application, including but not limited to prepreg, resin film, laminate, or printed circuit board.

[0031] Articles made from the resin composition provided in this application have one, more, or all of the following characteristics:

[0032] Visual inspection revealed that the prepreg had a smooth appearance and uniform color.

[0033] Referring to the method of IPC-TM-650 2.4.8, the copper foil tensile strength of the article is measured to be greater than or equal to 3.8 lb / inch;

[0034] Referring to the methods of IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, the moisture absorption and heat resistance of the product were tested, and no plate bursting occurred;

[0035] Referring to the method of IPC-TM-650-2.6.2.1, the water absorption rate of the product is measured to be less than or equal to 0.30%;

[0036] Referring to the method of JIS C2565, the dielectric loss of the product at room temperature and after being placed in an environment of 85°C and 85% relative humidity for 48 hours were measured at a frequency of 10 GHz. The calculated dielectric loss damp heat change rate of the product is less than or equal to 40%.

[0037] Visual inspection revealed that the substrate had no stripes on its surface. Attached Figure Description

[0038] Figure 1 This is a schematic diagram of the chemical linkage process between the first precursor and the second precursor.

[0039] Figure 2 SEM image of packing material C1 provided by the present invention.

[0040] Figure 3 The image shows a SEM image of filler X1, which is not part of this invention.

[0041] Figure 4 The image shows a SEM image of filler X2, which is not part of this invention. Detailed Implementation

[0042] To enable those skilled in the art to understand the features and effects of this application, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art in this application, and in case of conflict, the definitions in this specification shall prevail.

[0043] The theories or mechanisms described and disclosed herein, whether right or wrong, shall not in any way limit the scope of this application, that is, the content of this application may be implemented without being limited by any particular theory or mechanism.

[0044] In this document, "this application" means "this invention" or "this disclosure".

[0045] The terms “a,” “an,” “a,” or similar expressions are used herein to describe the components and technical features described in this application. Such descriptions are merely for convenience and to provide a general meaning for the scope of this application. Therefore, such descriptions should be understood to include one or at least one, and the singular includes the plural, unless clearly otherwise indicated.

[0046] In this article, "or a combination thereof" means "or any combination thereof", and "any one", "any kind", "any one" means "any one", "any kind", "any one".

[0047] In this document, the terms “comprising,” “including,” “having,” “containing,” or any other similar terms are open-ended transitional phrases, intended to encompass non-exclusive inclusions. For example, a composition or article thereof containing multiple elements is not limited to the elements listed herein, but may also include other elements not explicitly listed but typically inherent to the composition or article thereof. Furthermore, unless explicitly stated to the contrary, the term “or” is an inclusive “or,” not an exclusive “or.” For example, the condition “A or B” is satisfied in any of the following cases: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist). Furthermore, in this article, the interpretation of the terms “contains,” “includes,” “has,” and “contains” should be regarded as having been specifically disclosed and simultaneously covering closed conjunctions such as “composed of,” “composed of,” and “remaining as,” as well as conjunctions such as “essentially composed of,” “mainly composed of,” “mainly composed of,” “basically containing,” “basically composed of,” “basically composed of,” and “essentially containing.”

[0048] In this document, all features or conditions defined in the form of numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible subranges and individual numerical values ​​(including integers and fractions) within those ranges, particularly integer values. For example, range descriptions such as "1.0 to 8.0" or "between 1.0 and 8.0" should be considered as specifically disclosing all subranges such as 1.0 to 8.0, 1.0 to 7.0, 2.0 to 8.0, 2.0 to 6.0, 3.0 to 6.0, 4.0 to 8.0, 3.0 to 8.0, etc., and should be considered as covering endpoint values, particularly subranges defined by integer values, and should be considered as specifically disclosing individual numerical values ​​within those ranges such as 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, etc. Unless otherwise specified, the foregoing interpretation applies to all content throughout this application, regardless of its scope.

[0049] If a quantity, concentration, or other numerical value or parameter is expressed as a range, preferred range (or better range), or a series of upper and lower limits, it should be understood that this document has specifically disclosed all ranges consisting of any pair of upper or preferred values ​​(or better values) and lower or preferred values ​​(or better values) of that range, regardless of whether such ranges are disclosed separately. Furthermore, when a range of numerical values ​​is mentioned herein, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

[0050] In this document, numerical values ​​are to be understood as having a precision with significant digits, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover the range of 39.50 to 40.49.

[0051] 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 or any individual element within a Markush group or option list 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 or individual members within a Markush group or option list 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 and / or X2 and / or X3 and Y is Y1 and / or Y2 and / or Y3 has been fully described.

[0052] Unless otherwise specified, in this application, a compound refers to a chemical substance formed by two or more elements linked by chemical bonds, including, but not limited to, small molecule compounds and macromolecules. The term "compound" in this document is not limited to a single chemical substance, but can also be interpreted as a class of chemical substances having the same composition or the same properties.

[0053] Unless otherwise specified, a chemical reaction is the process by which molecules break down into atoms, and the atoms rearrange and recombine to form new molecules.

[0054] Unless otherwise specified, in this application, a polymer refers to the product formed by the polymerization reaction of monomers, often including an aggregate of many high molecules, each of which is composed of many simple structural units repeatedly linked by covalent bonds. The monomer is the compound that synthesizes the polymer. Polymers can include homopolymers, copolymers, prepolymers, etc., but are not limited to these. A homopolymer is a polymer polymerized from a single monomer. Copolymers include random copolymers (structures such as -AABABBBAAABBA-), alternating copolymers (structures such as -ABABABAB-), graft copolymers (structures such as -AA(A-BBBB)AA(A-BBBB)AAA-), and block copolymers (structures such as -AAAAA-BBBBBB-AAAAA-), etc. For example, the styrene-butadiene copolymer in this application can be interpreted as a styrene-butadiene random copolymer, a styrene-butadiene alternating copolymer, a styrene-butadiene graft copolymer, or a styrene-butadiene block copolymer. Prepolymers are polymers with lower molecular weights, falling between those of monomers and the final polymer. Prepolymers contain reactive functional groups that allow for further polymerization to yield fully cross-linked or hardened products with higher molecular weights. Polymers include, but are not limited to, oligomers. Oligomers, also known as low-molecular-weight polymers, are polymers composed of 2 to 20 repeating units, typically 2 to 5 repeating units.

[0055] Unless otherwise specified, "resin" in this application is a common name for a synthetic polymer, and in interpretation, it may include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and their polymers, etc., and is not limited thereto.

[0056] Unless otherwise specified, in this application, modified products include products after modification of the reactive functional groups of each resin, products after prepolymerization of each resin with other resins, products after crosslinking of each resin with other resins, products after copolymerization of each resin with other resins, etc.

[0057] Unless otherwise specified, the unsaturated bond referred to in this application refers to a reactive unsaturated bond, such as, but not limited to, an unsaturated double bond that can undergo cross-linking reactions with other functional groups, such as, but not limited to, an unsaturated carbon-carbon double bond that can undergo cross-linking reactions with other functional groups.

[0058] The unsaturated carbon-carbon double bonds described in this application are preferably, but are not limited to, vinyl, vinylbenzyl, (meth)acryloyl, allyl, or combinations thereof. When interpreting vinyl, it should include both vinyl and vinylidene. When interpreting (meth)acryloyl, it should include both acryloyl and methacryloyl.

[0059] Unless otherwise specified, the alkyl and alkenyl groups mentioned in this application are interpreted to include their various isomers. For example, propyl should be interpreted to include both n-propyl and isopropyl.

[0060] The maximum particle size mentioned in this invention, namely D100, represents the particle size value corresponding to the cumulative particle size distribution number of a filler sample reaching 100%. Its physical meaning is that the filler particles with a particle size less than or equal to this particle size value account for 100%.

[0061] Unless otherwise specified, in this application, parts by weight represent the relative number of parts by weight in the composition, and can be any unit of weight, such as, but not limited to, kilograms, grams, pounds, etc. For example, 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds can represent 100 kilograms of polyphenylene ether resin containing unsaturated carbon-carbon double bonds or 100 pounds of polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0062] It should be understood that the features disclosed in the various embodiments herein can be arbitrarily combined to form the technical solution of this application, as long as there is no contradiction in the combination of these features.

[0063] The present application will be described below with reference to specific embodiments and examples. It should be understood that these specific embodiments and examples are merely illustrative and are not intended to limit the scope or use of the present application. Unless otherwise stated, the methods, reagents, and conditions used in the examples are conventional methods, reagents, and conditions in the art.

[0064] In a first aspect, this application discloses a filler comprising a first precursor and a second precursor. The first precursor is a hollow filler with a surface coated with a first silane coupling agent, and the second precursor is a non-hollow filler with a surface coated with a second silane coupling agent. The first precursor and the second precursor are connected by covalent bonds formed by a chemical reaction between the first silane coupling agent and the second silane coupling agent on their surfaces.

[0065] The type of chemical reaction is not particularly limited and may include, but is not limited to, various types of organic chemical reactions, preferably addition reactions or substitution reactions. More preferably, it is an amino addition reaction, a mercapto addition reaction, or an epoxy ring-opening substitution reaction.

[0066] The shape of the hollow and non-hollow packing materials is not particularly limited, and may include, but is not limited to, spherical, fibrous, or granular shapes. Preferably, both the hollow and non-hollow packing materials are spherical.

