Resin composition, its products and use thereof

Abstract

This invention relates to resin compositions, articles thereof, and their uses. The resin composition comprises: 100 parts by weight of a thermosetting resin and 100 to 300 parts by weight of an inorganic filler; the volatile organic matter content of the resin composition, as measured according to IPC-TM-6502.4.24.6, is less than or equal to 2.0%; the shear viscosity change rate of the resin composition, as measured according to GB / T2794-2022 7.3, is 9 to 56%; and the dielectric loss coefficient of the cured resin obtained by curing the resin composition, as measured according to JIS C2565 at a frequency of 10 GHz, is less than or equal to 0.0080. When this resin composition is applied in the resin filling process of printed circuit boards, the resulting printed circuit boards show significant improvements in impedance stability, solder drift crack rate, and plastisol stability.

Description

Technical Field

[0001] This invention relates to resin compositions, articles thereof, and uses thereof, and particularly to a resin composition suitable for use in the resin filling process of printed circuit boards (PCBs). Background Technology

[0002] PCB resin filling (or resin filling process) is a new technology invented to reduce PCB design size to facilitate component assembly. It effectively improves the reliability and manufacturing capabilities of High Density Interconnect (HDI) substrates. Simultaneously, resin filling technology solves problems that cannot be addressed by using solder mask or lamination filling. By filling inner layer blind / buried / vias, trenches, or empty areas of thick copper circuits with resin before lamination, the conflict between controlling the dielectric layer thickness during lamination and the inner layer filling design is balanced. Filling vias with resin improves the reliability issues associated with solder mask filling.

[0003] However, current printing technologies primarily employ two methods: continuous filling and printing, and filling followed by printing. These methods place stringent requirements on the viscosity stability (shear viscosity change rate) of the resin composition (or ink) during use. Excessive shear viscosity change in the resin composition leads to poor squeegee stability in the filling printing process, resulting in uneven filling. Furthermore, with the increasing demands of high-frequency, high-speed information transmission in printed circuit boards (PCBs), the dielectric loss coefficient of the PCB substrate is decreasing. Current resin compositions used in filling processes still have relatively high dielectric loss coefficients, resulting in poor compatibility with the substrate and poor PCB impedance stability. Moreover, the high volatile organic content in existing resin compositions leads to a high rate of solder bleed cracking on the PCB after resin filling.

[0004] Therefore, there is an urgent need to develop resin compositions with moderate viscosity, small shear viscosity change rate, long shelf life, low volatile organic matter, low dielectric loss coefficient, low water absorption, low Z-axis thermal expansion coefficient, high copper foil tensile strength, excellent PCB impedance stability, low PCB tin drift crack rate, and excellent glue coating stability during resin filling to meet the needs of printed circuit boards for high-frequency and high-speed information transmission. Summary of the Invention

[0005] The main objective of this invention is to provide a resin composition that can solve at least one of the above-mentioned technical problems, an article made from the resin composition, and the use of the resin composition in a printed circuit board resin filling process (e.g., one or more of a printed circuit board via filling process, a printed circuit board slot filling process, or a printed circuit board circuit filling process).

[0006] A first aspect of the present invention provides a resin composition comprising the following components:

[0007] 100 parts by weight of thermosetting resin and 100 to 300 parts by weight of inorganic filler;

[0008] The volatile organic matter content of the resin composition, as measured according to IPC-TM-650 2.4.24.6, is less than or equal to 2.0%.

[0009] The shear viscosity change rate of the resin composition, measured according to method 7.3 of GB / T 2794-2022, is 9-56%.

[0010] The dielectric loss coefficient of the cured resin obtained by curing the resin composition is less than or equal to 0.0080, as measured at a frequency of 10 GHz according to the method of JIS C2565.

[0011] In this invention, a resin composition that can simultaneously satisfy the above three performance characteristics is applied in the resin filling process of printed circuit boards, and the resulting printed circuit boards have achieved significant improvements in impedance stability, tin drift crack rate and adhesive removal stability.

[0012] Preferably, the volatile organic matter content of the resin composition, as measured according to method IPC-TM-650 2.4.24.6, is less than or equal to 0.5%.

[0013] The dielectric loss coefficient of the cured resin obtained by curing the resin composition is less than or equal to 0.0041, as measured at a frequency of 10 GHz according to the method of JIS C2565.

[0014] Preferably, based on a total inorganic filler mass of 100 wt%, the inorganic filler comprises 50 to 100 wt% silica, and more preferably 80 to 100 wt% silica.

[0015] Preferably, based on a total inorganic filler mass of 100 wt%, the inorganic filler comprises 2 to 17 wt% surface porous silica, more preferably 2 to 12 wt% surface porous silica.

[0016] Preferably, the maximum particle size of the porous silica on the surface is 5–20 μm.

[0017] Preferably, the specific surface area of ​​the porous silica is 40–200 m². 2 / g.

[0018] Preferably, the maximum particle size of the porous silica on the surface is 5–15.9 μm.

[0019] Preferably, the specific surface area of ​​the porous silica is 10³ to 200 m². 2 / g.

[0020] Preferably, the thermosetting resin includes any one or a combination of polyolefins, acrylate compounds, maleimide resins, silicone resins, polyphenylene ether resins, benzoxazine resins, epoxy resins, reactive esters, phenolic resins, and cyanate ester resins.

[0021] Preferably, the resin composition does not contain organic solvents.

[0022] Preferably, the thermosetting resin comprises (A) a maleic anhydride-modified polyolefin and (B) a polyfunctional (meth)acrylate monomer and / or its oligomers; and

[0023] The inorganic filler includes (C) surface porous silica and (D) non-porous silica.

[0024] Preferably, the mass ratio of (A) maleic anhydride modified polyolefin: (B) polyfunctional (meth)acrylate monomer and / or its oligomer: (C) surface porous silica: (D) nonporous silica is 100:(30-90):(10-30):(150-350).

[0025] Preferably, the mass ratio of the porous silica on the surface of (C) to the non-porous silica of (D) is (1:5) to (1:35), and more preferably (1:8) to (1:35).

[0026] Preferably, the resin composition further includes any one or a combination of flame retardants, curing accelerators, polymerization inhibitors, dyes, surfactants, and toughening agents.

[0027] A second aspect of the present invention provides an article manufactured from the above-described resin composition, the article comprising a prepreg, a resin film, a laminate, or a printed circuit board.

[0028] A third aspect of the present invention provides an article made from the above-described resin composition, the article comprising a resin cured product obtained by curing the resin composition.

[0029] A fourth aspect of the present invention provides a printed circuit board manufactured by using the above-described resin composition in a printed circuit board resin filling process, the printed circuit board having one or more of the following characteristics:

[0030] The rate of tin bleed cracks in the resin-cured area of ​​the printed circuit board, measured according to the method of IPC-TM-650 2.4.13.1, is 0%.

[0031] The impedance amplitude of the resin-cured area of ​​the printed circuit board, as measured by a network analyzer, is less than or equal to 10%.

[0032] The continuous glue scraping time in the resin filling process of printed circuit boards is greater than or equal to 15 minutes.

[0033] A fifth aspect of the present invention provides the use of the above-described resin composition in a resin filling process for printed circuit boards.

[0034] Preferably, the printed circuit board resin filling process includes one or more of the following: printed circuit board via filling process, printed circuit board slot filling process, or printed circuit board circuit filling process.

[0035] Preferably, in the printed circuit board via-filling process, at least one hole of the printed circuit board is filled with a cured product of the resin composition.

[0036] And / or, in the printed circuit board filling process, at least one groove of the printed circuit board is filled with a cured product of the resin composition;

[0037] And / or, in the printed circuit board circuit filling process, at least one circuit void area of ​​the printed circuit board is covered with a cured resin composition.

[0038] The beneficial effects of this invention are:

[0039] The resin composition of the present invention, which simultaneously satisfies the requirements of volatile organic matter ≤2.0%, shear viscosity change rate 9-56%, and dielectric loss coefficient ≤0.0080, is used in the printing circuit board manufacturing process to produce a printed circuit board. This significantly improves the impedance stability, tin drift crack rate, and squeegee stability of the printed circuit board. In addition, the resin composition of the present invention, or various articles containing resin cured products prepared therefrom, can simultaneously possess low volatile organic matter, small shear viscosity change rate, and low dielectric loss coefficient. Preferably, at least one of the properties such as adhesive storage life, copper foil tensile strength, water absorption rate, and Z-axis thermal expansion coefficient is improved, which can meet the requirements of printed circuit boards for high-frequency and high-speed information transmission. Detailed Implementation

[0040] To enable those skilled in the art to clearly and correctly understand the technical content of this invention, the terms and symbols mentioned in this invention are generally described and defined below. Unless otherwise specified, all terms and symbols used in this invention (including scientific terms, technical terms, and general symbols, wherein general symbols include general mathematical symbols, general physical symbols, general chemical symbols, etc.) have the same meaning as commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0041] In this invention, "comprising," "including," "having," "containing," or any other similar terms are open-ended conjunctions, and unless otherwise specified, the use of these terms may also include other parts.

[0042] In this invention, "at least one or a combination thereof", "any one or a combination thereof", "any one or a combination thereof", and "more than one" should be interpreted as "using any one of the listed elements alone", "using any two of the listed elements in combination", or "using any three or more of the listed elements in combination".

[0043] In this invention, the numerical range represented by “equal to”, “=”, “greater than or equal to”, “≥”, “less than or equal to”, “≤”, “to”, “~”, “-”, “above” or “below” should be interpreted as including the endpoint values, and should cover all possible subranges and individual numerical values ​​within the range (numerical types include but are not limited to integers, decimals and fractions). For example, the numerical ranges represented by "equal to 3.0", "=3.0", "greater than or equal to 3.0", "≥3.0", "less than or equal to 3.0", "≤3.0", "above 3.0" or "below 3.0" all include the endpoint value "3.0"; the numerical ranges represented by "3.0 to 6.0", "between 3.0 and 6.0", "between 3.0 and 6.0", "3.0 to 6.0", and "3.0 to 6.0" all include the endpoint values ​​"3.0" and "6.0", and should be understood to include, but are not limited to, sub-ranges such as 3.0-5.0, 4.0-6.0, 5.0-6.0, and single values ​​such as 3.0, 4.0, 5.0, 5.5, and 6.0.

