Resin composition, its products and use thereof

Abstract

This invention relates to resin compositions, articles thereof, and their uses. The resin compositions comprise: (A) 100 parts by weight of maleic anhydride-modified polyolefin; (B) 1-30 parts by weight of alicyclic epoxy-modified siloxane having two or more alicyclic epoxy groups; and (C) 20-100 parts by weight of acrylate monomers, oligomers thereof, or combinations thereof, wherein the acrylate monomers have two or more unsaturated carbon-carbon double bonds. The resin compositions and articles thereof of this invention achieve significant improvements in at least the following properties: volatile organic matter, copper foil tensile strength, dielectric loss coefficient, and Z-axis thermal expansion coefficient. The resin compositions of this invention can be used in the resin filling process for printed circuit boards.

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 is a new technology invented to reduce PCB design size to accommodate component assembly, effectively improving the reliability and manufacturing capabilities of High Density Interconnect (HDI) technology. Simultaneously, resin filling technology solves problems that cannot be addressed by solder mask or lamination filling. For example, filling blind / buried / vias in the inner layers with resin or filling empty areas of thick copper circuits with resin before lamination balances the conflict between controlling the dielectric layer thickness during lamination and the inner layer filling design. For instance, filling vias with resin improves the reliability issues associated with solder mask filling. However, current resin filling processes primarily use resin compositions prepared from traditional epoxy resins combined with calcium carbonate, which have undesirable properties, such as high volatile organic compounds, low copper foil tensile strength, high dielectric loss coefficient, and high Z-axis thermal expansion coefficient, thus failing to meet the requirements of high-frequency, high-speed information transmission printed circuit boards. Summary of the Invention

[0003] The main objective of this invention is to provide a resin composition that can solve at least one of the above-mentioned problems, an article made from the resin composition, and the use of the resin composition in a printed circuit board via filling process, a printed circuit board slot filling process, or a printed circuit board circuit filling process.

[0004] A first aspect of the present invention provides a resin composition comprising:

[0005] (A) 100 parts by weight of maleic anhydride modified polyolefin;

[0006] (B) 1 to 30 parts by weight of an alicyclic epoxy-modified siloxane, wherein the alicyclic epoxy-modified siloxane has two or more alicyclic epoxy groups; and

[0007] (C) 20 to 100 parts by weight of acrylate monomers, oligomers thereof, or combinations thereof, wherein the acrylate monomers have two or more unsaturated carbon-carbon double bonds.

[0008] Preferably, the maleic anhydride-modified polyolefin includes any one or a combination of 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.

[0009] Preferably, the alicyclic epoxy-modified siloxane includes any one or a combination of the alicyclic epoxy-modified siloxane shown in formula (1) and the alicyclic epoxy-modified siloxane shown in formula (3):

[0010]

[0011] In equation (1): R 11 R 12 and R 13 Each is an alkyl group that is C1 to C3, and p is an integer from 1 to 15. There are a total of 2p R groups in formula (1). 12 , where each R 12 Each is independently the same or different; X is the group shown in formula (2):

[0012]

[0013] In equation (3), q represents an integer from 3 to 6, and there are a total of 2q R's in equation (3). 14 , where each R 14 Each is independently identical or different and each independently represents a C1 to C3 alkyl group.

[0014] Where R 15 Each of the above represents an alkyl group from C1 to C3, and X is the group shown in formula (2);

[0015] Furthermore, formula (3) contains at least two groups as shown in formula (2).

[0016] Preferably, the alicyclic epoxy-modified siloxane includes the alicyclic epoxy-modified siloxane shown in formula (3).

[0017] Preferably, the alicyclic epoxy-modified siloxane includes any one or a combination of the alicyclic epoxy-modified siloxane shown in formula (4), the alicyclic epoxy-modified siloxane shown in formula (5), the alicyclic epoxy-modified siloxane shown in formula (6), and the alicyclic epoxy-modified siloxane shown in formula (7):

[0018]

[0019]

[0020] Preferably, the acrylate monomer has two or three acrylate groups.

[0021] Preferably, the acrylate monomer comprises any one or a combination of tricyclodecanediethanol di(meth)acrylate, dioxanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0022] Preferably, the acrylate monomer or its oligomer has a glass transition temperature of 90°C or higher after curing.