[0067] The chemical composition of the hollow filler and non-hollow filler is not particularly limited, and may include any one or more organic or inorganic components suitable for the manufacture of prepregs, resin films, laminates, or printed circuit boards. The chemical compositions of the hollow filler and non-hollow filler may be the same or different. Specific examples of organic components include, but are not limited to, polytetrafluoroethylene, polyphenylene sulfide, polyetherimide, polyphenylene ether, polyethersulfone, silicone, or combinations thereof. For example, specific examples of inorganic components include, but are not limited to: glass, silicon dioxide (molten and non-molten), sodium oxide, calcium oxide, boron trioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, barium titanate, lead titanate, strontium titanate, calcium titanate, magnesium titanate, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanate, zinc molybdate, calcium molybdate, magnesium molybdate, zinc molybdate-modified talc, zinc oxide, zirconium oxide, mica, boehmite, calcined talc, talc, silicon nitride, calcined kaolin, or combinations thereof. Among these, glass is a commonly used inorganic component in the art, composed of a composite of various oxides, with silicon dioxide as its main component, optionally including aluminum oxide, sodium oxide, calcium oxide, boron trioxide, etc. For example, but not limited to, the iM30K insulated glass manufactured by 3M mainly contains 70-80 wt% silica, 3-8 wt% sodium oxide, 8-15 wt% calcium oxide, and 2-6 wt% boron trioxide. Preferably, the hollow filler is hollow silica, insulated glass, hollow silicone, or a combination thereof. Preferably, the non-hollow filler is silica or glass.

[0068] For example, specific examples of hollow packing materials applicable to this application include, but are not limited to, iM30K, iM16K, S32HS, S38HS or S60HS purchased from 3M, Ecosphere SID200Z or Ecosphere SID 311Z purchased from Trelleborg Emerson & Cuming, Inc., and BIONIC BUBBLE purchased from Sphere Services, Inc. TM Or VEA X-10, purchased from Trelleborg Fillite. 106 or 160W, E-SPHERES SL-75 purchased from Envirospheres Pty. Ltd., S1, S15, S20, S25, S32, S38, G38HS, G32HS, G15 or G22 purchased from SiLi Glass Beads Co., Ltd., and SBN04 or KBN06 purchased from Shima Trading Company.

[0069] The maximum particle size of the hollow and non-hollow fillers is not particularly limited. Preferably, the maximum particle size of the hollow filler is less than or equal to 100 μm, more preferably, the maximum particle size of the hollow filler is less than or equal to 50 μm. Preferably, the maximum particle size of the non-hollow filler is less than or equal to 15 μm, more preferably, the maximum particle size of the non-hollow filler is less than or equal to 7 μm.

[0070] The types of the first and second silane coupling agents are not particularly limited, as long as they can chemically react. Preferably, the first silane coupling agent includes, but is not limited to, silane coupling agents containing carbon-carbon double bonds, epoxy groups, mercapto groups, or amino groups, or combinations thereof. Preferably, the second silane coupling agent includes, but is not limited to, silane coupling agents containing carbon-carbon double bonds, epoxy groups, mercapto groups, or amino groups, or combinations thereof.

[0071] The silane coupling agents containing carbon-carbon double bonds, epoxy groups, mercapto groups, or amino groups described in this application are not particularly limited in terms of other functional groups besides carbon-carbon double bonds, epoxy groups, mercapto groups, or amino groups. For example, but not limited to, they may contain alkyl, aryl, alkyl-substituted aryl, halogen-substituted alkyl, halogen-substituted aryl, oxy groups, or combinations thereof.

[0072] For example, specific examples of the first and second silane coupling agents used in this application include, but are not limited to, the following products purchased from Shin Etsu: vinyltrimethoxysilane containing vinyl groups (brand name KBM-1003) and vinyltriethoxysilane containing vinyl groups (brand name KBE-1003); p-styrenetrimethylsilane containing styrene groups (brand name KBM-1403); 3-methacryloyloxypropylmethyldimethoxysilane containing methacryloyl groups (brand name KBM-502), 3-methacryloyloxypropyltrimethoxysilane containing methacryloyl groups (brand name KBM-503), and 3-methacryloyloxypropylmethyldimethoxysilane containing methacryloyl groups (brand name KBE-502). 3-Methacryloyloxypropyltriethoxysilane (KBE-503); 3-Acrylic acid propyltrimethoxysilane (KBM-5103, containing propylene groups); 2-(3,4-epoxyhexyl)ethanedimethyltrimethoxysilane (KBM-303, containing epoxy groups); 3-glycidyl ether oxypropylmethyldimethoxysilane (KBM-402); 3-glycidyl ether oxypropyltrimethoxysilane (KBM-403); and others. BE-402 is 3-glycidyl etheroxypropylmethyldiethoxysilane, and KBE-403 is 3-glycidyl etheroxypropyltriethoxysilane; mercapto-containing products include KBM-802 and KBM-803; amino-containing products include KBM-602 and KBM-603. Partially hydrolyzed products of propyltrimethoxysilane, 3-aminopropyltrimethoxysilane (KBM-903), 3-aminopropyltriethoxysilane (KBE-903), 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine (KBE-9103P), N-phenyl-3-aminopropyltrimethoxysilane (KBM-573), and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane (KBM-573) hydrochloride. Also, Z-6040 or Z-6020 purchased from Dow Corning, Y-9669 purchased from Momentive, and A-187 purchased from Union Carbide.

[0073] The amount of the first silane coupling agent is not particularly limited. For example, but not limited to, based on the weight of the hollow packing material, the weight of the first silane coupling agent added is 0.5% to 5% of the weight of the hollow packing material, preferably 0.5% to 3.5%. The amount of the second silane coupling agent is not particularly limited. For example, but not limited to, based on the weight of the non-hollow packing material, the weight of the second silane coupling agent added is 0.5% to 5% of the weight of the non-hollow packing material, preferably 0.5% to 2.5%.

[0074] In the filler, the weight ratio of the first precursor to the second precursor is not particularly limited, and the weight ratio is, for example, but not limited to, between 3:97 and 30:70, preferably between 10:90 and 25:75. For example, the weight ratio of the first precursor to the second precursor can be 3:97, 5:95, 10:90, 15:85, 20:80, 25:95, or 30:70. If too much of the first precursor is added, it will reduce the density of the filler, causing the filler to float on the surface of the adhesive and not be easily dispersed evenly in the adhesive.

[0075] Secondly, this application also discloses a method for manufacturing the packing material described in the first aspect, comprising the following steps:

[0076] Preparation of the first precursor: Hollow packing is stirred in an alkaline solution to obtain surface-hydroxylated hollow packing; the surface-hydroxylated hollow packing is stirred with a first silane coupling agent in a first solvent to obtain the first precursor, which is a hollow packing coated with the first silane coupling agent.

[0077] Preparation of the second precursor: The non-hollow filler is stirred in an alkaline solution to obtain a non-hollow filler with hydroxylated surface; the non-hollow filler with hydroxylated surface is stirred with a second silane coupling agent in a first solvent to obtain the second precursor, which is a non-hollow filler with a second silane coupling agent coated on its surface.

[0078] Chemical linking of the first and second precursors: The first and second precursors are mixed uniformly in a second solvent, and in the presence of a first curing accelerator, the first and second precursors are chemically linked through a chemical reaction between the first and second silane coupling agents coated on their respective surfaces, forming covalent bonds to obtain the filler. A schematic diagram of this preparation process is shown below. Figure 1 As shown, ~~~~~~ R1 represents the first silane coupling agent, ~~~~~ R2 represents the second silane coupling agent, white represents hollow packing, and black represents non-hollow packing.

[0079] In the above preparation steps, there is no particular restriction on the order of the preparation steps of the first precursor and the second precursor. For example, the first precursor can be prepared first, followed by the preparation of the second precursor, and then the chemical linkage between the first and second precursors can be performed. Alternatively, the second precursor can be prepared first, followed by the preparation of the first precursor, and then the chemical linkage between the first and second precursors can be performed. Yet another example is that the preparation of the first and second precursors can be performed simultaneously, and then the chemical linkage between the first and second precursors can be performed.

[0080] The alkaline solution described above is not particularly limited, and may include, but is not limited to, sodium hydroxide solution, potassium hydroxide solution, triethylamine, or potassium tert-butoxide. Preferably, in the preparation steps of the first precursor and the second precursor, the alkaline solution is a sodium hydroxide solution.

[0081] In the preparation steps of the first and second precursors described above, the temperature is controlled within the range of 20°C to 60°C, and the stirring time is controlled within the range of 1 to 8 hours. Preferably, in the preparation steps of the first and second precursors, the temperature is controlled within the range of 25°C to 55°C, and the stirring time is controlled within the range of 3 to 5 hours.

[0082] The type of the first solvent is not particularly limited; its main function is to disperse the filler. For example, the first solvent includes, but is not limited to, water, 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, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and other solvents or mixtures thereof. Preferably, the first solvent is a mixture of ethanol and water (ethanol to water volume ratio of 5 to 20:1).

[0083] The type of the second solvent is not particularly limited. For example, the second solvent includes, 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, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and other solvents or mixtures thereof. Preferably, the second solvent is toluene.

[0084] The first curing accelerator applicable to this application is not particularly limited to catalysts such as Lewis bases or Lewis acids. Lewis bases may include imidazole, boron trifluoride amine complexes, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP), or combinations thereof. Lewis acids may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, zinc, etc., and metal catalysts such as zinc octanoate and cobalt octanoate. The first curing accelerator also includes curing initiators, such as peroxides that can generate free radicals. Curing initiators include, but are not limited to: dibenzoyl peroxide (BPO), dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), di-tert-butyl peroxide, and di(tert-butylperoxy)hexane. The precursors are propylbenzene, 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-bis(benzoylperoxy)hexane, lauroyl peroxide, tert-hexyl peroxypentanoate, dibutylperoxyisopropylbenzene, bis(4-tert-butylcyclohexyl)peroxydicarbonate, or combinations thereof. Preferably, the first curing accelerator in the chemical linking step between the first and second precursors is a Lewis base. More preferably, the first curing accelerator in the chemical linking step between the first and second precursors is imidazole or triphenylphosphine.