[0044] In this invention, the numerical ranges represented by "greater than", ">", "less than", and "<" should be interpreted as excluding endpoint values. For example, the numerical ranges represented by "greater than 3.0", ">3.0", "less than 3.0", and "<3.0" all exclude the endpoint value "3.0".

[0045] In this invention, the numerical value has a precision, which is achieved by rounding up to the nearest whole number.

[0046] In this invention, "containing unsaturated carbon-carbon double bonds" means "containing unsaturated C=C double bond groups," such as, but not limited to, vinyl, vinylbenzyl, (meth)acryloyl, allyl, or combinations thereof. Wherein, "vinyl" should be interpreted to include both vinyl and vinylidene, and "(meth)acryloyl" should be interpreted to include both acryloyl and methacryloyl.

[0047] In this invention, the functional groups such as alkyl and alkenyl should be interpreted to include their various isomers. For example, "alkyl" means a group derived from aliphatic hydrocarbons and includes straight-chain, branched or cyclic groups. Furthermore, propyl should be interpreted to include n-propyl and isopropyl.

[0048] In this invention, the term "monomer" or "compound" should be interpreted to include its various isomers, such as, but not limited to, structural isomers, stereoisomers, etc.

[0049] In this invention, “parts by weight” should be interpreted as a relative number of parts by weight, which can be any unit of weight, such as, but not limited to, kilograms, grams, pounds, etc. For example, 100 parts by weight of thermosetting resin means that it can be 100 kilograms of thermosetting resin or 100 pounds of thermosetting resin.

[0050] In this invention, wt% represents weight (or mass) percentage.

[0051] In this invention, mil is a unit of thickness, 1 mil is approximately 25.4 micrometers, and ounce is a unit of thickness, 1 ounce is approximately 35 micrometers.

[0052] In this invention, the monomer refers to a molecule that can be covalently linked with the same or other molecules to form a polymer.

[0053] In this invention, the polymer refers to the product formed by the polymerization reaction of monomers. The polymer may include copolymers, homopolymers (self-polymers), etc., but is not limited thereto. Unless otherwise specified, the degree of polymerization (monomer conversion rate) of the polymer is not limited; for example, it can be a fully polymerized polymer (monomer conversion rate of 100%) or a partially polymerized polymer (monomer conversion rate, for example, but not limited to, between 10% and 90%, which may also be referred to as a "prepolymer" in this invention). The molecular weight of the polymer is not limited; for example, a polymer composed of 2 to 20 repeating units is called an oligomer (also known as a low-molecular-weight polymer). Typically, oligomers are polymers composed of 2 to 5 repeating units.

[0054] The copolymers described in this invention refer to products formed by polymerization of two or more different monomers, including random copolymers, alternating copolymers, graft copolymers or block copolymers, but this invention is not limited thereto.

[0055] The present invention will be described below with reference to specific embodiments and examples. These embodiments are merely illustrative examples of preferred implementations and do not limit the scope of protection of the present invention.

[0056] As described above, this invention mainly discloses a resin composition comprising the following components:

[0057] 100 parts by weight of thermosetting resin and 100 to 300 parts by weight of inorganic filler,

[0058] The volatile organic matter content of the resin composition, as measured according to IPC-TM-650 2.4.24.6, is less than or equal to 2.0%.

[0059] The shear viscosity change rate of the resin composition, measured according to method 7.3 of GB / T 2794-2022, is 9-56%.

[0060] The dielectric loss coefficient of the cured resin obtained by curing the resin composition is less than or equal to 0.0080, as measured at a frequency of 10 GHz according to the method of JIS C2565.

[0061] Preferably, the present invention discloses a resin composition for use in the resin filling process of printed circuit boards, comprising the following components:

[0062] 100 parts by weight of thermosetting resin and 100 to 300 parts by weight of inorganic filler,

[0063] The volatile organic matter content of the resin composition, as measured according to IPC-TM-650 2.4.24.6, is less than or equal to 2.0%.

[0064] The shear viscosity change rate of the resin composition, measured according to method 7.3 of GB / T 2794-2022, is 9-56%.

[0065] The dielectric loss coefficient of the cured resin obtained by curing the resin composition is less than or equal to 0.0080, as measured at a frequency of 10 GHz according to the method of JIS C2565.

[0066] Preferably, the dielectric loss coefficient of the cured resin obtained by curing the resin composition, measured at a frequency of 10 GHz according to the method of JIS C2565, is less than or equal to 0.0060; more preferably, the dielectric loss coefficient (Df) is less than or equal to 0.0041. The lower the dielectric loss coefficient, the better the impedance stability of the PCB after resin filling.

[0067] Preferably, the shear viscosity change rate of the resin composition, measured according to the method of GB / T 2794-2022 7.3, is 12-41%. The lower the shear viscosity change rate, the better the scraping stability during the resin filling process.

[0068] Preferably, the volatile organic matter content of the resin composition, as measured according to the method of IPC-TM-650 2.4.24.6, is less than or equal to 1.0%, more preferably, it is less than or equal to 0.5%.

[0069] In one embodiment of the present invention, the inorganic filler includes, but is not limited to, any one or a combination of silica (molten, non-molten, porous or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, iron oxide, boron oxide, zinc oxide, zirconium oxide, mica, boehmite, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, zinc molybdate, calcium molybdate, magnesium molybdate, ammonium molybdate, zinc molybdate-modified talc, calcined talc, talc, silicon nitride, zirconium tungstate, lithopone, and calcined kaolin.

[0070] The inorganic filler can be spherical, fibrous, plate-like, granular, flake-like, rod-like, or needle-like, preferably spherical. The inorganic filler can also be solid, hollow, or porous. Furthermore, the inorganic filler can be selectively pretreated with a silane coupling agent. In addition, the color of the inorganic filler is not particularly limited; it can be white, black, or light yellow, but is not limited thereto. The preparation method of the inorganic filler is also not particularly limited; for example, the preparation method of spherical silica (referred to as "spherical silica") can be a melt method, a chemical synthesis method, a direct combustion method, etc. Preferably, based on 100 wt% of the total mass of the inorganic filler, the inorganic filler includes 50-100 wt% silica, more preferably, it includes 80-100 wt% silica.

[0071] Preferably, based on a total inorganic filler mass of 100 wt%, the inorganic filler comprises 2 to 17 wt% surface porous silica; more preferably, the inorganic filler comprises 2 to 12 wt% surface porous silica.

[0072] In this invention, the porous silica on the surface is silica with a porous surface and a solid interior, including but not limited to solid silica with a porous surface treatment, and can be a self-made product or a commercially available product. Preferably, the porous silica on the surface is spherical silica with a porous surface and a solid interior, rod-shaped silica with a porous surface and a solid interior, or a combination thereof.

[0073] In this invention, the maximum particle size (D100 particle size) of the surface porous silica ranges, for example, but not limited to, 5–20 μm, and the specific surface area ranges, for example, but not limited to, 40–200 m². 2 / g. Preferably, the D100 particle size of the surface-porous silica ranges from 5 to 15.9 μm, and the specific surface area is 103 to 200 m². 2 / g.

[0074] In this invention, the porous silica can be a single porous solid silica or a mixture of two or more different porous solid silicas. Furthermore, the method for preparing the porous silica can be any method known in the art.

[0075] In this invention, the type and amount of thermosetting resin are not particularly limited and can be adjusted according to the characteristics of the resin composition and the cured resin obtained by curing. As long as the cured resin can achieve a dielectric loss coefficient of ≤0.0080, a shear viscosity change rate of 9-56%, and an organic volatile content of ≤2.0%, it is acceptable.

[0076] In a preferred embodiment of the present invention, the thermosetting resin includes any one or a combination of polyolefins, acrylate compounds, maleimide resins, silicone resins, polyphenylene ether resins, benzoxazine resins, epoxy resins, reactive esters, phenolic resins, and cyanate ester resins.

[0077] In a preferred embodiment of the present invention, based on a total thermosetting resin content of 100 wt%, the content of each polyolefin and acrylate compound is independently 1 to 99 wt%, for example, but not limited to 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 50 wt%, or 99 wt%, and the content of each maleimide resin, silicone resin, polyphenylene ether resin, benzoxazine resin, epoxy resin, reactive ester, phenolic resin, and cyanate ester resin is independently 0 to 98 wt%, for example, but not limited to 0 wt%, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 50 wt%, or 98 wt%.

[0078] In a preferred embodiment of the present invention, the thermosetting resin comprises 25-80 wt% polyolefin and 20-75 wt% acrylate compound, with a total thermosetting resin content of 100 wt%.

[0079] The polyolefin in the thermosetting resin can be a single polyolefin or a mixture of two or more different polyolefins. Preferably, the polyolefin content in the thermosetting resin is 25–80 wt%, more preferably 26–77 wt%.

[0080] In one embodiment of the present invention, the polyolefin includes maleic anhydride-modified polyolefin, other polyolefins different from the maleic anhydride-modified polyolefin, or combinations thereof. Preferably, the maleic anhydride-modified polyolefin accounts for 75-100 wt% of the polyolefin content. The modification methods involved in maleic anhydride modification can be various chemical modification methods known in the art, including but not limited to addition polymerization modification, which includes but is not limited to free radical polymerization, cationic polymerization, anionic polymerization, or coordination polymerization. For example, maleic anhydride monomers undergo addition polymerization with one or more olefin polymers to generate maleic anhydride-modified polyolefins. As another example, maleic anhydride monomers undergo addition polymerization with one or more olefin monomers to generate random, alternating, block, or graft copolymers, i.e., maleic anhydride-modified polyolefins.

[0081] The types of olefin polymers and olefin monomers suitable for the above modification methods are not particularly limited, and can be various olefin polymers and olefin monomers known in the art. In other words, maleic anhydride can be used to modify various polyolefin polymers and olefin monomers to obtain the maleic anhydride-modified polyolefins of the present invention.

[0082] The maleic anhydride-modified polyolefin in the resin composition can be a single maleic anhydride-modified polyolefin or a mixture of two or more different maleic anhydride-modified polyolefins.

[0083] The maleic anhydride-modified polyolefins include, but are not limited to, any one or a combination thereof, maleic anhydride addition polybutadiene, maleic anhydride addition polyisoprene, maleic anhydride addition styrene-butadiene copolymer, maleic anhydride addition styrene-isoprene copolymer, and maleic anhydride-styrene copolymer.