[0023] Preferably, the acrylate monomer or its oligomer has a glass transition temperature of 150°C or higher after curing.

[0024] Preferably, the resin composition does not contain organic solvents.

[0025] In one embodiment, the resin composition may further include, as needed, any one or a combination thereof of the following: other polyolefins different from the maleic anhydride-modified polyolefin, polyphenylene ether resin containing unsaturated carbon-carbon double bonds, benzoxazine resin, epoxy resin different from component B, reactive ester, phenolic resin, amine curing agent, polyamide, polyimide, cyanate ester resin, etc.

[0026] In one embodiment, the resin composition may further include, as needed, any one or a combination of: inorganic fillers, flame retardants, curing accelerators, polymerization inhibitors, dyes, surfactants, and toughening agents.

[0027] Preferably, the volatile organic matter content of the resin composition, as measured by the method of IPC-TM-650 2.4.24.6, is less than or equal to 0.63%.

[0028] A second aspect of the present invention provides an article made from the above-described resin composition, the article including, but not limited to, a prepreg, a resin film, a laminate, or a printed circuit board.

[0029] 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.

[0030] Preferably, the article has one or more of the following characteristics:

[0031] The tensile force on the copper foil measured according to the method of IPC-TM-650 2.4.8 is greater than or equal to 4.0 lb / in;

[0032] The dielectric loss coefficient measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0055;

[0033] 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 1.60%.

[0034] A fourth aspect of the present invention provides the use of the above-described resin composition in a resin filling process for printed circuit boards.

[0035] 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, and printed circuit board circuit filling process.

[0036] 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; and / or

[0037] In the printed circuit board filling process, at least one recess of the printed circuit board is filled with a cured product of the resin composition; and / or

[0038] 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.

[0039] The beneficial effects of this invention are:

[0040] The resin composition and its products of the present invention have achieved significant improvements in at least the following properties: volatile organic matter, tensile strength to copper foil, dielectric loss coefficient, and Z-axis thermal expansion coefficient. Detailed Implementation

[0041] 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.

[0042] 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.

[0043] In this invention, "any one or a combination thereof" and "one or more" should be interpreted as "using any one of the listed elements alone" or "using any two of the listed elements in combination" or "using any three or more of the listed elements in combination".

[0044] 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.

[0045] 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".

[0046] In this invention, the numerical value has a precision, which is achieved by rounding up to the nearest whole number.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] In this invention, “parts by weight” should be interpreted as a relative number of parts by weight, which can be any weight unit, such as, but not limited to, kilograms, grams, pounds, etc. For example, 100 parts by weight of maleic anhydride modified polyolefin means that it can be 100 kilograms of maleic anhydride modified polyolefin or 100 pounds of maleic anhydride modified polyolefin.

[0051] In this invention, wt% represents weight (or mass) percentage.

[0052] 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.

[0053] In this invention, the monomer refers to a molecule that can be covalently linked with the same or other molecules to form a polymer.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] As described above, this invention discloses a resin composition comprising the following components:

[0058] (A) 100 parts by weight of maleic anhydride modified polyolefin;

[0059] (B) 1 to 30 parts by weight of an alicyclic epoxy-modified siloxane, wherein the alicyclic epoxy-modified siloxane has two or more alicyclic epoxy groups.

[0060] (C) 20 to 100 parts by weight of acrylate monomers, oligomers thereof, or combinations thereof, wherein the acrylate monomers have two or more unsaturated carbon-carbon double bonds.

[0061] The maleic anhydride-modified polyolefin refers to a polyolefin obtained by modification with maleic anhydride. The modification methods involving maleic anhydride modification can be any chemical modification method 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 polyolefins to generate maleic anhydride-modified polyolefins (i.e., maleic anhydride addition polyolefins are generated). 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 (i.e., maleic anhydride olefin copolymers are generated).

[0062] The types of polyolefins and olefin monomers applicable to the above modification methods are not particularly limited, and can be various polyolefins and olefin monomers known in the art. In other words, maleic anhydride can be used to modify various different polyolefins and olefin monomers to obtain the maleic anhydride-modified polyolefins of the present invention.

[0063] In this invention, 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.

[0064] In this invention, the maleic anhydride-modified polyolefin may be any type of maleic anhydride-modified polyolefin known in the art, including but not limited to any one or a combination of 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.