[0085] In the chemical linking step between the first and second precursors described above, the temperature is controlled within the range of 60°C to 120°C, and the chemical reaction time is controlled within the range of 1 to 6 hours. Preferably, the temperature in the chemical linking step between the first and second precursors is controlled within the range of 85°C to 105°C, and the chemical reaction time is controlled within the range of 1 to 4 hours.

[0086] Thirdly, this application discloses a resin composition comprising the filler described in the first aspect above.

[0087] For example, the resin composition may include:

[0088] (A) Polyphenylene ether resin containing unsaturated carbon-carbon double bonds;

[0089] (B) Crosslinking agents containing unsaturated carbon-carbon double bonds; and

[0090] (C) Packing material.

[0091] The aforementioned polyphenylene ether resin containing unsaturated carbon-carbon double bonds is not particularly limited and can be any one or more polyphenylene ether resins containing unsaturated carbon-carbon double bonds suitable for the manufacture of prepregs, resin films, laminates or printed circuit boards, and can be any one or more commercially available products, self-made products or combinations thereof.

[0092] The polyphenylene ether resins used in this application all possess unsaturated carbon-carbon double bonds and a phenylene ether backbone. The unsaturated carbon-carbon double bonds are reactive functional groups, capable of self-polymerization upon heating, or undergoing free radical polymerization with other unsaturated components in the resin composition, ultimately resulting in cross-linking and curing. The cured product exhibits high heat resistance and low dielectric properties. Preferably, the polyphenylene ether resins containing unsaturated carbon-carbon double bonds include those with 2,6-dimethyl substitution on the phenylene ether backbone. The methyl group, after substitution, forms a steric hindrance, making it difficult for the oxygen atoms on the ether to form hydrogen bonds or van der Waals forces, thus reducing hygroscopicity and resulting in even lower dielectric properties.

[0093] Typically, the polyphenylene ether containing unsaturated carbon-carbon double bonds suitable for this application may have the structure shown in formula (1):

[0094]

[0095] Wherein, a and b are each independent positive integers from 1 to 30; preferably, a and b are each independent positive integers from 1 to 10; more preferably, a and b are each independent positive integers from 1 to 5.

[0096] -(OMO)- has the structure shown in equation (2) or equation (3):

[0097]

[0098] L has the structure shown in equation (4):

[0099]

[0100] Among them, R9, R 10 R 15 and R 16 Whether the atoms are the same or different, each is independently a halogen atom, a C1-C6 alkyl group, or a phenyl group; R 11 R 12 R 13 and R 14Whether the R9 and R1 are the same or different, each is independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, or a phenyl group; in some embodiments, R9, R1, R2, R3, R4, R5, R6, R7, R8, R9 ... 10 R 11 R 14 R 15 and R 16 Each is an independent methyl group, R 12 R 13 Each atom is an independent hydrogen atom;

[0101] R 17 R 18 R 19 R 20 R 21 R 22 R 23 and R 24 Whether the atoms are the same or different, each is independently a halogen atom, a C1-C6 alkyl group, a phenyl group, or a hydrogen atom; in some embodiments, R 17 R 18 R 23 and R 24 Each is a methyl group independently;

[0102] A is a C1-C20 straight-chain hydrocarbon group, a C1-C20 branched hydrocarbon group (such as a branched alkyl group), or a C3-C20 cyclic hydrocarbon group (such as a cycloalkyl group), preferably -CH2- or -C(CH3)2-;

[0103] R 25 R 26 R 27 and R 28 Whether they are the same or different, each is independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group or a phenyl group, preferably each is independently a hydrogen atom or -CH3;

[0104] Z has the structure shown in equation (5), equation (6), or equation (7):

[0105]

[0106] Among them, R 34 R 35 For hydrogen atoms; R 29 R 30 R 31 R 32 and R 33Whether identical or different, each is independently a hydrogen atom, a halogen atom, an alkyl group, or a halogen-substituted alkyl group. Preferably, the alkyl group is a C1-C6 alkyl group, and the halogen-substituted alkyl group is preferably a C1-C6 alkyl group substituted with halogen. Q3 and Q4 are each independently an organic group having at least one carbon atom, and the organic group optionally includes one or more of a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. In some embodiments, Q3 and Q4 are methylene (-CH2-). In some embodiments, R... 29 To R 33 Each is an independent hydrogen atom or a C1 to C6 alkyl group.

[0107] In some embodiments, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes, but is not limited to, vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2400 to 2800 (e.g., vinyl benzyl bisphenol A polyphenylene ether resin), (meth)acryloyl polyphenylene ether resins with a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Company), vinyl polyphenylene ether resins with a number average molecular weight of about 2200 to 3000, or combinations thereof. The vinyl polyphenylene ether resin may include various polyphenylene ether resins disclosed in U.S. Patent Application US20160185904A1, all of which are incorporated herein by reference. Among them, ethylene benzyl polyphenylene ether resin includes, but is not limited to, ethylene benzyl biphenyl polyphenylene ether resin, ethylene benzyl bisphenol A polyphenylene ether resin, or combinations thereof.

[0108] The crosslinking agents containing unsaturated carbon-carbon double bonds applicable to this application are not particularly limited, and include, but are not limited to, bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, diallyl bisphenol A, styrene, butadiene, decanadiene, octadiene, vinylcarbazole, acrylates, or combinations thereof. Isomers or prepolymers of these components are also included in the interpretation.

[0109] Unless otherwise specified, with (A) the total mass of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds being 100 parts by weight, the amount of crosslinking agent (B) containing unsaturated carbon-carbon double bonds added is preferably 5 to 40 parts by weight. If the amount of crosslinking agent containing unsaturated carbon-carbon double bonds added is too small or too large, the crosslinking density will not achieve the optimal effect, and the glass transition temperature will decrease.

[0110] Unless otherwise specified, with a total mass of (A) polyphenylene ether resin containing unsaturated carbon-carbon double bonds of 100 parts by weight, the amount of filler (C) added is preferably 50 to 130 parts by weight. If the amount of filler (C) added is too small, the dimensional stability of the product will decrease; if the amount of filler (C) added is too large, the filler will not be easily dispersed evenly in the adhesive, resulting in poor consistency of properties in different areas of the product.

[0111] In addition to the aforementioned (A) polyphenylene ether resin containing unsaturated carbon-carbon double bonds, (B) crosslinking agent containing unsaturated carbon-carbon double bonds, and (C) filler, the resin composition of this application may optionally be further supplemented with polyolefins.

[0112] The types of polyolefins applicable to this application are not particularly limited, and may be any one or more olefin polymers suitable for the manufacture of prepregs, resin films, laminates or printed circuit boards, and may be any one or more commercially available products, homemade products or combinations thereof.

[0113] The polyolefins described in this application include, but are not limited to, diene polymers, monoene polymers, hydrogenated diene polymers, or combinations thereof. The diene is a hydrocarbon compound containing two unsaturated carbon-carbon double bonds, and the monoene is a hydrocarbon compound containing one unsaturated carbon-carbon double bond. Typically, the number average molecular weight is between 1000 and 150000. Due to the large molecular weight of polyolefins and the regular, repeating carbon-carbon bonds in the main chain, the molecules have low polarity, which can reduce the dielectric properties of the cured product.

[0114] In some embodiments, specific examples of polyolefins include, but are not limited to: polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride-butadiene copolymer, polymethylstyrene, hydrogenated polybutadiene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-maleic anhydride terpolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, or combinations thereof. Modifications of these components are also included in the interpretation.

[0115] In some embodiments, the polyolefin is preferably a butadiene-based or isoprene-based diene polymer, a hydrogenated butadiene-based or hydrogenated isoprene-based hydrogenated diene polymer, or a combination thereof. Specific examples include, but are not limited to: polybutadiene, hydrogenated polybutadiene, polyisoprene, styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride-butadiene copolymer, or a combination thereof.

[0116] In some embodiments, this application uses hydrogenated styrene-butadiene block copolymer (G1726, SEBS) manufactured by Kraton Pharmaceuticals, polybutadiene (B-3000) manufactured by Nippon Soda, and styrene-butadiene block copolymer (SBS-C) manufactured by Nippon Soda.

[0117] Unless otherwise specified, the total mass of (A) polyphenylene ether resin containing unsaturated carbon-carbon double bonds is 100 parts by weight, and the amount of polyolefin added is preferably 13 to 35 parts by weight.

[0118] In addition to the aforementioned components, the resin composition of this application may further include, as needed, maleimide resin, benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, styrene-maleic anhydride, amine curing agent, polyamide, polyimide, or combinations thereof. Modified forms of these components are also included in the interpretation.

[0119] Unless otherwise specified, the total mass of (A) polyphenylene ether resin containing unsaturated carbon-carbon double bonds is 100 parts by weight, and the amount of any one of the following components can be from 1 part by weight to 100 parts by weight: maleimide resin, benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, styrene maleic anhydride, amine curing agent, polyamide and polyimide. The ratio between them can be adjusted as needed.

[0120] The maleimide resin used in the resin composition described in this application is not particularly limited and may be any one or more maleimide resins suitable for the manufacture of prepregs, resin films, laminates or printed circuit boards. In some embodiments, the maleimide resin includes, but is not limited to, 4,4'-diphenylmethane bismaleimide, polyphenylmethanemaleimide (or oligomer of phenylmethane maleimide), bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, and 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide. 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 Maleimide (VBM), maleimide resins containing aliphatic long-chain structures, prepolymers of diallyl compounds and maleimide resins, prepolymers of diamines and maleimide resins, prepolymers of polyfunctional amines and maleimide resins, prepolymers of acidic phenolic compounds and maleimide resins, or combinations thereof. Modifications of these components are also included in the interpretation.