[0084] The aforementioned maleic anhydride-styrene copolymer can be any type of maleic anhydride-styrene copolymer known in the art, wherein the ratio of styrene (St) to maleic anhydride (MA) can be 1 / 1, 2 / 1, 3 / 1, 4 / 1, 6 / 1, 8 / 1, or 12 / 1. Specific examples include, but are not limited to, the styrene-maleic anhydride copolymers manufactured and sold by Aurorium under the trade names XIRAN-1000, XIRAN-2000, XIRAN-3000, XIRANEF-40, and XIRAN-EF-80. In this invention, the other polyolefins that are different from maleic anhydride-modified polyolefins include, but are not limited to, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene polymer, vinyl-polybutadiene-urea polymer, polymethylstyrene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-butadiene-divinylbenzene polymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, epoxy-containing polybutadiene, divinylbenzene-styrene-ethylstyrene copolymer, and ethylene-divinylbenzene-styrene copolymer, or any combination thereof.

[0085] The divinylbenzene-styrene-ethylstyrene copolymers used in this invention may include various divinylbenzene-styrene-ethylstyrene copolymers disclosed in US Patent US20070129502A1, all of which are incorporated herein by reference.

[0086] The acrylate compound in the thermosetting resin includes, but is not limited to, any one or a combination of monofunctional (meth)acrylate monomers and / or oligomers having one (meth)acrylate group within the molecule, and polyfunctional (meth)acrylate monomers and / or oligomers having two or more (meth)acrylate groups within the molecule. In this invention, the acrylate compound may include any one or more (meth)acrylate monomers, or the acrylate compound may include any one or more (meth)acrylate oligomers, or the acrylate compound may include a mixture of any one or more (meth)acrylate monomers and any one or more (meth)acrylate oligomers. Preferably, the acrylate compound accounts for 20-75 wt% of the thermosetting resin, more preferably 23-56 wt%. Preferably, the polyfunctional (meth)acrylate monomer and / or oligomer accounts for 90-100 wt% of the acrylate compound.

[0087] The aforementioned acrylate compounds are liquid at room temperature. The relative molecular mass (Mr) of the aforementioned acrylate compounds is less than or equal to 2000, and the weight average molecular weight (Mw) of the oligomers obtained by polymerization of monofunctional or polyfunctional (meth)acrylate monomers is less than or equal to 2000.

[0088] The monofunctional (meth)acrylate monomers and / or their oligomers include, but are not limited to, any one or a combination thereof, of methyl (meth)acrylate and / or their oligomers, ethyl (meth)acrylate and / or their oligomers, propyl (meth)acrylate and / or their oligomers, and butyl (meth)acrylate and / or their oligomers.

[0089] The polyfunctional (meth)acrylate monomers and / or their oligomers include, but are not limited to, any one or a combination of difunctional acrylate monomers and / or their oligomers, trifunctional acrylate monomers and / or their oligomers, tetrafunctional acrylate monomers and / or their oligomers, pentafunctional acrylate monomers and / or their oligomers, and hexafunctional acrylate monomers and / or their oligomers, and the polyfunctional (meth)acrylate monomers and / or their oligomers may be self-made or purchased from Sartamomer.

[0090] Preferably, the polyfunctional (meth)acrylate monomer has two or three (meth)acrylate groups.

[0091] The polyfunctional (meth)acrylate monomers and / or their oligomers include, but are not limited to, any one or a combination thereof, of tricyclodecanediethanol di(meth)acrylate and / or its oligomers, dioxanediol di(meth)acrylate and / or its oligomers, dipropylene glycol di(meth)acrylate and / or its oligomers, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate and / or its oligomers, pentaerythritol tri(meth)acrylate and / or its oligomers, pentaerythritol tetra(meth)acrylate and / or its oligomers, di-trihydroxymethylpropane tetra(meth)acrylate and / or its oligomers, dipentaerythritol penta(meth)acrylate and / or its oligomers, and dipentaerythritol hexa(meth)acrylate and / or its oligomers.

[0092] Compared to acrylate monomers and / or oligomers that have only one (meth)acrylate group, the multifunctional (meth)acrylate monomers and / or oligomers of the present invention have a higher crosslinking density, resulting in products with better heat resistance.

[0093] The polyfunctional (meth)acrylate monomer and its oligomer, after being heated to complete curing, have a glass transition temperature greater than or equal to 80°C, that is, the cured polyfunctional (meth)acrylate monomer and its oligomer have a glass transition temperature greater than or equal to 80°C. Preferably, the polyfunctional (meth)acrylate monomer and its oligomer, after being heated to complete curing, have a glass transition temperature greater than or equal to 90°C. Preferably, the polyfunctional (meth)acrylate compound and its oligomer, after being heated to complete curing, have a glass transition temperature greater than or equal to 150°C.

[0094] In this invention, the acrylate compound not only participates in the crosslinking reaction but also dissolves and dilutes the resin composition. Preferably, the resin composition of this invention does not require the addition of additional organic solvents, and the resulting resin composition has extremely low volatile content, moderate viscosity, and stable shelf life.

[0095] Preferably, the resin composition does not include organic solvents. The resin composition does not include any one or a combination of alcohols, ethers, ketones, aromatic hydrocarbons, esters, and amides. Organic solvents include, but are not limited to: methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, propylene glycol methyl ether acetate, dimethylformamide, dimethylacetamide, and other solvents or mixtures thereof.

[0096] The maleimide resin in the thermosetting resin can be any type of maleimide resin known in the art. Preferably, the content of maleimide resin in the thermosetting resin is 0-15 wt%, and more preferably 3-11 wt%.

[0097] Specific examples of the maleimide resin include, but are 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-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinyl benzyl maleimide Maleimide (VBM), maleimide containing an indene structure, maleimide containing an isopropyl and meta-arylene structure, maleimide containing a biphenyl alkylene structure, maleimide containing an aliphatic structure with 10 to 50 carbon atoms, or any combination thereof.

[0098] Unless otherwise specified, the aforementioned maleimide resins should be interpreted to include their modifiers, such as, but not limited to, 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, prepolymers of cyanate esters and maleimide resins, or combinations thereof.

[0099] Specific examples of maleimide resins include, but are not limited to, maleimide resins manufactured by Daiwakasei Industry Co., Ltd. under trade names such as 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; maleimide resins manufactured by KI Chemical Industry Co., Ltd. under trade names such as BMI-70 and BMI-80; and maleimide resins manufactured by Nippon Kayaku Co., Ltd. under trade names such as MIR-3000 or MIR-5000.

[0100] Maleimides with an aliphatic structure containing 10 to 50 carbon atoms, or imide-elongated maleimide resins, may include various imide-elongated maleimide resins disclosed in Taiwan Patent Application Publication No. TW200508284A, all of which are incorporated herein by reference. Specific examples of maleimides with an aliphatic structure containing 10 to 50 carbon atoms suitable for use in this invention include, but are not limited to, maleimide resins manufactured by DesignerMolecules Inc. under trade names such as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000. The structure of the said aliphatic maleimide with an aliphatic structure containing 10 to 50 carbon atoms includes a maleimide group and an aliphatic group bonded to the maleimide group.

[0101] The maleimide containing isopropyl and meta-aryl structures includes the maleimide shown in formula (1), the maleimide containing biphenyl alkylene structures includes the maleimide shown in formula (2), and the maleimide containing indane structures includes the maleimide shown in formula (3).

[0102]

[0103] In equation (1), p2 represents the average degree of polymerization, and p2 can be a value from 1 to 10.

[0104]

[0105] In equation (2), p3 represents the average degree of polymerization, and p3 can be a value from 1 to 10.

[0106]

[0107] In equation (3), R1 and R2 are independently the same or different, and each independently represents C1 to C2. 10 The alkyl group, m1 represents the number of R1 groups, and each m1 is an integer from 0 to 4 independently, n1 represents the number of R2 groups, and each n1 is an integer from 0 to 3 independently, p1 represents the average degree of polymerization, and p1 can be a value from 0.5 to 20.

[0108] Unless otherwise specified, the cyanate-modified maleimide resin (or maleimide triazine resin) used in this invention is not particularly limited and can be any type of maleimide triazine resin known in the art. Specific examples include, but are not limited to: maleimide triazine resin obtained by polymerizing maleimide resin with bisphenol A type cyanate resin; maleimide triazine resin obtained by polymerizing maleimide resin with bisphenol F type cyanate resin; maleimide triazine resin obtained by polymerizing maleimide resin with phenolic phenolic cyanate resin; and maleimide triazine resin obtained by polymerizing maleimide resin with cyanate resin containing a dicyclopentadiene structure. The maleimide triazine resin can be obtained by polymerizing the aforementioned maleimide resin and the aforementioned cyanate resin in any molar ratio; the molar ratio of maleimide resin to cyanate resin can be 1:1 to 10, for example, but not limited to 1:1, 1:2, 1:4, 1:6, 1:8, or 1:10.

[0109] In this invention, the silicone resin can be any type of silicone resin known in the art. Preferably, the silicone resin accounts for 0-10 wt% of the thermosetting resin. Specific examples include, but are not limited to, polyalkyl silicone resins, polyaryl silicone resins, polyalkylaryl silicone resins, modified silicone resins, or combinations thereof. Modified silicone resins include, but are not limited to, amino-modified silicone resins, epoxy-modified silicone resins, methacrylamide-modified silicone resins, hydroxyl-modified silicone resins, carboxyl-modified silicone resins, or combinations thereof. Preferably, the amino-modified silicone resins applicable to this application include, for example, amino-modified silicone resins manufactured by Shin-Etsu Chemical Industry Co., Ltd. under the 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 manufactured by Toray-Dow Corning Co., Ltd. under the trade names BY-16-853U, BY-16-853, BY-16-853B, etc.; amino-modified silicone resins manufactured by Momentive Performance Materials JAPAN Co., Ltd. under the trade names XF42-C5742, XF42-C6252, XF42-C5379, etc.; or combinations thereof. The epoxy-modified silicone resins applicable to this application include, for example, the X-22-163 series manufactured by Shin-Etsu Chemical Industry Co., Ltd. The methacrylamide-modified silicone resins applicable to this application include, for example, the X-22-164 series manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0110] In this invention, the polyphenylene ether resin used is not particularly limited and can be any type of polyphenylene ether resin known in the art, and can be any one or more commercially available products, homemade products, or combinations thereof, such as including but not limited to hydroxyl polyphenylene ether resins (e.g., SA90, SA120, available from SABIC), polyphenylene ether resins containing unsaturated carbon-carbon double bonds, or combinations thereof. The polyphenylene ether resins containing unsaturated carbon-carbon double bonds include any one or a combination of vinyl benzyl polyphenylene ether resin, (meth)acrylate-based polyphenylene ether resin, vinyl polyphenylene ether resin, and allyl polyphenylene ether resin. Preferably, the polyphenylene ether resin accounts for 0-10 wt% of the thermosetting resin.