[0065] The aforementioned maleic anhydride-styrene copolymer can be any type of maleic anhydride-styrene copolymer known in the art, wherein the molar 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, maleic anhydride-styrene copolymers sold by Cray Valley under the trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80, or maleic anhydride-styrene copolymers sold by Polyscope under the trade names C400, C500, C700, and C900.

[0066] In this invention, compared to 100 parts by weight of maleic anhydride-modified polyolefin, the resin composition further includes 1 to 30 parts by weight of an alicyclic epoxy-modified siloxane, wherein the alicyclic epoxy-modified siloxane has two or more alicyclic epoxy groups, such as, but not limited to, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, and 30 parts by weight of the alicyclic epoxy-modified siloxane. Preferably, the alicyclic epoxy-modified siloxane is present in 4 to 30 parts by weight.

[0067] In this invention, the aforementioned "alicyclic epoxy-modified siloxane (having two or more alicyclic epoxy groups)" can also be referred to as "siloxane having two or more alicyclic epoxy groups." The alicyclic epoxy-modified siloxane is a siloxane containing two or more alicyclic epoxy groups and a siloxane skeleton in one molecule. In the alicyclic epoxy groups, the epoxy groups are directly bonded to the alicyclic hydrocarbon. The siloxane skeleton is a siloxane skeleton formed by two or more Si atoms and O atoms connected by covalent bonds. The siloxane skeleton can be a cyclic skeleton, a linear skeleton, a cage-like skeleton, or a ladder-like skeleton. When the siloxane skeleton is a cyclic skeleton, the alicyclic epoxy-modified siloxane (having two or more alicyclic epoxy groups) can be referred to as a cyclic siloxane having two or more alicyclic epoxy groups. When the siloxane skeleton is a linear skeleton, the alicyclic epoxy-modified siloxane (having two or more alicyclic epoxy groups) can be referred to as a linear siloxane having two or more alicyclic epoxy groups.

[0068] In this invention, the aforementioned "alicyclic epoxy modified siloxane (having two or more alicyclic epoxy groups)" can be any type of siloxane having two or more alicyclic epoxy groups known in the art.

[0069] Specific examples of the siloxanes having two or more alicyclic epoxy groups include, but are not limited to, any one or a combination of the alicyclic epoxy-modified siloxanes shown in formula (1) and the alicyclic epoxy-modified siloxanes shown in formula (3), wherein formula (1) is a linear siloxane having two or more alicyclic epoxy groups, and formula (3) is a cyclic siloxane having two or more alicyclic epoxy groups:

[0070]

[0071] In equation (1), R 11 R 12 and R 13 Each is an alkyl group that is C1 to C3, and p is an integer from 1 to 15. There are a total of 2p R groups in formula (1). 12 , where each R 12 They are independently the same or different; for example, when p is 2, there are a total of 4 R in equation (1). 12 Each R 12Each is independent and its structure may be the same or different, where X is the group shown in formula (2):

[0072]

[0073] In equation (3), q represents an integer from 3 to 6, and there are a total of 2q R's in equation (3). 14 , where each R 14 They are independently the same or different. For example, when q is 4, there are a total of 8 R in equation (3). 14 Each R 14 Each is independent and may have the same or different structures, and formula (3) contains at least two groups shown in formula (2).

[0074] In equation (3), R 14 Each independently represents a C1 to C3 alkyl group,

[0075] Among them, R 15 Each of the above represents an alkyl group from C1 to C3, and X is the group shown in formula (2).

[0076] The alicyclic epoxy modified siloxane (having two or more alicyclic epoxy groups) can be any siloxane containing two or more alicyclic epoxy groups and a siloxane skeleton in one molecule, or it can be a mixture of two or more siloxanes containing two or more alicyclic epoxy groups and a siloxane skeleton in one molecule.

[0077] Preferably, the alicyclic epoxy modified siloxane is an alicyclic epoxy modified siloxane containing two or more alicyclic epoxy groups in one molecule and having a cyclic siloxane skeleton.

[0078] Preferably, the alicyclic epoxy-modified siloxane includes the alicyclic epoxy-modified siloxane shown in formula (3).