[0121] For example, maleimide resins such as, but not limited to, those with trade names 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 manufactured by Daiwakasei Industry Co., Ltd., or those with trade names BMI-70, BMI-80 and others manufactured by KI Chemical Co., Ltd.

[0122] For example, maleimide resins containing aliphatic long-chain structures, or imide-elongated maleimide resins, may include various imide-elongated maleimide resins disclosed in Taiwan Patent Application TW200508284A, all of which are incorporated herein by reference. Maleimide resins containing aliphatic long-chain structures applicable to this application include, but are not limited to, maleimide resins manufactured by the designer's subsidiaries under trade names such as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000.

[0123] The examples of benzoxazine resins suitable for the resin compositions described in this application are not particularly limited, and may include various benzoxazine resins known in the art, including but not limited to bisphenol A type benzoxazine resins, bisphenol F type benzoxazine resins, phenolphthalein type benzoxazine resins, dicyclopentadiene type benzoxazine resins, phosphorus-containing benzoxazine resins, diamine type benzoxazine resins, vinyl-containing benzoxazine resins, or combinations thereof. The diamine type benzoxazine resins include diaminodiphenyl ether type benzoxazine resins, diaminobisphenol F type benzoxazine resins, diaminobiphenyl type benzoxazine resins, or combinations thereof. For example, the benzoxazine resin may include, but is not limited to, benzoxazine resins manufactured by Huntsman under the trade names LZ-8260, LZ-8270, LZ-8280, LZ-8290 or LPY 11051, benzoxazine resins manufactured by Changchun Resin under the trade name PF-3500, or benzoxazine resins manufactured by Showa Polymer Co., Ltd. under the trade name HFB-2006M.

[0124] The epoxy resin suitable for the resin composition described in this application 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, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional 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, and isocyanate-modified epoxy resin. The phenolic epoxy resin may be phenol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenol benzaldehyde epoxy resin, phenol aralkyl novolac epoxy resin, or o-cresol novolac epoxy resin; the phosphorus-containing epoxy resin may be 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) epoxy resin, DOPO-HQ epoxy resin, or a combination thereof.The aforementioned DOPO epoxy resin may include DOPO-containing phenol novolacepoxy resin, DOPO-containing o-cresol novolacepoxy resin, DOPO-containing bisphenol-A novolacepoxy resin, or combinations thereof; the aforementioned DOPO-HQ epoxy resin may include DOPO-HQ-containing phenol novolac epoxy resin, DOPO-HQ-containing o-cresol novolac epoxy resin, DOPO-HQ-containing bisphenol-A novolac epoxy resin, or combinations thereof.

[0125] The silicone resin suitable for the resin composition described in this application may be any type of silicone resin known in the art, including but not limited to polyalkyl silicone resin, polyaryl silicone resin, polyalkylaryl silicone resin, modified silicone resin or a combination thereof. Preferably, the silicone resin applicable to this application is an amino-modified silicone resin, such as, but not limited to, amino-modified silicone resins produced by Shin-Etsu Chemical Industry Co., Ltd. under trade names KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-9409, X-22-1660B-3, etc.; amino-modified silicone resins produced by Toray-Dow Corning Co., Ltd. under trade names BY-16-853U, BY-16-853, BY-16-853B, etc.; amino-modified silicone resins produced by Momentive Performance Materials JAPAN Co., Ltd. under trade names XF42-C5742, XF42-C6252, XF42-C5379, etc., or combinations thereof.

[0126] There are no particular limitations on the cyanate resins suitable for the resin compositions described in this application; any cyanate resin having an Ar-OC≡N structure is acceptable, wherein Ar can be a substituted or unsubstituted aromatic group. The cyanate resins of this application include, but are not limited to, phenolic cyanate resins, bisphenol A cyanate resins, bisphenol F cyanate resins, cyanate resins containing a dicyclopentadiene structure, cyanate resins containing a naphthalene ring structure, phenolphthalein cyanate resins, adamantane cyanate resins, fluorene cyanate resins, or combinations thereof. Phenolic cyanate resins may include bisphenol A phenolic cyanate resins, bisphenol F phenolic cyanate resins, phenolic cyanate resins, or combinations thereof. The aforementioned cyanate ester resins include, but are not limited to, cyanate ester resins produced by Arxada AG 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, ULL-950S, HTL-300, CE-320, LVT-50, and LeCy.

[0127] The active ester suitable for the resin composition described in this application can be any type of active polyester resin known in the art, including but not limited to various commercially available active polyester resin products. For example, but not limited to, active polyester resins manufactured by Dai Nippon Ink Chemical under the trade names HPC-8000 and HPC-8150.

[0128] The phenolic resins suitable for the resin compositions described in this application include, but are not limited to, monofunctional, difunctional, or polyfunctional phenolic resins, including all phenolic resins known for use in the manufacture of prepregs, such as phenolic resins, phenoloxy resins, phenolic resins, etc. Phenolic resins include phenolic resins, o-methylphenolic resins, and bisphenol A resins.

[0129] The styrene-maleic anhydride suitable for the resin composition described in this application can be any type of styrene-maleic anhydride known in the art, wherein the ratio of styrene (S) to maleic anhydride (MA) can be 1:1, 2:1, 3:1, 4:1, 6:1, 8:1, or 12:1. Suitable styrene-maleic anhydrides for this application include, but are not limited to, those manufactured by Cray Valley under trade names such as SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80, or those manufactured by Polyscope under trade names such as C400, C500, C700, and C900.

[0130] Amine curing agents suitable for the resin compositions described in this application include, but are not limited to, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, dicyandiamide, or combinations thereof.

[0131] The polyamide used in the resin composition described in this application may be any type of polyamide resin known in the art, including but not limited to various commercially available polyamide resin products.

[0132] The polyimide suitable for the resin composition described in this application may be any type of polyimide resin known in the art, including but not limited to various commercially available polyimide resin products.

[0133] Furthermore, in addition to the aforementioned components, the resin composition of this application may selectively further include, as needed, a flame retardant, a second curing accelerator, a polymerization inhibitor, a third solvent, a third silane coupling agent, a surfactant, a dye, a toughening agent, or a combination thereof.

[0134] Unless otherwise specified, the amount of flame retardant used in the resin composition described in this application may be adjusted as needed, with the total mass of (A) polyphenylene ether resin containing unsaturated carbon-carbon double bonds being 100 parts by weight, and the amount of flame retardant being, for example, but not limited to, 1 to 100 parts by weight.

[0135] The flame retardant suitable for the resin composition described in this application may be any one or more flame retardants suitable for the manufacture of prepregs, resin films, laminates, or printed circuit boards, such as, but not limited to, bromine-containing flame retardants or phosphorus-containing flame retardants. Bromine-containing flame retardants preferably include decabromodiphenyl ethane, and phosphorus-containing flame retardants are preferably ammonium polyphosphate, p-hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tri(2-carboxyethyl)phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), or resorcinol bis-(dixylenyl)phosphate. phosphate), RDXP (such as commercially available products such as PX-200, PX-201, PX-202, etc.), phosphazene compounds (such as commercially available products such as SPB-100, SPH-100, SPV-100, etc.), melamine polyphosphate, DOPO and its derivatives (such as bisDOPO compounds) or resins, diphenylphosphine oxide (DPPO) and its derivatives (such as bisDPPO compounds) or resins, melamine cyanurate and tri-hydroxy ethylisocyanurate, aluminum phosphonate (such as products such as OP-930, OP-935, etc.) or combinations thereof.

[0136] For example, flame retardants can be DPPO compounds (such as bisDPPO compounds), DOPO compounds (such as bisDOPO compounds), DOPO resins (such as DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), DOPO-bonded epoxy resins, etc., where DOPO-PN is DOPO phenolic resin, and DOPO-BPN can be bisphenol A phenolic resin (DOPO-bisphenol Anovolac, DOPO-BPAN), DOPO-bisphenol F phenolic resin (DOPO-bisphenol F novolac, DOPO-BPFN), or DOPO-bisphenol S phenolic resin (DOPO-bisphenol S novolac, DOPO-BPSN), etc., bisphenol phenolic resins.

[0137] Unless otherwise specified, with the total mass of polyphenylene ether resin containing unsaturated carbon-carbon double bonds (A) being 100 parts by weight, the amounts of the second curing accelerator, polymerization inhibitor, third silane coupling agent, surfactant, and dye used in this application can be adjusted as needed. The amount of any of the above components is, for example, but not limited to, 1 to 20 parts by weight. Preferably, the amount of the second curing accelerator can be 0.5 to 5.0 parts by weight, more preferably 0.5 to 0.6 parts by weight.

[0138] The type of second curing accelerator suitable for the resin composition described in this application is not particularly limited, and may include any one or a combination thereof listed above as the first curing accelerator. Preferably, the second curing accelerator is the aforementioned curing initiator, more preferably 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne.

[0139] The polymerization inhibitors suitable for the resin compositions described in this application serve to suppress the polymerization reaction. Specific examples are not particularly limited, and may include various molecular-type polymerization inhibitors, stable free radical-type polymerization inhibitors, or combinations thereof known in the art. For example, molecular-type polymerization inhibitors suitable for this application include, but are not limited to, phenolic compounds, quinone compounds, aromatic amine compounds, aromatic nitro compounds, sulfur-containing compounds, variable-valence metal chlorides, or combinations thereof. More specifically, molecular-type polymerization inhibitors suitable for this application include, but are not limited to, phenol, hydroquinone, 4-tert-butylcatechol, benzoquinone, chloroquinone, 1,4-naphthoquinone, trimethylquinone, aniline, nitrobenzene, Na₂S, FeCl₃, CuCl₂, or combinations thereof. For example, stable free radical-type polymerization inhibitors suitable for this application include, but are not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine (DPPH), triphenylmethyl, or combinations thereof.