[0111] The polyphenylene ether resin containing unsaturated carbon-carbon double bonds of the present invention has unsaturated carbon-carbon double bonds and a phenylene ether backbone, wherein the unsaturated carbon-carbon double bonds are reactive functional groups, which can self-polymerize upon heating, or undergo free radical polymerization with other components containing unsaturated bonds in the resin composition and ultimately crosslink and cure. Preferably, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes a polyphenylene ether resin containing unsaturated carbon-carbon double bonds in which the phenylene ether backbone is substituted with 2,6-dimethyl groups. After substitution, the methyl groups form steric barriers, making it difficult for the oxygen atoms on the ether to form hydrogen bonds or van der Waals forces, thus preventing moisture absorption.

[0112] Polyphenylene ether resins containing unsaturated carbon-carbon double bonds include, but are 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 Corporation), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Corporation), 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)acrylate-based polyphenylene ether resins with a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from SABIC), vinyl polyphenylene ether resins with a number average molecular weight of about 2200 to 3000, or combinations thereof. The vinyl polyphenylene ether resins may include all types of polyphenylene ether resins disclosed in U.S. Patent Application US20160185904A1, all of which are incorporated herein by reference. Vinyl benzyl polyphenylene ether resins include, but are not limited to, vinyl benzyl biphenyl polyphenylene ether resins, vinyl benzyl bisphenol A polyphenylene ether resins, or combinations thereof.

[0113] The benzoxazine resin may be any type of benzoxazine resin known in the art. Preferably, the benzoxazine resin accounts for 0-10 wt% of the thermosetting resin. Specific examples include, but are not limited to, bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, phenolphthalein type benzoxazine resin, dicyclopentadiene type benzoxazine resin, phosphorus-containing benzoxazine resin, diamine type benzoxazine resin, and phenyl, vinyl, or allyl modified benzoxazine resins or combinations thereof. Applicable commercially available benzoxazine resins include those sold by Huntsman under the trade names LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8298 (modified benzoxazine resin), LZ-82818 (bisphenol F type benzoxazine resin), and LZ-82919 (bisphenol A type benzoxazine resin); or those produced by Changchun Resin Co., Ltd. under the trade name PF-3500 (diaminodiphenyl ether type benzoxazine resin); or those produced by Showa Polymer Co., Ltd. under the trade name HFB-2006M (phosphorus-containing benzoxazine resin); or those sold by Kolon Industries, Inc. of Korea under the trade names KZH-5031 (allyl modified benzoxazine resin) and KZH-5032 (phenyl modified benzoxazine resin). The diamine-type benzoxazine resin may be a diaminodiphenylmethane benzoxazine resin, a diaminodiphenyl ether type benzoxazine resin, a diaminodiphenyl sulfone benzoxazine resin, a diaminodiphenyl sulfide benzoxazine resin, or a combination thereof, and is not limited thereto.

[0114] The epoxy resin can be any type of epoxy resin known in the art. Preferably, the epoxy resin accounts for 0-10 wt% of the thermosetting resin. From the perspective of improving the heat resistance of the resin composition, the epoxy resin includes, but is not limited to, any one or a combination of, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional phenolic epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin (e.g., naphthol-type epoxy resin and naphthyl ether-type epoxy resin), benzofuran-type epoxy resin, and isocyanate-modified epoxy resin. In this invention, 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. In this invention, the phosphorus-containing epoxy resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin, or a combination thereof. The aforementioned DOPO epoxy resin may be selected from one or more of the following: DOPO-containing phenol novolac epoxy resin, DOPO-containing o-cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin.The aforementioned DOPO-HQ epoxy resin may be selected from one or more of the following: DOPO-HQ-containing phenol novolac epoxyresin, DOPO-HQ-containing o-cresol novolacepoxy resin, and DOPO-HQ-containing bisphenol-Anovolac epoxy resin, and is not limited thereto.

[0115] The epoxy resins mentioned include, but are not limited to, RE310S, RE410S (the above are bisphenol A type epoxy resins manufactured by Nippon Chemical Co., Ltd.), YD-128 (bisphenol A type epoxy resins manufactured by Nippon Steel Chemical), 828US, jER828EL, 825, 828EL (the above are bisphenol A type epoxy resins manufactured by Mitsubishi Chemical Co., Ltd.), RE303S, RE304S, RE403S, RE404S (the above are bisphenol F type epoxy resins manufactured by Nippon Chemical Co., Ltd.), jE807, 1750 (the above are bisphenol F type epoxy resins manufactured by Mitsubishi Chemical Co., Ltd.), HP4032, HP4032D, HP4032SS (the above are naphthalene type epoxy resins manufactured by DIC), and HP4032H (naphthalene type epoxy resins manufactured by DIC). The following epoxy resins are available: EXA-7311, EXA-7311-G3, EXA-7311-G4, EXA-7311-G4S, HP-6000 (the above are naphthalene ether type epoxy resins manufactured by DIC), HP-4700, HP-4710 (the above are naphthalene type tetrafunctional epoxy resins manufactured by DIC), N-690 (cresol phenolic varnish type epoxy resin manufactured by DIC), N-695 (cresol phenolic varnish type epoxy resin manufactured by DIC), HP-7200, HP-7200HH, HP-7200H, HP-7200L (the above are dicyclopentadiene type epoxy resins manufactured by DIC), and YX7700 (phenol aralkyl type epoxy resin manufactured by Mitsubishi Chemical Corporation).

[0116] The active ester suitable for the resin composition of the present invention can be any type of active polyester resin known in the art, including but not limited to various commercially available active polyester resin products. Specific examples include, but are not limited to, polyester resins containing a dicyclopentadiene structure and polyester resins containing a naphthalene ring structure, including but not limited to the active polyester resins sold by DIC Corporation under the trade names HPC-8000-65T or HPC-8150-62T. Preferably, the active ester accounts for 0 to 10 wt% of the thermosetting resin.

[0117] In this invention, the phenolic resin can be any type of phenolic resin known in the art. Specific examples include, but are not limited to, phenolic resins or phenoxy resins, wherein the phenolic resin includes at least one or a combination of phenolic resin, o-methylphenolic resin, bisphenol A phenolic resin, naphthol phenolic resin, biphenyl phenolic resin, and dicyclopentadienol resin, and is not limited thereto. The phenolic resin suitable for the resin composition of this invention can be any type of phenolic resin known in the art, including but not limited to YP-50, YP50S, YP55, YP70, and YPB-43C (manufactured by Nippon Steel Chemicals, phenoxy resin). Preferably, the phenolic resin accounts for 0-10 wt% of the thermosetting resin.

[0118] In this invention, the cyanate resin can be any type of cyanate resin known in the art, such as compounds having an Ar-OC≡N structure, wherein Ar can be a substituted or unsubstituted aromatic group. From the perspective of improving the heat resistance of the resin composition, specific examples 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. The phenolic cyanate resin can be bisphenol A phenolic cyanate resin, bisphenol F phenolic cyanate resin, or combinations thereof. The cyanate ester resin may be a cyanate ester resin produced and sold by Arxada AG under trade names such as Primaset PT-15, PT-30, PT-30S, PT-60, PT-60S, BA-200, BA-230S, BA-3000, BA-3000S, BA-4000, BA-4000S, DT-4000, DT-7000, ULL-950S, HTL-300, CE-320, LVT-50, LVT-100, LECy, etc. Preferably, the cyanate ester resin accounts for 0 to 10 wt% of the thermosetting resin.

[0119] In a preferred embodiment, with regard to improving the shelf life of the resin composition, the resin composition of the present invention preferably comprises:

[0120] (A) Maleic anhydride modified polyolefin;

[0121] (B) Multifunctional (meth)acrylate monomers and / or their oligomers;

[0122] (C) Porous silica surface;

[0123] (D) Non-porous silica.

[0124] Preferably, the content ratio of component (A): component (B): component (C): component (D) is 100:(30-90):(10-30):(150-350).

[0125] In one embodiment, the content ratio of the (C) surface porous silica to the (D) non-porous silica is (1:5) to (1:35), preferably (1:8) to (1:35).

[0126] The maleic anhydride-modified polyolefin, the multifunctional (meth)acrylate monomer and / or its oligomers, and the surface porous silica are as described above.

[0127] The non-porous silica is silica that has no pores on its surface or inside. Preferably, the non-porous silica is spherical silica that has no pores on its surface or inside.

[0128] In addition to the aforementioned components, the resin composition of the present invention may also include, as needed, any one or a combination of flame retardants, curing accelerators, polymerization inhibitors, dyes, surfactants, and toughening agents.

[0129] In one embodiment of the present invention, the flame retardant may be any type of flame retardant known in the art, such as, but not limited to, phosphorus-containing flame retardants or bromine-containing flame retardants. Bromine-containing flame retardants preferably include decabromodiphenyl ethane, and phosphorus-containing flame retardants preferably include hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tri(2-carboxyethyl)phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphonate (DMMP), and resorcinol bis(dixylenyl)phosphate. phosphate), RDX (such as commercially available products like PX-200, PX-201, PX-202, etc.), phosphazene compounds (such as commercially available products SPB-100, SPH-100, etc., which do not contain unsaturated carbon-carbon double bonds, or commercially available products like SPV-100, etc., allyl phosphazene compounds, or commercially available or self-made vinyl phosphazene compounds), ammonium polyphosphate, melamine polyphosphate, (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) compounds and their derivatives or resins (e.g., bisDOPO compounds), diphenylphosphine oxide (DPPO) compounds and their derivatives or resins (e.g., bisDPPO compounds), melamine cyanurate (melamine... cyanurate) and trishydroxyethylisocyanurate, aluminum phosphonates (such as OP-930, OP-935, etc.) or combinations thereof.