[0079] Preferably, the alicyclic epoxy-modified siloxane includes any one or a combination of the alicyclic epoxy-modified siloxane shown in formula (4), the alicyclic epoxy-modified siloxane shown in formula (5), the alicyclic epoxy-modified siloxane shown in formula (6), and the alicyclic epoxy-modified siloxane shown in formula (7). The structures of formulas (4) to (7) are as described above.

[0080] In this invention, compared to 100 parts by weight of maleic anhydride-modified polyolefin, the resin composition further comprises 20 to 100 parts by weight of acrylate monomers, oligomers thereof, or combinations thereof, wherein the acrylate monomers have two or more unsaturated carbon-carbon double bonds. For example, but not limited to, a total of 20, 30, 40, 50, 60, 70, 80, 90, or 100 parts by weight of acrylate monomers, oligomers thereof, or combinations thereof, wherein the acrylate monomers have two or more unsaturated carbon-carbon double bonds.

[0081] The acrylate monomers (having two or more unsaturated carbon-carbon double bonds), their oligomers, or combinations thereof can be described as acrylate monomers (having two or more unsaturated carbon-carbon double bonds) and / or their oligomers. Compared to acrylate monomers having only one unsaturated carbon-carbon double bond, the acrylate monomers (having two or more unsaturated carbon-carbon double bonds) of the present invention have a higher crosslinking density, resulting in products with superior heat resistance. In the present invention, the types of acrylate monomers (having two or more unsaturated carbon-carbon double bonds) and their oligomers in the resin composition are not particularly limited. For example, the resin composition may include any one or more acrylate monomers (having two or more unsaturated carbon-carbon double bonds), or the resin composition may include oligomers of any one or more acrylate monomers (having two or more unsaturated carbon-carbon double bonds), or the resin composition may include a mixture of any one or more acrylate monomers (having two or more unsaturated carbon-carbon double bonds) and oligomers of any one or more acrylate monomers (having two or more unsaturated carbon-carbon double bonds).

[0082] The aforementioned acrylate monomer (having two or more unsaturated carbon-carbon double bonds) is preferably a compound having two or more acrylate groups (e.g., two, three, four, five, six, etc.). More preferably, the acrylate monomer (having two or more unsaturated carbon-carbon double bonds) is an acrylate monomer having two or three acrylate groups.

[0083] In this invention, the aforementioned "acrylate monomer (having two or more unsaturated carbon-carbon double bonds)" can also be referred to as "bifunctional or higher acrylate monomer". The bifunctional or higher acrylate monomer and / or its oligomers can be any type of bifunctional or higher acrylate monomer and / or oligomers obtained by polymerizing bifunctional or higher acrylate monomers known in the art. The bifunctional or higher acrylate monomer and / or its oligomers include, but are not limited to, any one or a combination of: bifunctional 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 bifunctional or higher acrylate monomers and their oligomers can be self-made or purchased from Sartamomer.

[0084] The aforementioned acrylate monomers (having two or more unsaturated carbon-carbon double bonds) and their oligomers are liquid at room temperature. The relative molecular mass (Mr) of the aforementioned acrylate monomers (having two or more unsaturated carbon-carbon double bonds) is less than or equal to 2000, and the weight average molecular weight (Mw) of the oligomers obtained by polymerizing the aforementioned acrylate monomers (having two or more unsaturated carbon-carbon double bonds) is less than or equal to 2000.

[0085] The aforementioned acrylate monomers (having two or more unsaturated carbon-carbon double bonds) and / or their oligomers include any one or a combination of the following: 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.

[0086] The acrylate monomer (having two or more unsaturated carbon-carbon double bonds) and its oligomer, after curing, have a glass transition temperature greater than or equal to 90°C, i.e., the cured product of the acrylate monomer (having two or more unsaturated carbon-carbon double bonds) and its oligomer has a glass transition temperature greater than or equal to 90°C. Preferably, the cured product of the acrylate monomer (having two or more unsaturated carbon-carbon double bonds) and its oligomer has a glass transition temperature greater than or equal to 150°C. The glass transition temperature of the cured product can be measured using the method described in IPC-TM-650 2.4.24.5 (2012) with reference to thermomechanical analysis (TMA).