[0140] The main function of adding a third solvent to the resin composition in this application is to dissolve the various components in the resin composition, change the solid content of the resin composition, and adjust the viscosity of the resin composition. The type of third solvent suitable for the resin composition described in this application is not particularly limited, and includes, but is not limited to, any one or a combination thereof listed above as the second solvent.

[0141] The third silane coupling agent suitable for the resin composition described in this application may include silane compounds (such as, but not limited to, siloxane compounds), specific examples including but not limited to aminosilane compounds, epoxide silane compounds, vinyl silane compounds, ester silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, acryloyloxy silane compounds, or combinations thereof.

[0142] The types of surfactants suitable for use in the resin compositions described in this application are not particularly limited. The main function of adding surfactants in this application is to enable the filler to be uniformly dispersed in the resin composition.

[0143] Dyeing agents suitable for the resin compositions described in this application may include, but are not limited to, dyes or pigments.

[0144] The main function of adding toughening agents in this application is to improve the toughness of the resin composition. Toughening agents include, but are not limited to, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, and other rubbers.

[0145] Unless otherwise specified, the amount of toughening agent used in the resin composition may be adjusted as needed, such as, but not limited to, 5 to 50 parts by weight, of a total mass of (A) polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

[0146] The resin compositions of the various embodiments of this application can be processed into various articles, including but not limited to prepregs, resin films, laminates, or printed circuit boards, through various processing methods.

[0147] For example, the resin composition described in this application can be made into a prepreg.

[0148] In one embodiment, the prepreg of this application has a reinforcing material and a layer disposed on the reinforcing material, the layer being formed by heating the aforementioned resin composition to a semi-cured state (B-stage) at high temperature. The baking temperature for producing the prepreg is, for example, between 120°C and 180°C. The reinforcing material can be any of a fiber material, woven fabric, or nonwoven fabric, and the woven fabric is preferably glass fiber cloth. There are no particular limitations on the type of glass fiber cloth; it can be commercially available glass fiber cloth suitable for various printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth, L-type glass fiber cloth, or Q-type glass fiber cloth, wherein the fiber type includes yarn and roving, and the form can include open or closed fibers. The aforementioned nonwoven fabric preferably includes liquid crystal resin nonwoven fabric, such as, but not limited to, polyester nonwoven fabric, polyurethane nonwoven fabric, etc. The aforementioned woven fabric may also include liquid crystal resin woven fabric, such as, but not limited to, polyester woven fabric or polyurethane woven fabric, etc. This reinforcing material can increase the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material may also be selectively pretreated with a silane coupling agent. The prepreg then undergoes subsequent heating and curing (C-stage) to form an insulating layer.

[0149] In one embodiment, the resin compositions are uniformly mixed to form a varnish, which is then placed in an impregnation tank. Fiberglass cloth is then immersed in the impregnation tank to allow the resin compositions to adhere to the fiberglass cloth. Finally, the cloth is heated and baked at an appropriate temperature until it reaches a semi-cured state, thus obtaining a semi-cured sheet.

[0150] For example, the resin composition article described in this application can also be a resin film, which is formed by baking and heating the resin composition to a semi-cured state. For example, the resin composition can be selectively coated onto a liquid crystal resin film, a polyethylene terephthalate film (PET film), or a polyimide film, and then baked at an appropriate temperature to a semi-cured state to form a resin film. Alternatively, the resin compositions of various embodiments of this application can be coated onto copper foil to ensure uniform adhesion, and then baked at an appropriate temperature to a semi-cured state to obtain a resin film.

[0151] For example, the resin composition described in this application can be used to form various laminates comprising at least two metal foils and at least one insulating layer disposed between the two metal foils. The insulating layer can be formed by curing the aforementioned resin composition under high temperature and high pressure (C-stage). Applicable curing temperatures are, for example, between 190°C and 220°C, preferably between 200°C and 210°C, and the curing time is 90 to 180 minutes, preferably 120 to 150 minutes. The aforementioned insulating layer can be obtained by curing the aforementioned prepreg or resin film. The aforementioned metal foils can be made of copper, aluminum, nickel, platinum, silver, gold, or alloys thereof, such as copper foil. In a preferred embodiment, the laminate is a copper foil substrate.

[0152] In one embodiment, the aforementioned multilayer board can be further processed into a printed circuit board.

[0153] One method for manufacturing the printed circuit board according to this application involves using a double-sided copper-clad laminate (e.g., product EM-827, available from Taikoo Electronics Materials) with a thickness of 28 mils and 1 ounce HTE (High Temperature Elongation) copper foil. 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 roughening treatment to create a surface texture. 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 190°C to 220°C for 90 to 180 minutes to cure the insulating layer material of the prepreg. Finally, various circuit board processes known in the art, such as blackening, drilling, and copper plating, are performed on the outermost copper foil to obtain the printed circuit board.

[0154] In one or more embodiments, the resin compositions disclosed in this application and various articles prepared therefrom preferably have one, more, or all of the following characteristics:

[0155] Visual inspection revealed that the prepreg had a smooth appearance and uniform color.

[0156] Referring to the method of IPC-TM-650 2.4.8, the copper foil tensile strength of the above-mentioned product is measured to be greater than or equal to 3.8 lb / inch, for example, the copper foil tensile strength is between 3.8 lb / inch and 5.0 lb / inch.

[0157] The moisture absorption and heat resistance of the above products were tested according to the methods of IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, and no board cracking was observed.

[0158] Referring to the method of IPC-TM-650-2.6.2.1, the water absorption rate of the above-mentioned product is measured to be less than or equal to 0.30%, for example, the water absorption rate is between 0.14% and 0.30%.

[0159] Referring to the method of JIS C2565, the dielectric loss of the above-mentioned products was measured at a frequency of 10 GHz at room temperature and after being placed in an environment of 85°C and 85% relative humidity for 48 hours. The calculated dielectric loss damp heat change rate of the above-mentioned products was less than or equal to 40%, for example, the dielectric loss damp heat change rate was between 14% and 40%.

[0160] Visual inspection revealed that the substrate had no streaks.

[0161] This application describes the preparation of resin compositions of the examples according to the dosages in Tables 1 and 2, and the preparation of resin compositions of the comparative examples according to the dosages in Tables 3 and 4, and further prepares them into various test samples or articles.

[0162] The chemical reagents used in the following examples and comparative examples are as follows:

[0163] 1. Polyphenylene ether resin containing unsaturated carbon-carbon double bonds: Methacrylamide polyphenylene ether resin, trade name SA9000, purchased from Sabic.

[0164] 2. Polyphenylene ether resin containing unsaturated carbon-carbon double bonds: Ethylene benzyl polyphenylene ether resin, trade name OPE-2st 1200, purchased from Mitsubishi Gas Chemical Company.

[0165] 3. Polyphenylene ether resin containing unsaturated carbon-carbon double bonds: Ethylene benzyl polyphenylene ether resin, trade name OPE-2st 2200, purchased from Mitsubishi Gas Chemical Company.

[0166] 4. Crosslinking agent containing unsaturated carbon-carbon double bonds: triallyl isocyanurate, trade name TAIC, purchased from Chin Yu Enterprise Co., Ltd.

[0167] 5. Crosslinking agent containing unsaturated carbon-carbon double bonds: divinylbenzene, trade name DVB, purchased from Sigma Aldrich.

[0168] 6. Crosslinking agent containing unsaturated carbon-carbon double bonds: bis(vinylphenyl)ethane, trade name BVPE, purchased from Linchuan Chemical.

[0169] 7. Silane coupling agent: 3-methacryloyloxypropyltrimethoxysilane, trade name KBM-503, purchased from ShinEtsu.

[0170] 8. Silane coupling agent: 3-glycidyl etheroxypropyltrimethoxysilane, trade name KBM-403, purchased from ShinEtsu.

[0171] 9. Silane coupling agent: 3-aminopropyltrimethoxysilane, trade name KBM-903, purchased from Shin Etsu.

[0172] 10. Silane coupling agent: Phenylacetyltrimethoxysilane, trade name KBM-103, purchased from Shin Etsu.

[0173] 11. Silane coupling agent: 3-mercaptopropylmethyldimethoxysilane, trade name KBM-802, purchased from Shin Etsu.

[0174] 12. Non-hollow filler: Spherical silica, trade name SC2500, purchased from Admatechs.

[0175] 13. Non-hollow filler: Spherical silica, trade name SC1050, purchased from Admatechs.

[0176] 14. Hollow core filler: Spherical insulating glass, trade name iM30K, purchased from 3M Company.

[0177] 15. Hollow filler: Spherical hollow silica, purchased from Qichen New Materials.

[0178] 16. Polyolefin: Polybutadiene, trade name B-3000, purchased from Japan Soda.

[0179] 17. Polyolefin: Hydrogenated styrene-butadiene block copolymer, trade name G1726, purchased from Kraton, USA.

[0180] 18. Polyolefin: Styrene-butadiene block copolymer, trade name SBS-C, purchased from Japan Soda.

[0181] 19. Second hardening accelerator, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, trade name 25B, purchased from Nippon Oils & Fats Co., Ltd.

[0182] 20. Second and third solvents: toluene, purchased from Sinopec.