[0130] The flame retardant may be a flame retardant sold by Katayama Chemical Industry Co., Ltd., such as, but not limited to, V1, V2, V3, V4, V5, V7, S-2, S-4, E-4c, E-7c, E-8g, E-9g, E-10g, E-100, B-3, W-1o, W-2h, W-2o, W-3o, W-4o, OX-1, OX-2, OX-4, OX-6, OX-6+, OX-7, OX-7+, OX-13, BPE-1, BPE-3, HyP-2, API-9, CMPO, ME-20, C-1R, C-1S, C-3R, C-3S, or C-11R. The flame retardant of the present invention may include one or more of the above-mentioned flame retardants. Unless otherwise specified, the resin composition of the present invention may further include 1 to 100 parts by weight of flame retardant, preferably 1 to 50 parts by weight of flame retardant, but is not limited thereto, compared to 100 parts by weight of thermosetting resin.

[0131] In one embodiment of the present invention, the curing accelerator may include a Lewis base or a Lewis acid catalyst. The Lewis base may include one or more of the following: imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MZ), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). The Lewis acid may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, zinc, etc., and metal catalysts such as zinc octoate and cobalt octoate. The curing accelerator also includes a curing initiator (or initiator), such as a peroxide that can generate free radicals. Curing initiators include, but are not limited to, diisopropylbenzene peroxide (DCP), tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (DYBP), di-tert-butyl peroxide (DTBP), bis(tert-butylperoxyisopropyl)benzene (BIBP), or combinations thereof. Relative to 100 parts by weight of the thermosetting resin, the resin composition of the present invention may further include 0.001 parts by weight to 20 parts by weight of a curing accelerator, preferably 0.01 parts by weight to 15 parts by weight of a curing accelerator, more preferably 0.5 parts by weight to 10 parts by weight of a curing accelerator, but is not limited thereto.

[0132] In one embodiment of the present invention, the polymerization inhibitor may include, but is not limited to, 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, nitroxide-stabilized free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfur free radicals (e.g., including but not limited to dithioesters), hydroquinone, p-methoxyphenol, p-benzoquinone, phenthiazide, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), or combinations thereof. The aforementioned nitroxide-stabilized free radicals may include, but are not limited to, 2,2,6,6-tetramethyl-1-oxy-piperidine, 2,2,6,6-substituted-1-piperidineoxy radicals, or 2,2,5,5-substituted-1-pyrrolidineoxy radicals derived from cyclic hydroxylamines. As substituents, preferably alkyl groups having four or fewer carbon atoms, such as methyl or ethyl. The specific nitroxide free radical compounds are not limited, and examples include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidineoxy radical, 2,2,6,6-tetraethyl-1-piperidineoxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidineoxy radical, 2,2,5,5-tetramethyl-1-pyrrolidineoxy radical, 1,1,3,3-tetramethyl-2-isodihydroindoleoxy radical, N,N-di-tert-butylamineoxy radical, etc. Stable free radicals such as galvinoxyl radicals can also be used instead of nitroxide free radicals. The polymerization inhibitors suitable for the resin compositions of the present invention can also be products derived from the substitution of hydrogen atoms or groups of atoms in the inhibitor by other atoms or groups. For example, products derived from the substitution of hydrogen atoms in the inhibitor by groups such as amine, hydroxyl, and carbonyl groups. The resin composition of the present invention may further include 0.001 to 20 parts by weight of a polymerization inhibitor, preferably 0.001 to 10 parts by weight of a polymerization inhibitor, but is not limited thereto, relative to 100 parts by weight of the thermosetting resin.

[0133] In one embodiment of the present invention, the dyeing agent may include, but is not limited to, dyes or pigments. The resin composition of the present invention may further include 0.001 to 10 parts by weight of dyeing agent, preferably 0.01 to 5 parts by weight of dyeing agent, but is not limited thereto, relative to 100 parts by weight of thermosetting resin.

[0134] The types of surfactants suitable for use in the resin compositions of the present invention are not particularly limited. The main function of adding surfactants in the present invention is to enable the filler to be uniformly dispersed in the resin composition. The resin composition of the present invention may further include 0.001 to 10 parts by weight of surfactant, preferably 0.01 to 5 parts by weight, relative to 100 parts by weight of thermosetting resin, but is not limited thereto.

[0135] In one embodiment of the present invention, the main function of adding a toughening agent is to improve the toughness of the resin composition. Suitable toughening agents for the present invention may include, but are not limited to, carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, ethylene propylene rubber, and other compounds or combinations thereof. Relative to 100 parts by weight of thermosetting resin, the resin composition of the present invention may further include 1 to 20 parts by weight of toughening agent, preferably 3 to 10 parts by weight of toughening agent, but is not limited thereto.

[0136] The resin compositions of the foregoing embodiments can be made into various articles, such as components for various electronic products, including but not limited to prepregs, resin films, laminates or printed circuit boards.

[0137] The resin composition of the present invention can be made into a prepreg, which includes a reinforcing material and a layer disposed on the reinforcing material. The layer is obtained by heating the aforementioned resin composition at a high temperature to form a semi-cured state (B-stage). The baking temperature for making the prepreg is between 120°C and 180°C, preferably between 120°C and 160°C. The reinforcing material can be any of a fiber material, woven fabric, or nonwoven fabric, and the woven fabric preferably includes glass fiber cloth. There is no particular limitation on the type of glass fiber cloth; it can be any type of glass fiber cloth suitable for 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, Q-type glass fiber cloth, or QL-type glass fiber cloth (a glass fiber cloth with a mixed structure made of Q glass and L glass). The glass fibers include yarn and roving, etc., and the form includes open or closed fibers, with end face shapes including round or flat shapes. The aforementioned nonwoven fabric preferably includes liquid crystal resin nonwoven fabric, such as polyester nonwoven fabric, polyurethane nonwoven fabric, etc., but is not limited thereto. The aforementioned fabric may also include liquid crystal resin fabric, such as polyester fabric or polyurethane fabric, and is not limited thereto. 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 subsequently undergoes heating and curing (C-stage) to form an insulating layer.

[0138] The resin compositions of various embodiments of the present invention can be made into resin films, which are obtained by baking and heating the aforementioned resin compositions to form a semi-cured state (B-stage). The resin compositions can be selectively coated onto liquid crystal resin films, polytetrafluoroethylene films (PTFE films), polyethylene terephthalate films (PET films), polyimide films (PI films), copper foils (including but not limited to copper foils with a thickness of 28 mils and a 1 ounce HVLP (hyper very low profile)) or resin-coated copper foils (RCC), and then baked and heated to form a semi-cured state, thereby forming a resin film from the resin compositions.

[0139] The resin compositions of various embodiments of the present invention can be used to form various laminates comprising at least two metal foils and at least one insulating layer 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 250°C, preferably between 200°C and 220°C, with a curing time of 90 to 180 minutes, preferably 120 to 150 minutes. Applicable pressing pressures are, for example, between 300 psi and 550 psi, preferably between 400 psi and 500 psi. 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 (including but not limited to copper foil with a thickness of 28 mils and a 1-ounce HVLP (hyper very low profile)). In a preferred embodiment, the laminate is a copper foil substrate.

[0140] The aforementioned multilayer board can be further processed into a printed circuit board. One method of manufacturing the printed circuit board of this invention involves using a double-sided copper foil substrate (e.g., product EM-891, available from Taiguang Electronic Materials (Kunshan) Co., Ltd.) with a thickness of 28 mils and 1 ounce HVLP (hyper very low profile) 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 circuitry, the aforementioned prepreg, and the copper foil are stacked sequentially, and then heated at 190°C to 245°C for 90 to 240 minutes using a vacuum lamination apparatus to cure the insulating material of the prepreg. Next, various circuit board processes known in the art, such as blackening, drilling, and copper plating, are performed on the outermost copper foil to obtain a printed circuit board.

[0141] Articles made from the aforementioned resin composition contain reinforcing or supporting materials and semi-cured or cured products obtained by heating and chemically cross-linking the resin composition.

[0142] The present invention also provides an article comprising a cured resin obtained by fully curing the resin composition through a heating process (C-stage). The applicable curing temperature in the heating process is, for example, between 150°C and 250°C, preferably between 170°C and 220°C, and the curing time is between 60 and 240 minutes, preferably between 60 and 180 minutes.

[0143] The shape of the cured resin is not particularly limited and can be layered, blocky, granular, or other shapes. The preparation method of the cured resin is not particularly limited and can be obtained by heating and completely curing it in a mold of a specific shape. The mold of a specific shape includes, but is not limited to, a laminated board or printed circuit board with grooves, various holes in a printed circuit board, or open areas of the circuit lines in a printed circuit board; it can also be obtained by coating it on a support material and heating and completely curing it.

[0144] For example, the aforementioned article contains only a cured resin obtained by curing the resin composition. As another example, the aforementioned article contains a cured resin obtained by curing the resin composition and a support material. The support material includes, but is not limited to, a liquid crystal resin film, a polytetrafluoroethylene film (PTFE film), a polyethylene terephthalate film (PET film), a polyimide film (PI film), and a metal foil.

[0145] This invention also provides an application of the above-mentioned resin composition in the resin filling process of printed circuit boards (PCBs). The resin filling process includes, but is not limited to, PCB hole plugging, PCB slot filling, and PCB circuit filling processes. This invention further provides an application of the above-mentioned resin composition in the hole plugging process of printed circuit boards. For example, in the manufacturing process of a printed circuit board, a multilayer board is first drilled, and electroplating is selectively performed according to process requirements, followed by a hole plugging process. For example, after drilling, electroplating can be performed first to create electrical conductivity between the upper and lower copper foils, followed by the hole plugging process; or, after drilling, the hole plugging process can be performed first, and then the multilayer board after the hole plugging process can be drilled a second time. The diameter of the second drilled hole is usually smaller than that of the first drilled hole, and copper is electroplated onto the wall of the second drilled hole. The resin composition of this invention is particularly suitable for the hole plugging process of printed circuit boards. The resin composition of this invention can be inserted into the hole and completely cured before various subsequent circuit board processing techniques known in the art are performed. Specifically, at least one hole of the printed circuit board is filled with a cured resin composition, and then the printed circuit board is subjected to various subsequent circuit board processing techniques known in the art.