[0087] In this invention, the acrylate monomer (having two or more unsaturated carbon-carbon double bonds) and its oligomers not only participate in crosslinking reactions but also dissolve and dilute 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. Preferably, the resin composition does not contain organic solvents. The resin composition does not contain any one or a combination of alcohols, ethers, ketones, aromatic hydrocarbons, acetates, and amides. The resin composition does not contain any one or a combination of the following organic solvents: 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, etc., or mixtures thereof.

[0088] In addition to the aforementioned components, the resin composition of the present invention may, as needed, include any one or a combination thereof of other polyolefins different from the maleic anhydride-modified polyolefin, polyphenylene ether resins containing unsaturated carbon-carbon double bonds, benzoxazine resins, epoxy resins different from component (B), reactive esters, phenolic resins, amine curing agents, polyamides, polyimides, and cyanate ester resins.

[0089] In the resin composition of the present invention, the amount of other polyolefins, polyphenylene ether resins containing unsaturated carbon-carbon double bonds, benzoxazine resins, epoxy resins different from component B, reactive esters, phenolic resins, amine curing agents, polyamides, polyimides, or cyanate ester resins relative to 100 parts by weight of the maleic anhydride-modified polyolefin is not particularly limited, and may be from 1 part by weight to 100 parts by weight, for example, but not limited to 1 part by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 50 parts by weight, or 100 parts by weight. The amount of amine curing agent relative to 100 parts by weight of the maleic anhydride-modified polyolefin is also not particularly limited, and may be from 1 to 15 parts by weight, for example, but not limited to 1 part by weight, 4 parts by weight, 7.5 parts by weight, 12 parts by weight, or 15 parts by weight.

[0090] The resin composition of the present invention may also include other polyolefins different from maleic anhydride-modified polyolefins. In this invention, the types of other polyolefins are not particularly limited, and can be any type of polyolefin known in the art, and can be any one or more commercially available products, homemade products, or combinations thereof. Other polyolefins suitable for the present invention 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.

[0091] 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.

[0092] In this invention, there are no particular limitations on the polyphenylene ether resin containing unsaturated carbon-carbon double bonds that are applicable to this invention. It can be any type of polyphenylene ether resin containing unsaturated carbon-carbon double bonds 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 any one or combination of vinyl benzyl polyphenylene ether resin, (meth)acryloyloxy polyphenylene ether resin, vinyl polyphenylene ether resin, and allyl polyphenylene ether resin.

[0093] 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.

[0094] 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 Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Company), vinyl benzyl polyphenylene ether resins with a number average molecular weight of about 2400 to 2800 (e.g., vinyl benzyl bisphenol A polyphenylene ether resin), (meth)acryloyloxy polyphenylene ether resins with a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic Company), vinyl polyphenylene ether resins with a number average molecular weight of about 2200 to 3000, or combinations thereof. The vinyl polyphenylene ether 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 resin includes, but is not limited to, vinyl benzyl biphenyl polyphenylene ether resin, vinyl benzyl bisphenol A polyphenylene ether resin, or combinations thereof.

[0095] The benzoxazine resin may be any type of benzoxazine resin known in the art. 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 products include, for example, Huntsman's trade names LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8298 (phenolphthalein type benzoxazine resin), LZ-8280 (bisphenol F type benzoxazine resin), LZ-8290 (bisphenol A type benzoxazine resin), or Kolon Industries' trade names KZH-5031 (vinyl 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.

[0096] The epoxy resin different from component (B) can be any type of epoxy resin known in the art. From the perspective of improving the heat resistance of the resin composition, the epoxy resin different from component (B) includes, but is not limited to, any one or a combination thereof, such as 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), 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-cresolnovolac 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 phenolnovolac epoxy resin, DOPO-HQ-containing o-cresolnovolac epoxy resin, and DOPO-HQ-containing bisphenol-A novolac epoxy resin, and is not limited thereto.

[0097] The active esters suitable for the resin compositions described in this invention can be various active polyester resins 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, such as, but not limited to, active polyester resins produced by Dai Nippon Ink Chemical under the trade names HPC-8000, HPC-8150, or HPC-8800.

[0098] 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.

[0099] In this invention, the amine curing agent can be any type of amine curing agent known in the art. Specific examples include, but are not limited to, at least one or a combination of diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfide, and dicyandiamide.