[0183] In Tables 1 to 4, "appropriate amount" of solvent means the amount of solvent used to obtain the ideal solid content of the resin composition. For example, the solid content of the adhesive in Tables 1 to 4 is 65 wt%.

[0184] The homemade chemical reagents used in the examples and comparative examples were prepared as follows:

[0185] Preparation Example C1

[0186] Preparation of the first precursor: Hollow packing material iM30K was stirred at high speed in a 15% NaOH solution at 50°C for 3 hours, then washed with water until neutral, filtered, and dried at 100°C to obtain surface-hydroxylated hollow packing material; then the surface-hydroxylated hollow packing material and the first silane coupling agent KBM-503 (1.5% of the mass of hollow packing material) were added to the first solvent obtained by mixing ethanol and water (volume ratio of ethanol to water is 10:1), and stirred at high speed at 50°C for 4 hours, filtered, and dried at 80°C to obtain the first precursor C1-1.

[0187] Preparation of the second precursor: The hollow packing material iM30K was replaced with the non-hollow packing material SC2500. The mixture was stirred at high speed for 2 hours at 50°C in a 5% NaOH solution. The second silane coupling agent was KBM-802 (1.0% of the mass of the non-hollow packing material). The remaining steps were performed in the same manner as the preparation steps of the first precursor to obtain the second precursor Cl-2.

[0188] Chemical linking of the first and second precursors: 20 g of the first precursor C1-1 and 180 g of the second precursor C1-2 were added to 500 mL of the second solvent, toluene, and mixed thoroughly. Under the action of 0.5 g of the first curing accelerator, triphenylphosphine, the mixture was stirred at high speed at 95 °C for 2 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was vacuum dried at 70 °C to obtain a white solid powder C1, i.e., filler C1. Figure 2 The image shows SEM images of packing material C1, where large-diameter spheres represent hollow packing material and small-diameter spheres represent non-hollow packing material.

[0189] Preparation Example C2

[0190] Preparation of the first precursor: Hollow packing material iM30K was stirred at high speed for 3 hours at 50°C in a 15% NaOH solution, then washed with water until neutral, filtered, and dried at 100°C to obtain surface-hydroxylated hollow packing material; then the surface-hydroxylated hollow packing material and the first silane coupling agent KBM-403 (1.5% of the mass of hollow packing material) were added to the first solvent obtained by mixing ethanol and water (volume ratio of ethanol to water is 10:1), and stirred at high speed for 4 hours at 50°C, filtered, and dried at 80°C to obtain the first precursor C2-1.

[0191] Preparation of the second precursor: The hollow packing material iM30K was replaced with the non-hollow packing material SC2500. The mixture was stirred at high speed for 2 hours at 50°C in a 5% NaOH solution. The second silane coupling agent was KBM-903 (1.0% of the mass of the non-hollow packing material). The remaining steps were performed in the same way as the preparation steps of the first precursor to obtain the second precursor C2-2.

[0192] Chemical linking of the first and second precursors: 20 g of the first precursor C2-1 and 180 g of the second precursor C2-2 were added to 500 mL of the second solvent, toluene, and mixed thoroughly. Under the action of 0.5 g of the first curing accelerator, 2-ethyl-4-methylimidazole, the mixture was stirred at 100 °C for 2.5 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was vacuum dried at 70 °C to obtain a white solid powder C2, i.e., filler C2.

[0193] Preparation Example C3

[0194] Preparation of the first precursor: Hollow packing material iM30K was stirred at high speed in a 15% NaOH solution at 50°C for 3 hours, then washed with water until neutral, filtered, and dried at 100°C to obtain surface-hydroxylated hollow packing material; then the surface-hydroxylated hollow packing material and the first silane coupling agent KBM-802 (1.5% of the mass of the hollow packing material) were added to the first solvent obtained by mixing ethanol and water (volume ratio of ethanol to water is 10:1), and stirred at high speed at 50°C for 4 hours, filtered, and dried at 80°C to obtain the first precursor C3-1.

[0195] Preparation of the second precursor: The hollow packing material iM30K was replaced with the non-hollow packing material SC2500. The mixture was stirred at high speed for 2 hours at 50 °C in a 5% NaOH solution. The second silane coupling agent was KBM-503 (1.0% of the mass of the non-hollow packing material). The remaining steps were performed in the same way as the preparation steps of the first precursor to obtain the second precursor C3-2.

[0196] Chemical linking of the first and second precursors: 20 g of the first precursor C3-1 and 180 g of the second precursor C3-2 were added to 500 mL of the second solvent, toluene, and mixed thoroughly. Under the action of 0.5 g of the first curing accelerator, triphenylphosphine, the mixture was stirred at high speed at 95 °C for 2 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was vacuum dried at 70 °C to obtain a white solid powder C3, i.e., filler C3.

[0197] Preparation Example C4

[0198] Preparation of the first precursor: Hollow packing material iM30K was stirred at high speed in a 15% (w / w) NaOH solution at 50°C for 3 hours, then washed with water until neutral, filtered, and dried at 100°C to obtain surface-hydroxylated hollow packing material. Then, the surface-hydroxylated hollow packing material and the first silane coupling agent KBM-903 (0.5% of the hollow packing material's mass) were added to a first solvent obtained by mixing ethanol and water (ethanol to water volume ratio 10:1), and stirred at high speed at 50°C for 4 hours. After filtration and drying at 80°C, the first precursor C4-1 was obtained.

[0199] Preparation of the second precursor: The hollow packing material iM30K was replaced with the non-hollow packing material SC2500. The mixture was stirred at high speed for 2 hours at 50 °C in a 5% NaOH solution. The second silane coupling agent was KBM-403 (0.5% of the mass of the non-hollow packing material). The remaining steps were performed in the same way as the preparation steps of the first precursor to obtain the second precursor C4-2.

[0200] Chemical linking of the first and second precursors: 20 g of the first precursor C4-1 and 180 g of the second precursor C4-2 were added to 500 mL of the second solvent, toluene, and mixed thoroughly. Under the action of 0.5 g of the first curing accelerator, 2-ethyl-4-methylimidazole, the mixture was stirred at 100 °C for 2.5 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was vacuum dried at 70 °C to obtain a white solid powder C4, i.e., filler C4.

[0201] Preparation Example C5

[0202] Preparation of the first precursor: Same as preparation example C1.

[0203] Preparation of the second precursor: Same as preparation example C1.

[0204] Chemical linking of the first and second precursors: 6 g of the first precursor C1-1 and 194 g of the second precursor C1-2 were added to 500 mL of the second solvent, toluene, and mixed thoroughly. Under the action of 0.5 g of the first curing accelerator, triphenylphosphine, the mixture was stirred at high speed at 95 °C for 2 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was vacuum dried at 70 °C to obtain a white solid powder C5, i.e., filler C5.

[0205] Preparation Example C6

[0206] Preparation of the first precursor: Same as preparation example C1.

[0207] Preparation of the second precursor: Same as preparation example C1.

[0208] Chemical linking of the first and second precursors: 40 g of the first precursor C1-1 and 160 g of the second precursor C1-2 were added to 500 mL of the second solvent, toluene, and mixed thoroughly. Under the action of 0.5 g of the first curing accelerator, triphenylphosphine, the mixture was stirred at high speed at 95 °C for 2 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was dried under vacuum at 70 °C to obtain a white solid powder C6, i.e., filler C6.

[0209] Preparation Example C7

[0210] Preparation of the first precursor: Hollow packing material iM30K was stirred at high speed for 3 hours at 50°C in a 15% NaOH solution, then washed with water until neutral, filtered, and dried at 100°C to obtain surface-hydroxylated hollow packing material; then the surface-hydroxylated hollow packing material and the first silane coupling agent KBM-503 (3.5% of the mass of hollow packing material) were added to the first solvent obtained by mixing ethanol and water (volume ratio of ethanol to water is 10:1), and stirred at high speed for 4 hours at 50°C, filtered, and dried at 80°C to obtain the first precursor C7-1.

[0211] Preparation of the second precursor: The hollow packing material iM30K was replaced with the non-hollow packing material SC2500. The mixture was stirred at high speed for 2 hours at 50 °C in a 5% NaOH solution. The second silane coupling agent was KBM-802 (1.0% of the mass of the non-hollow packing material). The remaining steps were performed in the same manner as the preparation steps of the first precursor to obtain the second precursor C7-2.

[0212] Chemical linking of the first and second precursors: 50 g of the first precursor C7-1 and 150 g of the second precursor C7-2 were added to 500 mL of the second solvent, toluene, and mixed thoroughly. Under the action of 0.5 g of the first curing accelerator, triphenylphosphine, the mixture was stirred at high speed at 95 °C for 2 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was vacuum dried at 70 °C to obtain a white solid powder C7, i.e., filler C7.

[0213] Preparation Example C8

[0214] Preparation of the first precursor: Same as preparation example C1.

[0215] Preparation of the second precursor: Same as preparation example C1.

[0216] Chemical linking of the first and second precursors: 60 g of the first precursor C1-1 and 140 g of the second precursor C1-2 were added to 500 mL of the second solvent, toluene, and mixed thoroughly. Under the action of 0.5 g of the first curing accelerator, triphenylphosphine, the mixture was stirred at high speed at 95 °C for 2 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was vacuum dried at 70 °C to obtain a white solid powder C8, i.e., filler C8.

[0217] Preparation Example C9

[0218] Preparation of the first precursor: Hollow silica filler was stirred at high speed in a 5% NaOH solution at 50°C for 2 hours, then washed with water until neutral, filtered, and dried at 100°C to obtain surface-hydroxylated hollow filler; then the surface-hydroxylated hollow filler and the first silane coupling agent KBM-503 (1.5% of the mass of the hollow filler) were added to the first solvent obtained by mixing ethanol and water (volume ratio of ethanol to water is 10:1), and stirred at high speed at 50°C for 4 hours, filtered, and dried at 80°C to obtain the first precursor C9-1.