[0146] This invention also provides an application of the above-described resin composition in the groove filling process of a printed circuit board. For example, during the fabrication of a printed circuit board, a groove is formed in a non-circuit area of ​​the multilayer board, and the groove is filled with resin adhesive. The resin-filled area is then cured and leveled before various subsequent circuit board processing techniques known in the art are performed. Specifically, at least one groove of the printed circuit board is filled with a cured product of the resin composition before the printed circuit board undergoes various subsequent circuit board processing techniques known in the art. The groove walls may be electroplated or unplated.

[0147] This invention also provides an application of the above-described resin composition in the circuit filling process of printed circuit boards. For example, in the manufacturing process of a printed circuit board, after the multilayer board is first processed to form inner layer circuits, a circuit filling process is selectively performed according to the copper thickness of the inner layer circuits. The resin composition of this invention is particularly suitable for the circuit filling process of printed circuit boards. After the resin composition of this invention is filled into the circuit empty areas (i.e., areas without circuits) and completely cured, various subsequent circuit board processing techniques known in the art are performed. Specifically, at least one circuit empty area of ​​the printed circuit board is covered with the cured resin composition, and then the printed circuit board is subjected to various subsequent circuit board processing techniques known in the art.

[0148] The resin composition disclosed in this invention is used in the printed circuit board filling process to prepare a printed circuit board containing a cured resin, which preferably has one or more of the following characteristics:

[0149] The tin drift crack rate of the printed circuit board, measured according to the method of IPC-TM-650 2.4.13.1, is 0%.

[0150] The via impedance amplitude of the printed circuit board measured using a network analyzer with a time domain reflector (TDR) module is ≤10%, for example, via impedance amplitude <5%, or between 5% and 10%.

[0151] In the resin filling process of printed circuit boards, the continuous glue scraping time is ≥15 minutes, for example, between 15 minutes and 1 hour, or for example, the continuous glue scraping time is >1 hour.

[0152] Preferably, the resin composition disclosed in this invention, or various articles containing resin cured products prepared therefrom, preferably have one or more of the following characteristics:

[0153] The resin composition has a shelf life of more than 90 days.

[0154] The volatile organic matter content of the resin composition, as measured according to the method of IPC-TM-650 2.4.24.6, is less than or equal to 0.50%, for example, between 0.10% and 0.50%.

[0155] The dielectric loss coefficient measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0041, for example, between 0.0035 and 0.0041;

[0156] The pull force on the copper foil, measured according to the method of IPC-TM-650 2.4.8, is greater than or equal to 5.9 lb / in, for example, between 4.3 lb / in and 5.9 lb / in;

[0157] The Z-axis thermal expansion coefficient, measured according to the method of IPC-TM-650 2.4.24.5, is less than or equal to 1.70%, for example, between 1.00% and 1.70%.

[0158] The water absorption rate measured according to IPC-TM-650 2.6.2.1 and IPC-TM-650 2.6.16.1 is less than or equal to 0.30%; for example, between 0.21% and 0.30%.

[0159] The shear viscosity change rate of the resin composition, measured according to the method of GB / T 2794-2022 7.3, is 9-56%.

[0160] By optimizing the dielectric loss coefficient, volatile organic matter content, and shear viscosity change rate of the resin composition, the tin bleed crack rate, impedance stability, and adhesive scraping stability of the printed circuit board containing the resin curing material prepared by the resin filling process for printed circuit boards can be further improved.

[0161] The resin compositions of the embodiments and comparative examples of the present invention were prepared using various raw materials from the following sources in accordance with the amounts specified in Tables 1 to 9, and were further prepared into various test samples.

[0162] The chemical raw materials used in the embodiments and comparative examples of this invention are as follows:

[0163] Ricon 131MA5: Maleic anhydride addition polybutadiene, purchased from Cray Valley SA.

[0164] Ricon 130MA8: Maleic anhydride addition polybutadiene, purchased from Cray Valley SA.

[0165] Ricon 130MA13: Maleic anhydride addition polybutadiene, purchased from Cray Valley SA.

[0166] Ricon 131MA10: Maleic anhydride addition polybutadiene, purchased from Cray Valley SA.

[0167] Ricon 156MA17: Maleic anhydride addition polybutadiene, purchased from Cray Valley SA.

[0168] Ricon 184MA6: Maleic anhydride addition styrene-butadiene copolymer, purchased from Cray Valley SA.

[0169] XIRAN-EF80: Maleic anhydride-styrene copolymer, purchased from Aurorium.

[0170] Ricon 130: Polybutadiene, purchased from Cray Valley SA.

[0171] G1726: Hydrogenated styrene-butadiene-styrene block copolymer, purchased from Kraton Corporation.

[0172] SBS-A: Styrene-butadiene block copolymer, specifically styrene-butadiene-styrene triblock copolymer, purchased from Japan Soda.

[0173] SR833S: Tricyclodecanediethanol diacrylate, with the following structural formula, purchased from Sartomer, and its cured product has a glass transition temperature of approximately 180°C.

[0174]

[0175] SR368NS: Tris(2-hydroxyethyl)isocyanurate triacrylate, with the following structural formula, purchased from Sartomer, whose cured product has a glass transition temperature of approximately 272°C.

[0176]

[0177] Oligomer of SR833S: Oligomer of tricyclodecanediethanol diacrylate, obtained by polymerization of tricyclodecanediethanol diacrylate, with a weight-average molecular weight of less than 2000, and a glass transition temperature of approximately 180°C for its cured product.

[0178] SR295 NS: Pentaerythritol tetraacrylate, with the following structural formula, purchased from Sartomer, whose cured product has a glass transition temperature of approximately 103°C.

[0179]

[0180] SR399 NS: Dipentaerythritol pentaacrylate, with the following structural formula, purchased from Sartomer, whose cured product has a glass transition temperature of approximately 90°C.

[0181]

[0182] DPHA: Dipentaerythritol hexaacrylate, with the following structural formula, purchased from Sartomer, and its cured product has a glass transition temperature of approximately 90°C.

[0183]

[0184] Maleimide as shown in formula (1): commercially available, where p2 is a value from 1 to 10.

[0185] Maleimide as shown in formula (2): commercially available, where p3 is a value from 1 to 10.

[0186] Maleimide as shown in formula (3): commercially available, wherein R1 is methyl, m1 is 2, n1 is 0, and p1 is a value from 0.5 to 20.

[0187] BMI-5100: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, with the following structural formula, purchased from Daiwakasei Industry Co., Ltd.

[0188]

[0189] BMI-2300: Polyphenylene maleimide, with the following structural formula, where p4 is a value from 1 to 10, purchased from Daiwakasei Industry Co., Ltd.

[0190]

[0191] BMI-4000: Bisphenol A diphenyl ether bismaleimide, structural formula as shown below, purchased from Daiwakasei Industry Co., Ltd.

[0192]

[0193] BMI-1000: 4,4'-diphenylmethane bismaleimide, structural formula as shown below, purchased from Daiwakasei Industry Co., Ltd.

[0194]

[0195] BMI-1500: Maleimide with an aliphatic structure containing 10 to 50 carbon atoms, with the following structural formula, where p5 is a value from 1 to 10, purchased from the designer's molecular company.

[0196]

[0197] BMI-3000: Maleimide with an aliphatic structure containing 10 to 50 carbon atoms, with the following structural formula, where p6 is a value from 1 to 10, purchased from the designer's molecular company.

[0198]

[0199] BMI-1700: Maleimide with an aliphatic structure containing 10 to 50 carbon atoms, with the following structural formula, where p7 is a value from 1 to 10, purchased from the designer's molecular company.

[0200]

[0201] SA9000: (Methacryl)acryloyl polyphenylene ether resin, purchased from Saudi Basic Industries Corporation (SABIC).

[0202] OPE-2st 2200: Ethylene benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical Co., Ltd.

[0203] OPE-2st 1200: Ethylene benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical Co., Ltd.

[0204] B-461: Organosilicon resin, purchased from Guangdong Zhonglianbang Fine Chemical Co., Ltd.

[0205] X-22-161A: Amino-modified silicone resin, purchased from Shin-Etsu Chemical Industry Co., Ltd.

[0206] BY-16-853B: Amino-modified silicone resin, purchased from Toray-Dow Corning Co., Ltd.

[0207] XF42-C5379: Amino-modified silicone resin, purchased from Momentive Performance Materials Japan.

[0208] BA-230S: Bisphenol A cyanate, purchased from Arxada AG.

[0209] HTL-300: Vinyl functionalized cyanate, purchased from Arxada AG.

[0210] CE-320: Cyanate ester resin, purchased from Arxada AG.

[0211] HP 6000: Naphthalene ether type epoxy resin, purchased from DIC.

[0212] HP 7200: Dicyclopentadiene type epoxy resin, purchased from DIC.

[0213] YX7700: Phenolic aralkyl type epoxy resin, purchased from Mitsubishi Chemical Corporation.

[0214] YD-128: Bisphenol A type epoxy resin, purchased from Nippon Steel Chemicals.

[0215] LZ-82919: Bisphenol A type benzoxazine resin, purchased from Huntsman.

[0216] KZH-5031: Vinyl-modified benzoxazine resin, purchased from Kolon Industries, Inc., South Korea.

[0217] PF-3500: Diaminodiphenyl ether type benzoxazine resin, purchased from Changchun Resin Company.

[0218] HPC-8000-65T: Reactive polyester resin, purchased from DIC Corporation.

[0219] HPC-8150-62T: Reactive polyester resin, purchased from DIC Corporation.

[0220] YP-50: Phenoxy resin, purchased from Nippon Steel Chemicals.

[0221] DCP: dicumyl peroxide, purchased from Japanese oils and fats.

[0222] P1: Solid spherical silica with porous surface treatment, D100 particle size 5μm, specific surface area 200m2 / g, commercially available.

[0223] P2: Solid spherical silica with porous surface treatment, D100 particle size 10μm, specific surface area 130m2 / g, commercially available.

[0224] P3: Solid spherical silica with porous surface treatment, D100 particle size 15.9μm, specific surface area 103m2 / g, commercially available.

[0225] P4: Solid spherical silica with porous surface treatment, D100 particle size 20μm, specific surface area 40m2 / g, commercially available.

[0226] Nano silica: YA050C-MJE, average particle size 0.050μm, specific surface area 61.8m2 / g, Admatechs, Japan.