[0100] In this invention, the polyamide can be any type of polyamide known in the art. Specific examples include, but are not limited to, various commercially available polyamide resin products.

[0101] In this invention, the polyimide can be any type of polyimide known in the art. Specific examples include, but are not limited to, various commercially available polyimide resin products.

[0102] 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. Cyanate ester resins can be those produced by Arxada under trade names such as PrimasetPT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL-950S, HTL-300, CE-320, LVT-50, and LeCy.

[0103] In addition to the aforementioned components, the resin composition of the present invention may also include, as needed, any one or a combination of inorganic fillers, flame retardants, curing accelerators, polymerization inhibitors, dyes, surfactants, and toughening agents.

[0104] In this invention, the inorganic filler can be any type of inorganic filler known in the art, including but not limited to: silica, alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, barium titanate, lead titanate, strontium titanate, calcium titanate, magnesium titanate, barium zirconate, lead zirconate, magnesium zirconate, lead zirconate titanate, zinc molybdate, calcium molybdate, magnesium molybdate, ammonium molybdate, zinc molybdate-modified talc, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, zirconium tungstate, litharge, calcined kaolin, or combinations thereof. Furthermore, the inorganic filler can be spherical (including solid or hollow spheres), fibrous, plate-like, granular, flake-like, or needle-like, and can be selectively pretreated with a silane coupling agent. Furthermore, the color of the inorganic filler is not particularly limited, and it can be various colors such as 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., but is not limited thereto. Relative to 100 parts by weight of the maleic anhydride-modified polyolefin, the resin composition of the present invention may further include 10 parts by weight to 500 parts by weight of the inorganic filler, preferably 50 parts by weight to 400 parts by weight of the inorganic filler, more preferably 150 parts by weight to 350 parts by weight of the inorganic filler, but is not limited thereto.

[0105] In this invention, the flame retardant can 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 methylphosphonate (DMMP), and resorcinol bis(dixylenyl)phosphate. phosphate), RDXP (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 tri-hydroxyethyl isocyanate, aluminum phosphonates (such as OP-930, OP-935, etc.) or combinations thereof.

[0106] 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 a flame retardant, preferably 1 to 50 parts by weight, but not limited thereto, in addition to 100 parts by weight of the maleic anhydride-modified polyolefin.

[0107] In this 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, ethyltriphenylphosphonium 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 octanoate and cobalt octanoate. 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 (25B), 2,5-dimethyl-2,5-ditert-butylperoxy-3-hexyne (DTBP), and bis(tert-butylperoxyisopropyl)benzene (BIBP) or combinations thereof. Relative to 100 parts by weight of the maleic anhydride-modified polyolefin, 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 1 part by weight to 10 parts by weight of a curing accelerator, but is not limited thereto.

[0108] In this 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 with 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. Relative to 100 parts by weight of the maleic anhydride-modified polyolefin, the resin composition of the present invention may further include 0.001 parts by weight to 20 parts by weight of a polymerization inhibitor, preferably 0.001 parts by weight to 10 parts by weight of a polymerization inhibitor, but is not limited thereto.

[0109] In this invention, the dyeing agent may include, but is not limited to, dyes or pigments. The resin composition of this invention may further include 0.001 to 10 parts by weight of the dyeing agent, preferably 0.01 to 5 parts by weight, but not limited thereto, relative to 100 parts by weight of the maleic anhydride-modified polyolefin.

[0110] The type of surfactant used in the resin composition of the present invention is not particularly limited. The main function of adding surfactant 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, but is not limited thereto, relative to 100 parts by weight of the maleic anhydride-modified polyolefin.

[0111] In this invention, the main function of adding a toughening agent is to improve the toughness of the resin composition. Suitable toughening agents for this 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 the maleic anhydride-modified polyolefin, the resin composition of this 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.

[0112] The aforementioned resin composition can be made into various articles, such as components used in various electronic products, including but not limited to prepregs, resin films, laminates or printed circuit boards.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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 layer 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.

[0117] 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.

[0118] The present invention also provides an article comprising a cured resin obtained by curing (C-stage) the resin composition, wherein the curing is performed by a heating process. The applicable curing temperature in the heating process is, for example, between 150°C and 250°C, preferably between 170°C and 200°C, and the curing time is between 60 and 240 minutes, preferably between 60 and 180 minutes.