[0219] Preparation of the second precursor: The hollow silica was replaced with non-hollow filler SC1050, and the second silane coupling agent was KBM-802 (2.5% of the mass of the non-hollow filler). The remaining steps were performed in the same way as the preparation steps of the first precursor to obtain the second precursor C9-2.

[0220] Chemical linking of the first and second precursors: 20 g of the first precursor C9-1 and 180 g of the second precursor C9-2 were added to 500 mL of the second solvent, toluene, and mixed thoroughly. Under the action of 0.5 g of the first curing accelerator, triphenylphosphine, the mixture was stirred at high speed at 95 °C for 2 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was vacuum dried at 70 °C to obtain a white solid powder, C9, i.e., filler C9.

[0221] Preparation Example X1

[0222] Hollow packing material iM30K was stirred at high speed in a 15% NaOH solution at 50°C for 3 hours, then washed with water until neutral, filtered, and dried at 100°C to obtain surface-hydroxylated hollow packing material. Non-hollow packing material SC2500 was stirred at high speed in a 5% NaOH solution at 50°C for 2 hours, then washed with water until neutral, filtered, and dried at 100°C to obtain surface-hydroxylated non-hollow packing material. 20 g of surface-hydroxylated hollow packing material, 180 g of surface-hydroxylated non-hollow packing material, 0.3 g of KBM-802 silane coupling agent (1.5% of the hollow packing material's mass), and 1.8 g of KBM-503 silane coupling agent (1.0% of the non-hollow packing material's mass) were added to 500 mL of toluene, followed by 0.5 g of triphenylphosphine. The mixture was stirred at high speed at 95°C for 2 hours. Cool to room temperature, let stand for 12 hours, pour off the upper liquid, and dry the solid part under vacuum at 70°C to obtain a white solid powder X1. Figure 3 The image shows SEM images of packing material X1, where large-diameter spheres are hollow packing material and small-diameter spheres are non-hollow packing material.

[0223] Preparation Example X2

[0224] Hollow packing material iM30K was stirred at high speed in a 15% (w / w) NaOH solution at 50°C for 3 hours. After washing with water until neutral, it was filtered and dried at 100°C to obtain surface-hydroxylated hollow packing material. Then, the surface-hydroxylated hollow packing material and KBM-802 silane coupling agent (1.5% of the hollow packing material's mass) were added to a mixed solvent of ethanol and water (ethanol to water volume ratio 10:1). The mixture was stirred at high speed at 50°C for 4 hours, filtered, and dried at 80°C to obtain KBM-802 pretreated hollow packing material X2-1.

[0225] Using the same method, the hollow packing material iM30K was replaced with the non-hollow packing material SC2500. The mixture was then stirred at high speed for 2 hours at 50°C in a 5% (w / w) NaOH solution. 1.5% KBM-802 was replaced with 1.0% KBM-103, resulting in the KBM-103 pretreated non-hollow packing material X2-2. Note that KBM-103 does not chemically react with KBM-802 and cannot form covalent bonds with it.

[0226] 20 g of X2-1 and 180 g of X2-2 were added to 500 mL of toluene, along with 0.5 g of triphenylphosphine. The mixture was stirred at high speed at 95 °C for 2 hours. After cooling to room temperature and standing for 12 hours, the supernatant was discarded, and the solid portion was dried under vacuum at 70 °C to obtain a white solid powder X2. Figure 4 The image shows SEM images of packing material X2, where the large-diameter spheres are hollow packing material and the small-diameter spheres are non-hollow packing material.

[0227] The characteristic tests of Examples E1 to E16 and Comparative Examples 1 to 10 were conducted by preparing the test samples as follows and then performing the tests according to the specific test conditions. The results are listed in Tables 1 to 4.

[0228] 1. Precursor Sheet: The resin compositions of the examples (listed in Tables 1 and 2) and the resin compositions of the comparative examples (listed in Tables 3 and 4) were selected respectively. The resin compositions were uniformly mixed to form a varnish with a solid content of 65 wt%. The varnish was placed in an impregnation tank, and then glass fiber cloth (e.g., L-glass fiber fabric of specification 2116 or L-glass fiber fabric of specification 1080) purchased from Asahi Co., Ltd. was immersed in the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. The mixture was heated at 130°C to 170°C to form a semi-cured state (B-Stage) to obtain a precursor sheet.

[0229] 2. Copper Foil Substrate (6-ply, formed by laminating six prepreg sheets): Two 35-micron thick ultra-low surface roughness (HVLP) copper foils and six 2116 L-glass fiber cloths were prepared, impregnated with prepreg sheets prepared from each test sample (each example or comparative example). Each prepreg sheet contained approximately 55 wt% resin. The prepreg sheets were stacked in the following order: one HVLP copper foil, six prepreg sheets, and one HVLP copper foil. The prepreg sheets were then laminated under vacuum conditions, a pressure of 420 psi, and 200°C for 2 hours to form a copper foil substrate. The six stacked prepreg sheets cured to form an insulating layer between the two copper foils, with an insulating layer containing approximately 55 wt% resin.

[0230] 3. Copper-free substrate (6-ply, made of six prepreg sheets laminated together): The copper foil substrate mentioned above is etched to remove two copper foils to obtain a copper-free substrate (6-ply). This copper-free substrate is made of six prepreg sheets laminated together. The resin content of the copper-free substrate is about 55wt%.

[0231] 4. Copper-free substrate (2-ply, formed by laminating two prepreg sheets): Two 18-micron thick ultra-low surface roughness (HVLP) copper foils and two 1080 L-glass fiber cloths impregnated with prepreg sheets prepared from each test sample (each set of examples or comparative examples) were prepared. The copper foil, two prepreg sheets, and copper foil were then laminated in that order and pressed under vacuum conditions, a pressure of 420 psi, and 200°C for 2 hours to form a copper foil-containing substrate (2-ply, formed by laminating two prepreg sheets). Next, the copper foil substrate was etched to remove the copper foil from both sides to obtain a copper-free substrate (2-ply). This copper-free substrate was formed by laminating two prepreg sheets, and the resin content of the copper-free substrate (2-ply) was approximately 70 wt%.

[0232] For the aforementioned test substance, the characteristics were analyzed in the following manner.

[0233] 1. Appearance of prepreg

[0234] The prepregs prepared by impregnating each test sample (each set of examples or comparative examples) with the L-glass fiber cloth of the above 2116 were visually observed to see if the appearance of the prepreg was flat and the color was uniform. If the appearance of the prepreg was flat and the color was uniform, it was marked as "OK"; if the appearance of the prepreg was not flat or the color was not uniform, it was marked as "NG".

[0235] 2. Copper foil peeling strength (P / S)

[0236] The copper foil substrate (composed of six prepreg sheets laminated together) was selected as the test sample. The copper foil tensile strength was measured using a universal tensile testing machine, referring to the method in IPC-TM-650 2.4.8. Higher copper foil tensile strength indicates stronger adhesion between the copper foil and the insulating layer. Copper foil substrates prepared using HVLP copper foil generally have lower copper foil tensile strength, and improving copper foil tensile strength is technically challenging. A difference in copper foil tensile strength greater than or equal to 0.2 lb / inch indicates a significant difference.

[0237] 3. Moisture absorption and heat resistance test (pressure cooking test, PCT)

[0238] In the moisture absorption and heat resistance test, the copper-free substrate (6-ply) mentioned above was selected as the test sample. Following the method in IPC-TM-650 2.6.16.1, the substrate underwent a pressure cooking test (PCT) for 5 hours (temperature 121℃, relative humidity 100%). Then, following the method in IPC-TM-650 2.4.23, it was immersed in a tin bath at a constant temperature of 288℃, and removed after 20 seconds to observe for any board bursting. Three samples of the same specifications were tested in each group. If any sample showed board bursting (marked X), it indicated partial interlayer delamination or blistering of the substrate's insulating layer. If the test result was no board bursting (marked O), it indicated no interlayer delamination or blistering occurred. OOO represents no board bursting in any of the three samples, XXX represents board bursting in all three samples, OXX represents two board bursting and one non-blistering out of the three samples, and OOX represents one board bursting and two non-blistering out of the three samples.

[0239] 4. Water absorption rate

[0240] The copper-free substrate (6-ply) described above was selected as the test sample. The water absorption rate of the copper-free substrate after immersion in water for 24 hours was measured according to the method in IPC-TM-650-2.6.2.1. A lower water absorption rate indicates better moisture resistance of the substrate. A difference in water absorption rate greater than or equal to 0.05% indicates a significant difference.

[0241] 5. Dielectric loss rate under damp heat (Df rate under damp heat)

[0242] The copper-free substrate (2-ply, composed of two prepreg sheets laminated together) was selected as the test sample. A microwave dielectric analyzer (purchased from AET Corporation, Japan) was used, and the dielectric loss of each sample was measured at 10 GHz at room temperature (approximately 25°C) according to JIS C2565 method. This result was denoted as Df1. After cleaning each sample with distilled water, it was placed at 85°C and 85% relative humidity for 48 hours, and its dielectric loss at 10 GHz was measured again, denoted as Df2. The damp-heat change rate of Df2% was calculated as ((Df2-Df1) / Df1)*100%. A lower damp-heat change rate indicates better dielectric stability. A difference in the damp-heat change rate of dielectric loss greater than or equal to 5% indicates a significant difference.