[0227] Hollow silica: purchased from Suzhou Jinyi New Material Technology Co., Ltd.

[0228] Chemically synthesized spherical silica (spherical SiO2 (synthetic method)): The median particle size D50 is about 1.5±0.5μm. It is prepared by microemulsion method and the surface is treated with silane coupling agent. The chemically synthesized spherical silica was purchased from Suzhou Jinyi New Material Technology Co., Ltd.

[0229] The composition (all units are parts by weight) and sample characteristic test results of the resin compositions of the embodiments and comparative examples of the present invention are shown in Tables 1 to 9:

[0230] Table 1. Composition and property test results of the resin compositions in Examples E1 to E5

[0231]

[0232]

[0233] Table 2. Composition and property test results of resin compositions in Examples E6 to E10

[0234]

[0235]

[0236] Table 3. Composition and property test results of resin compositions of comparative examples C1 to C7.

[0237]

[0238]

[0239] Table 4. Composition and property test results of the resin compositions in Examples E11 to E15

[0240]

[0241] Table 5. Composition and property test results of the resin compositions of Examples E16 to E20

[0242]

[0243] Table 6. Composition and property test results of the resin compositions of Examples E21 to E25

[0244]

[0245] Table 7. Composition and property test results of the resin compositions of Examples E26 to E30:

[0246]

[0247] Table 8. Composition and property test results of the resin compositions of Comparative Examples C8-C11 and Examples E31-E32

[0248]

[0249] Table 9. Composition and property test results of the resin compositions of Examples E33-E34 and Comparative Examples C12-C14

[0250]

[0251] In this invention, the characteristic tests of the embodiments and comparative examples are conducted by preparing the test samples in the following manner and then performing the tests according to specific test conditions.

[0252] 1. Adhesives containing inorganic fillers

[0253] According to the dosages in Tables 1 to 9, each component of each embodiment or comparative example was added to a mixing tank and stirred. The mixture was completely dissolved and uniformly mixed at an environment of 25°C to 80°C to form a resin composition containing inorganic fillers, which is called an adhesive containing inorganic fillers.

[0254] 2. Copper foil-containing resin cured products

[0255] Prepare a mold (e.g., a fully cured laminate), and carve grooves into the mold. Place the resin containing inorganic fillers prepared in the examples or comparative examples into the grooves. Cover the upper and lower surfaces with copper foil (e.g., 1 oz HVLP copper foil). Perform pressure-curing (C-Stage) under high temperature, high pressure, and vacuum conditions. The curing temperature is between 200°C and 210°C, the curing time is between 120 and 150 minutes, and the pressure is between 400 psi and 500 psi. After complete curing, use a CNC molding machine (model TQZX-II) with a 1.6 mm diameter milling cutter to mill the sample according to the shape of the grooves, obtaining a resin cured product with copper foil covering the upper and lower surfaces, referred to as copper foil-containing resin cured product, used for testing the tensile strength of copper foil.

[0256] 3. Does not contain copper foil resin cured products

[0257] The copper foil-containing resin cured product was etched to remove the copper foil from the upper and lower surfaces to obtain a copper foil-free resin cured product, which was used to test the dielectric loss coefficient, Z-axis thermal expansion coefficient and water absorption rate.

[0258] The characteristic analysis items and test methods of the resin composition and its products of the present invention are described below:

[0259] 1. Varnish shelf life

[0260] The above-mentioned adhesive solution, free of inorganic fillers, was placed at 25°C and observed daily by personnel for the presence of brown solid precipitates. The viscosity of the adhesive solution was also tested daily for 90 days, and the time when precipitates appeared or the viscosity changed by 10% or more was recorded. If no precipitates were observed after 90 days, and the viscosity change was less than 10%, it was marked as >90, indicating a shelf life greater than 90 days (e.g., 91 to 180 days, 91 to 100 days, or 91 to 95 days). If at least one precipitate (usually brown) approximately 0.5 to 5 mm in length was produced, it was marked as precipitation, and observation was stopped, with the number of days since precipitation recorded. Precipitation in the adhesive solution can cause variations and deterioration in the properties of the subsequently cured resin. If no precipitates were found, but the viscosity change was 10% or more, observation was stopped, and the number of days with a viscosity change of 10% or more was recorded.

[0261] 2. Percent of volatile organic compounds

[0262] The above-mentioned adhesive containing inorganic fillers was selected as the test sample. The sample was placed in a test aluminum pan and heated from 50°C to 550°C at a heating rate of 10°C / min, referring to the method described in IPC-TM-6502.4.24.6 (2012). The weight loss percentage (in %) at 150°C was recorded, which represents the volatile organic matter content of the resin composition. The lower the volatile organic matter content of the resin composition, the better it is for improving the processability of the resin filling process and the yield of the product.

[0263] 3. Copper foil tensile strength (or copper foil peel strength, P / S)

[0264] The above-mentioned copper foil-containing resin cured product was cut into rectangular samples with a width of 24 mm and a length greater than 60 mm. The surface copper foil was etched, leaving only a strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. The tensile strength was measured using a universal tensile testing machine at room temperature (approximately 25°C) according to the method described in IPC-TM-650 2.4.8 (2012) to determine the force required to pull the copper foil away from the surface of the cured product, in units of lb / in.

[0265] 4. Dissipation factor (Df)

[0266] The above-mentioned copper foil-free resin cured products were selected as test samples. Each test sample was measured at room temperature (approximately 25°C) and at a frequency of 10 GHz using a microwave dielectric analyzer (purchased from AET Corporation, Japan) in accordance with the method described in JIS C2565 (1992).

[0267] 5. Z-axis thermal expansion coefficient (percent of thermal expansion, z-axis, Z-PTE)

[0268] The aforementioned copper foil-free cured resin was selected as the test sample, and thermomechanical analysis (TMA) was performed according to IPC-TM-650 2.4.24.5 (2012). The temperature was increased from 50℃ to 260℃ at a rate of 10℃ per minute, and the Z-axis thermal expansion coefficient (in %) of each test sample was measured within the temperature range of 50℃ to 260℃. When the measured value of the Z-axis thermal expansion coefficient of the cured resin was less than or equal to 1.7%, and the difference in the measured value of the Z-axis thermal expansion coefficient was greater than or equal to 0.1%, it indicated a significant difference between different samples (because the cured resin does not contain reinforcing materials, reducing the Z-axis thermal expansion coefficient presents significant technical difficulties).

[0269] 6. Water absorption rate

[0270] The above-mentioned copper foil-free resin cured product was selected as the test sample. Following the method described in IPC-TM-650 2.6.2.1 (2012), the sample was baked in an oven at 105±10℃ for 1 hour, then removed and cooled at room temperature (approximately 25℃) for 10 minutes. The sample weight was then measured as W1. Following the method described in IPC-TM-650 2.6.16.1, the sample underwent a pressure cooking test (PCT) for 3 hours (temperature 121℃, relative humidity 100%) to absorb moisture. After removal, cooling, and drying the sample surface, the sample weight was measured as W2. The water absorption rate was calculated using the following formula:

[0271] Water absorption rate (%) = [(W2-W1) / W1]*100%.

[0272] 7. Shear viscosity change rate

[0273] The above-mentioned adhesive containing inorganic fillers was selected as the test sample. Referring to the method described in GB / T 2794-2022 7.3, a TA DHR-2 flat plate rheometer was used to test the viscosity of the adhesive containing inorganic fillers at different shear rates. The test parameters were adjusted as follows: the upper conical plate of the flat plate rheometer had a diameter of 40 mm and an angle of 2°; the temperature of its bottom plate was 25°C. Before the test, the sample was placed on the bottom plate and kept at a constant temperature for 120 s. During the test, the shear rate range of the flat plate rheometer was set from 2.86 s⁻¹ to 57.30 s⁻¹, with an increment of 10 s⁻¹. After the test, the viscosity (rad / s) versus shear rate (s⁻¹) was obtained. The viscosity of the adhesive at a shear rate of 2.86 1 / s was recorded as N1, and the shear rate was 28.6 rad / s. The viscosity of the adhesive at 1 / s is N2, and the viscosity change rate (%) of the adhesive is [(N1-N2) / N1]*100%.

[0274] The inorganic filler-containing adhesives prepared in Examples E1-E10 and Comparative Examples C1-C7 were used in the printed circuit board filling process. The characteristic analysis items and test methods of the printed circuit boards are described below:

[0275] 1. Solder floating crack rate

[0276] (1) Preparation of via-filled copper clad laminate

[0277] Prepare two 3-ounce high-temperature high-elongation (HTE) copper foils and two prepregs made of 106 fiberglass cloth (e.g., product EM-890, available from Taiguang Electronic Materials (Kunshan) Co., Ltd.). Stack them in the order of one HVLP copper foil, two prepregs, and one HVLP copper foil. Press them together under vacuum conditions, pressure of 500 psi, and 210°C for 2 hours to form a copper-containing inner layer substrate. Perform browning treatment on both sides of the copper-containing inner layer substrate. Then, drill holes in the browned copper-containing inner layer substrate and perform a hole-filling process. Fill the holes with the adhesive containing inorganic fillers prepared in the aforementioned examples E1-E10 or comparative examples C1-C7 to obtain a hole-filled copper-containing inner layer substrate. Heat the oven to 175°C and place the hole-filled copper-containing inner layer substrate in the oven for 1 hour. Then, allow it to cool naturally to 80°C to obtain a hole-filled copper-clad laminate.

[0278] (2) Evaluation of substrate preparation

[0279] Prepare four prepregs made of 1078 L-glass fiber cloth (e.g., product EM-890, which can be purchased from Taiguang Electronic Materials (Kunshan) Co., Ltd.) and one of the above-mentioned via-filled copper clad laminates. Stack the prepregs, via-filled copper clad laminates, and prepregs alternately in the following order. Then, stack one 18-micron thick HVLP copper foil on the outermost front and back sides respectively. Press the substrate under vacuum conditions, pressure of 500 psi, and 210°C for 2 hours to form the evaluation substrate.