[0119] 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.

[0120] 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.

[0121] The present 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, one or more of the following: PCB via filling process, PCB slot filling process, and PCB circuit filling process. For example, the resin composition can be applied to any one of the aforementioned processes, any two of the aforementioned processes, or all three of the aforementioned processes simultaneously.

[0122] This invention also provides the use 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 processes known in the art are performed. Specifically, at least one hole of the printed circuit board is filled with the cured resin composition, and then the printed circuit board is subjected to various subsequent circuit board processing processes known in the art.

[0123] This invention also provides a use 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 ​​a 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 in the printed circuit board is filled with a cured product of the resin composition, and then the printed circuit board is subjected to various subsequent circuit board processing techniques known in the art. The groove walls may be electroplated or unplated.

[0124] This invention also provides the use 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, whereby the resin composition of this invention is filled into circuit empty areas (i.e., areas without circuits) and completely cured before various subsequent circuit board processing processes 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 before the printed circuit board is subjected to various subsequent circuit board processing processes known in the art.

[0125] The resin compositions disclosed in this invention, or various articles containing resin cured products prepared therefrom, preferably have one or more of the following characteristics:

[0126] The volatile organic matter content of the resin composition, as determined by the method of IPC-TM-650 2.4.24.6, is less than or equal to 0.63%, for example, between 0.17% and 0.63%, or for example, between 0.17% and 0.55%.

[0127] The tensile strength to the copper foil measured according to the method of IPC-TM-650 2.4.8 is greater than or equal to 4.0 lb / in, for example, between 4.0 lb / in and 5.3 lb / in;

[0128] The dielectric loss coefficient measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0055, for example, between 0.0044 and 0.0055;

[0129] 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 1.60%, for example, between 1.10% and 1.60%, or between 1.10% and 1.55%.

[0130] The tin-floating crack rate is between 0% and 10%, as measured by the method of IPC-TM-650 2.4.13.1, for example, the tin-floating crack rate is 0%.

[0131] 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 5, and were further prepared into various test samples.

[0132] The chemical raw materials used in the embodiments and comparative examples of the present invention are as follows:

[0133] Ricon 131MA5: Maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0134] Ricon 130MA8: Maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0135] Ricon 130MA13: Maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0136] Ricon 131MA10: Maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0137] Ricon 156MA17: Maleic anhydride addition polybutadiene, purchased from Cray Valley.

[0138] Ricon 184MA6: Maleic anhydride addition styrene-butadiene copolymer, purchased from Cray Valley.

[0139] EF80: Maleic anhydride-styrene copolymer, purchased from Cray Valley.

[0140] SR833S: Tricyclodecanediethanol diacrylate, with the following structural formula, purchased from Sartomer, and its cured product has a glass transition temperature of approximately 180°C.

[0141]

[0142] 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.

[0143]

[0144] 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.

[0145] SR295 NS: Pentaerythritol tetraacrylate, with the following structural formula, purchased from Sartomer, whose cured product has a glass transition temperature of approximately 103°C.

[0146]

[0147] SR399 NS: Dipentaerythritol pentaacrylate, with the following structural formula, purchased from Sartomer, whose cured product has a glass transition temperature of approximately 90°C.

[0148]

[0149] DPHA: Dipentaerythritol hexaacrylate, with the following structural formula, purchased from Sartomer, and its cured product has a glass transition temperature of approximately 90°C.

[0150]

[0151] G1726: Hydrogenated styrene-butadiene-styrene block copolymer, purchased from Kraton.

[0152] Ricon 130: Polybutadiene, purchased from Cray Valley.

[0153] SBS-C: Styrene-butadiene block copolymer, specifically styrene-butadiene-styrene triblock copolymer, purchased from Japan Soda.

[0154] DCP: dicumyl peroxide, purchased from Japanese oils and fats.

[0155] X-40-2669, purchased from Shin-Etsu Silicone Co., Ltd., has the structure shown in formula (4).

[0156] X-40-2678, purchased from Shin-Etsu Silicone Co., Ltd., has the structure shown in formula (5).

[0157] KR470, purchased from Shin-Etsu Silicones, has the structure shown in formula (6).

[0158] YL9029, purchased from Mitsubishi Chemical, has the structure shown in formula (7).