[0243] 6. Stripes on the substrate appearance

[0244] Select the above-mentioned copper-free substrate (6-ply) and visually inspect the appearance of the copper-free substrate for stripes. If no stripes appear on the appearance of the copper-free substrate, record it as "none". If stripes appear on the appearance of the copper-free substrate, use a vernier caliper to measure the length of the stripes in millimeters (mm).

[0245] [Table 1] Composition (parts by weight) of the resin compositions of Examples E1 to E8 and test results of the characteristics of their products

[0246]

[0247] [Table 2] Composition (parts by weight) of the resin compositions of Examples E9 to E16 and test results of the characteristics of their products

[0248] [Table 3] Composition (parts by weight) of the resin compositions of Comparative Examples 1-5 and test results of the characteristics of their products

[0249] [Table 4] Composition (parts by weight) of the resin compositions of Comparative Examples 6-10 and test results of the characteristics of their products

[0250]

[0251] The following phenomena can be observed from Tables 1 to 4.

[0252] Example E1 using packing C1 is compared to Comparative Example 1 using packing X1 and Comparative Example 2 using packing X2. Figure 2 , Figure 3 and Figure 4 It can be seen that the hollow filler surface of C1 has a relatively large number of non-hollow fillers connected to it, the hollow filler surface of X1 has significantly fewer non-hollow fillers connected to it, and the hollow filler surface of X2 has almost no non-hollow fillers connected to it. The characteristic results show that Example E1, compared to Comparative Examples 1 and 2, exhibits superior moisture absorption and heat resistance, low Df (hygrothermal change rate), low water absorption, and high copper foil tensile strength. Furthermore, the prepreg has a smooth appearance and uniform color, and the substrate has no streaks.

[0253] Compared with Comparative Examples 3, 4, 5, 6, and 7, which respectively added fillers C1 to C9, Examples E1 to E16 using fillers C1-1 and C1-2, C1-1 and C3-2, M30K and C3-2, and SC2500, respectively, show that Examples E1 to E16 can simultaneously possess excellent moisture absorption and heat resistance, low Df damp heat change rate, low water absorption, and high copper foil tensile strength, and the prepreg has a smooth appearance and uniform color, and the substrate has no stripes.

[0254] Compared to Comparative Example 7, which added hollow filler without surface pretreatment and non-hollow filler without surface pretreatment, and Comparative Examples 8 to 10, which added hollow filler without surface pretreatment, non-hollow filler without surface pretreatment, and different silane coupling agents, Example E1 using filler C1 exhibits superior moisture absorption and heat resistance, low Df hygrothermal change rate, low water absorption, and high copper foil tensile strength. Furthermore, the prepreg has a smooth appearance and uniform color, and the substrate has no streaks.

[0255] The above embodiments are merely illustrative in nature and are not intended to limit the embodiments of this application or the application or use of such embodiments. In this application, terms such as "example" mean "as an example, illustration, or description." Any exemplary embodiment herein is not necessarily to be interpreted as preferred or more advantageous than other embodiments, unless otherwise indicated.

[0256] Furthermore, although at least one exemplary embodiment or comparative example has been presented in the foregoing embodiments, it should be understood that numerous variations are still possible in this application. It should also be understood that the embodiments described herein are not intended to limit the scope, use, or configuration of the claimed technical solution in any way. Rather, the foregoing embodiments will provide a simple guide for those skilled in the art to implement one or more of the described embodiments and their equivalents. Moreover, the claims include known equivalents and all foreseeable equivalents at the time of filing of this patent application.

Claims

1. A packing material, characterized in that, The filler includes a first precursor and a second precursor. The first precursor is a hollow filler coated with a first silane coupling agent; The second precursor is a non-hollow filler coated with a second silane coupling agent; The hollow filler is hollow glass or hollow silica, and the non-hollow filler is silica or glass; The maximum particle size of the hollow filler is less than or equal to 100 μm, and the maximum particle size of the non-hollow filler is less than or equal to 15 μm. Furthermore, the first precursor and the second precursor are connected by covalent bonds formed by the chemical reaction between the first silane coupling agent and the second silane coupling agent on the surface, and the weight ratio of the first precursor to the second precursor is 3:97 to 30:

70.

2. The packing material as described in claim 1, characterized in that, The first silane coupling agent and the second silane coupling agent are each independently a silane coupling agent containing carbon-carbon double bonds, epoxy groups, mercapto groups, amino groups, or combinations thereof.

3. The packing material as described in claim 1, characterized in that, The amount of the first silane coupling agent is 0.5% to 5% of the weight of the hollow filler, and the amount of the second silane coupling agent is 0.5% to 5% of the weight of the non-hollow filler.

4. A method for preparing the filler as described in claim 1, characterized in that, Includes the following steps: Preparation of the first precursor: Hollow packing is stirred in an alkaline solution to obtain surface-hydroxylated hollow packing; the surface-hydroxylated hollow packing is stirred with the first silane coupling agent in a first solvent to obtain the first precursor, wherein the first precursor is a hollow packing coated with the first silane coupling agent. Preparation of the second precursor: The non-hollow filler is stirred in an alkaline solution to obtain a non-hollow filler with hydroxylated surface; the non-hollow filler with hydroxylated surface and the second silane coupling agent are stirred in the first solvent to obtain the second precursor, the second precursor being a non-hollow filler with the second silane coupling agent coated on its surface. Chemical linking of the first precursor and the second precursor: The weight ratio of the first precursor to the second precursor is controlled to be 3:97 to 30:

70. The first precursor and the second precursor are mixed evenly in the second solvent. In the presence of the first curing accelerator, the first precursor and the second precursor are chemically linked by the first silane coupling agent and the second silane coupling agent coated on their respective surfaces to form covalent bonds, thereby obtaining the filler.

5. The method for preparing the filler as described in claim 4, characterized in that, The first silane coupling agent and the second silane coupling agent are each independently a silane coupling agent containing carbon-carbon double bonds, epoxy groups, mercapto groups, amino groups, or combinations thereof; and / or The alkaline solution includes sodium hydroxide solution, potassium hydroxide solution, triethylamine or potassium tert-butoxide; and / or The first solvent includes water, methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or mixtures thereof; and / or The second solvent includes methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether, dimethylformamide, dimethylacetamide, azirmonomethylpyrrolidone, or mixtures thereof; and / or The first curing accelerator includes Lewis base, curing initiator, or a combination thereof; and / or The temperatures for the preparation steps of the first precursor and the second precursor are controlled to be between 20°C and 60°C, and the stirring times are between 1 and 8 hours, respectively; and / or The temperature of the chemical linking step between the first precursor and the second precursor is controlled at 60°C to 120°C, and the time for the chemical reaction to occur is controlled at 1 to 6 hours.

6. A resin composition, characterized in that, The resin composition comprises: (A) Polyphenylene ether resin containing unsaturated carbon-carbon double bonds; (B) Crosslinking agents containing unsaturated carbon-carbon double bonds; and, (C) The packing material according to any one of claims 1 to 3.

7. The resin composition according to claim 6, characterized in that, The polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes vinyl benzyl polyphenylene ether resin, (meth)acryloyl polyphenylene ether resin, vinyl polyphenylene ether resin, or combinations thereof.

8. The resin composition according to claim 6, characterized in that, The crosslinking agent containing unsaturated carbon-carbon double bonds includes bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, tert-butylstyrene, triallyl isocyanurate, triallyl cyanurate, 1,2,4-trivinylcyclohexane, diallyl bisphenol A, styrene, butadiene, decanadiene, octadiene, vinylcarbazole, acrylates, or combinations thereof.

9. The resin composition according to claim 6, characterized in that, Based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition comprises 5 to 40 parts by weight of the crosslinking agent containing unsaturated carbon-carbon double bonds and 50 to 130 parts by weight of the filler.

10. The resin composition according to claim 6, characterized in that, Based on 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition further comprises 13 to 35 parts by weight of a polyolefin, wherein the polyolefin includes polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, styrene-butadiene-maleic anhydride terpolymer, vinyl-polybutadiene-urea oligomer, maleic anhydride-butadiene copolymer, polymethylstyrene, hydrogenated polybutadiene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated styrene-butadiene-maleic anhydride terpolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, or combinations thereof.

11. The resin composition according to claim 6, characterized in that, The resin composition further includes maleimide resin, benzoxazine resin, epoxy resin, silicone resin, cyanate ester resin, reactive ester, phenolic resin, styrene-maleic anhydride, amine curing agent, polyamide, polyimide, or combinations thereof.

12. The resin composition according to claim 6, characterized in that, The resin composition further includes a flame retardant, a second curing accelerator, a polymerization inhibitor, a third solvent, a third silane coupling agent, a surfactant, a dye, a toughening agent, or a combination thereof.

13. An article characterized in that, The article is made from the resin composition according to any one of claims 6 to 12, and the article includes a prepreg, a resin film, a laminate, or a printed circuit board.

14. The article of claim 13, characterized in that, The article has one, more, or all of the following characteristics: Visual inspection revealed that the prepreg had a smooth appearance and uniform color. Referring to the method of IPC-TM-650 2.4.8, the copper foil tensile strength of the article is measured to be greater than or equal to 3.8 lb / inch; The moisture absorption and heat resistance of the product were tested according to the methods of IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, and no plate bursting was observed. Referring to the method of IPC-TM-650-2.6.2.1, the water absorption rate of the product is measured to be less than or equal to 0.30%; Referring to the method of JIS C2565, the dielectric loss of the product at room temperature and after being placed in an environment of 85°C and 85% relative humidity for 48 hours were measured at a frequency of 10 GHz. The calculated dielectric loss damp heat change rate of the product is less than or equal to 40%. Visual inspection revealed that the laminated plate had no stripes.

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