[0280] (3) Determination of the rate of tin-bleached cracks

[0281] The aforementioned single evaluation substrate was cut into 18 samples of 8 cm * 10 cm. Each sample was placed in a tin bath at 288°C for 10 seconds to tin-bleach, and then removed and cooled for 120 seconds. This cycle was repeated 20 times. The samples were sliced ​​and prepared in the drilled area. An optical microscope was used to observe whether there were cracks in the resin-filled area inside the holes of each sample. Cracks refer to the cracking inside the resin. For a single evaluation substrate, the tin-bleaching crack rate = number of cracked holes * 100% / total number of holes. The lower the tin-bleaching crack rate, the better. A lower tin-bleaching crack rate indicates stronger bonding between the resin components and a higher yield of the plugging process.

[0282] 2. Impedance stability

[0283] A commercially available high-density interconnect substrate (20-layer HDI substrate) with a characteristic impedance of 95 ohms was selected. Inorganic filler-containing adhesive prepared according to Examples E1-E10 or Comparative Examples C1-C7 of this invention was filled into its vias, and the resin composition was heated to fully cure. A network analyzer with a time-domain reflectometry (TDR) module (test parameters: 40 GHz, 25°C) was used to detect the impedance between the 2nd and 19th layers of the HDI substrate, obtaining an impedance curve. Due to the different materials used in the via region and the circuit region, the impedance changes when a signal passes through the via region, causing vibrations in the impedance curve. The smaller the amplitude of the via region impedance relative to the circuit region impedance, the better the impedance stability, and thus the better the signal transmission performance of the printed circuit board. Here, A represents an amplitude of via region impedance relative to the circuit region impedance <5%, B represents an amplitude of via region impedance relative to the circuit region impedance 5 to 10%, and C represents an amplitude of via region impedance relative to the circuit region impedance >10%.

[0284] 3. Stability of adhesive application

[0285] The inorganic filler-containing adhesives prepared in Examples E1-E10 or Comparative Examples C1-C7 were selected as test samples. Vacuum screen printing was used for squeegee filling, i.e., the inorganic filler-containing adhesive was filled into the holes. After the squeegee speed was adjusted, the viscosity of the resin decreased as squeegeeing continued, resulting in insufficient resin filling in the hole-filling area. At this point, the machine needed to be stopped and parameters adjusted, such as adjusting the squeegee speed or replacing the resin. A longer continuous squeegeeing time indicates better squeegee stability and better thixotropic resistance of the adhesive. A represents a continuous squeegeeing time > 1 hour; B represents a continuous squeegeeing time of 15 minutes to 1 hour; C represents a continuous squeegeeing time < 15 minutes.

[0286] Based on the comprehensive reference to the characteristic test results in Tables 1 to 9, the following phenomena can be clearly observed:

[0287] The resin compositions of Examples E1 to E10 have an organic volatile content of less than or equal to 2.0%, a shear viscosity change rate of 9 to 56%, and a dielectric loss coefficient (Df) of less than or equal to 0.0080. The resin compositions of Comparative Examples C1 to C7 do not meet one or more of the above characteristics. The printed circuit boards prepared by the resin compositions of Examples E1 to E10 show significant improvements in impedance stability, tin drift crack rate, and squeegee stability compared to the printed circuit boards prepared by the resin compositions of Comparative Examples C1 to C7.

[0288] A comparison of Examples E11 to E30 with Comparative Examples C8 and C9 shows that, compared to adding 10 to 30 parts by weight of surface porous silica (based on a maleic anhydride-modified polyolefin content of 100 parts by weight), when the amount of surface porous silica used is not in the range of 10 to 30 parts by weight, the articles made from the resin composition exhibit a significantly deteriorated shear viscosity change rate.

[0289] A comparison of Examples E11 to E30 with Comparative Examples C10 and E31 shows that, compared to the addition of 30 to 90 parts by weight of polyfunctional (meth)acrylate monomers and / or their oligomers (based on a maleic anhydride-modified polyolefin content of 100 parts by weight), when the amount of polyfunctional (meth)acrylate monomers and / or their oligomers used is not in the range of 30 to 90 parts by weight, the articles made from the resin composition show a significant deterioration in terms of adhesive shelf life.

[0290] Comparing Examples E11 to E30 with Comparative Example C11, it can be seen that when no maleic anhydride-modified polyolefin is added to the resin composition, the articles made from the resin composition show significant deterioration in terms of shelf life, volatile organic matter, dielectric loss coefficient, copper foil tensile strength, water absorption rate, and shear viscosity change rate compared to adding 100 parts by weight of maleic anhydride-modified polyolefin.

[0291] Examples E11 to E30, using maleic anhydride-modified polyolefins, polyfunctional (meth)acrylate monomers, oligomers thereof, or combinations thereof, and surface porous silica, compared to Examples E32 to E34 (E32 with added polybutadiene Ricon 130, E33 with added hydrogenated styrene-butadiene-styrene block copolymer G1726, and E34 with added styrene-butadiene-styrene triblock copolymer SBS-A), which used other polyolefins, polyfunctional (meth)acrylate monomers, oligomers thereof, or combinations thereof, and surface porous silica, respectively, articles made from the resin compositions achieved significant improvements in at least the following properties: shelf life, volatile organic matter, and tensile strength to copper foil.

[0292] Examples E11 to E30 use maleic anhydride-modified polyolefins, polyfunctional (meth)acrylate monomers, oligomers thereof, or combinations thereof, and surface porous silica. Compared to Comparative Example C12 (C12 with added bisphenol A type epoxy resin YD-128), which uses resins other than maleic anhydride-modified polyolefins, polyfunctional (meth)acrylate monomers, oligomers thereof, or combinations thereof, and surface porous silica, articles made from the resin compositions show significant improvements in at least the following properties: shelf life, volatile organic matter, dielectric loss coefficient, water absorption, and shear viscosity change rate.

[0293] Examples E11 to E30 use maleic anhydride-modified polyolefins, polyfunctional (meth)acrylate monomers, oligomers thereof, or combinations thereof, and surface porous silica. Compared to Comparative Examples C13 to C14 (C13 with added nano silica YA050C MJE, C14 with added hollow silica), which use maleic anhydride-modified polyolefins, polyfunctional (meth)acrylate monomers, oligomers thereof, or combinations thereof, and other silica particles different from surface porous silica), articles made from the resin compositions show significant improvements in at least the following property: shear viscosity change rate.

Claims

1. A resin composition, characterized in that, The resin composition comprises the following components: 100 parts by weight of thermosetting resin and 100 to 300 parts by weight of inorganic filler; The volatile organic matter content of the resin composition, as measured according to IPC-TM-650 2.4.24.6, is less than or equal to 2.0%. The shear viscosity change rate of the resin composition, measured according to method 7.3 of GB / T 2794-2022, is 9-56%. The dielectric loss coefficient of the cured resin obtained by curing the resin composition is less than or equal to 0.0080, as measured at a frequency of 10 GHz according to the method of JIS C2565.

2. The resin composition according to claim 1, characterized in that, The volatile organic matter content of the resin composition, as measured according to method IPC-TM-6502.4.24.6, is less than or equal to 0.5%. The dielectric loss coefficient of the cured resin obtained by curing the resin composition is less than or equal to 0.0041, as measured at a frequency of 10 GHz according to the method of JIS C2565.

3. The resin composition according to claim 1, characterized in that, Based on a total inorganic filler mass of 100 wt%, the inorganic filler comprises 50 to 100 wt% silica.

4. The resin composition according to claim 1, characterized in that, Based on a total inorganic filler mass of 100 wt%, the inorganic filler includes 2 to 17 wt% surface porous silica.

5. The resin composition according to claim 4, characterized in that, The specific surface area of ​​the porous silica on the surface is 40–200 m². 2 / g.

6. The resin composition according to claim 4, characterized in that, The specific surface area of ​​the porous silica on the surface is 103-200 m². 2 / g.

7. The resin composition according to claim 1, characterized in that, The thermosetting resin includes any one or a combination of polyolefins, acrylate compounds, maleimide resins, silicone resins, polyphenylene ether resins, benzoxazine resins, epoxy resins, reactive esters, phenolic resins, and cyanate ester resins.

8. The resin composition according to claim 1, characterized in that, The resin composition does not contain organic solvents.

9. The resin composition according to claim 1, characterized in that, The thermosetting resin comprises (A) maleic anhydride-modified polyolefin and (B) polyfunctional (meth)acrylate monomers and / or oligomers thereof; and The inorganic filler includes (C) surface porous silica and (D) non-porous silica.

10. The resin composition according to claim 9, characterized in that, The mass ratio of (A) maleic anhydride modified polyolefin: (B) polyfunctional (meth) acrylate monomer and / or its oligomer: (C) surface porous silica: (D) nonporous silica is 100:(30-90):(10-30):(150-350).

11. The resin composition according to claim 9, characterized in that, The mass ratio of the porous silica on surface (C) to the non-porous silica on surface (D) is (1:5) to (1:35).

12. The resin composition according to claim 1, characterized in that, The resin composition further includes any one or a combination of flame retardants, curing accelerators, polymerization inhibitors, dyes, surfactants, and toughening agents.

13. An article made from the resin composition according to any one of claims 1 to 12, characterized in that, The products include prepregs, resin films, laminates, or printed circuit boards.

14. An article made from the resin composition according to any one of claims 1 to 12, characterized in that, The article comprises a cured resin obtained by curing the resin composition.

15. A printed circuit board manufactured using the resin composition of any one of claims 1 to 12 in a resin-filling process for a printed circuit board, characterized in that, The printed circuit board has one or more of the following characteristics: The rate of tin drift cracking in the resin-cured area of ​​the printed circuit board, measured according to the method of IPC-TM-650 2.4.13.1, is 0%. The impedance amplitude of the resin-cured area of ​​the printed circuit board, as measured by a network analyzer, is less than or equal to 10%. The continuous glue scraping time in the resin filling process of printed circuit boards is greater than or equal to 15 minutes.

16. Use of a resin composition according to any one of claims 1 to 12 in a resin filling process for printed circuit boards.

17. The use according to claim 16, characterized in that, The printed circuit board resin filling process includes one or more of the following: printed circuit board via filling process, printed circuit board slot filling process, or printed circuit board circuit filling process.

18. The use according to claim 17, characterized in that, In the printed circuit board via-filling process, at least one hole of the printed circuit board is filled with a cured product of the resin composition. And / or, in the printed circuit board filling process, at least one groove of the printed circuit board is filled with a cured product of the resin composition; And / or, in the printed circuit board circuit filling process, at least one circuit void area of ​​the printed circuit board is covered with a cured resin composition.

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