[0159] X-22-173BX: Non-alicyclic epoxy-modified linear siloxane with an epoxy equivalent of 2500 g / mol, purchased from Shin-Yue Chemical.

[0160] The structure of the KBM-303 is as follows:

[0161]

[0162] Chemically synthesized spherical silica (spherical SiO2): Median particle size D 50 The spherical silica particles, approximately 1.5 ± 0.5 μm in size, were prepared by microemulsion and treated with silane coupling agent. They were purchased from Jinyi Inorganic New Materials Co., Ltd.

[0163] 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 5:

[0164] Table 1. Composition (parts by weight) and property test results of the resin compositions of Examples E1 to E6.

[0165]

[0166]

[0167] Table 2. Composition (parts by weight) and property test results of the resin compositions of Examples E7 to E12.

[0168]

[0169] Table 3. Composition (parts by weight) and property test results of the resin compositions of Examples E13 to E19

[0170]

[0171] Table 4. Composition (parts by weight) and property test results of resin compositions of comparative examples C1 to C5

[0172]

[0173]

[0174] Table 5. Composition (parts by weight) and property test results of the comparative examples C6-C10 resin compositions.

[0175]

[0176]

[0177] 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.

[0178] 1. Adhesives containing inorganic fillers

[0179] According to the dosages in Tables 1 to 5, 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 referred to as an adhesive containing inorganic fillers.

[0180] 2. Copper foil-containing resin cured products

[0181] 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 ounce HVLP copper foil). Perform pressure-curing (C-Stage) under high temperature, high pressure, and vacuum conditions. The curing temperature is between 170°C and 180°C, the curing time is between 60 and 90 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.

[0182] 3. Does not contain copper foil resin cured products

[0183] 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.

[0184] For the aforementioned samples to be tested, the test methods and their characteristic analysis items are described below:

[0185] 1. Percent of volatile organic compounds

[0186] 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.

[0187] 2. Peeling strength (P / S) of copper foil

[0188] 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.

[0189] 3. Dissipation factor (Df)

[0190] 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).

[0191] 4. Z-axis thermal expansion coefficient (percent of thermal expansion, z-axis, Z-PTE)

[0192] 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 1.6%, and the difference in the measured value of the Z-axis thermal expansion coefficient was greater than or equal to 0.02%, 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).

[0193] 5. Solder floating crack rate

[0194] (1) Preparation of via-filled copper clad laminate

[0195] 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 or comparative examples 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.

[0196] (2) Evaluation of substrate preparation

[0197] 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.

[0198] (3) Determination of the rate of tin-bleached cracks

[0199] 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 of ​​the through-hole 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 a stronger bonding force between the resin components and a higher yield of the plugging process.

[0200] Based on the comprehensive reference to the characteristic test results in Tables 1 to 5, the following phenomena can be clearly observed:

[0201] The resin compositions of Examples E2 to E19 contain 4 to 30 parts by weight of siloxane having two or more alicyclic epoxy groups, while the resin composition of Example E1 contains 1 part by weight of siloxane having two or more alicyclic epoxy groups. The articles prepared from the resin compositions of Examples E2 to E19 show a significant improvement in the rate of tin bleaching cracks compared to the articles prepared from the resin composition of Example E1.

[0202] The resin compositions of Examples E1-E4 and E6-E19 contain alicyclic epoxy-modified siloxanes that contain two or more alicyclic epoxy groups per molecule and have a cyclic skeleton. The resin composition of Example E5 contains alicyclic epoxy-modified siloxanes that contain two alicyclic epoxy groups per molecule and have a linear skeleton. The articles prepared from the resin compositions of Examples E1-E4 and E6-E19 show a significant improvement in volatile organic matter content compared to the articles prepared from the resin composition of Example E5.

[0203] Comparing Examples E1 to E19 with Comparative Examples C1 to C2, it can be seen that: compared to adding 1 to 30 parts by weight of a siloxane having two or more alicyclic epoxy groups, when the amount of the siloxane having two or more alicyclic epoxy groups used is not in the range of 1 to 30 parts by weight, the articles made from the resin composition show a significant deterioration in the rate of tin bleaching cracks.

[0204] Comparing Examples E1 to E19 with Comparative Examples C3 to C4, it can be seen that: compared to adding 20 to 100 parts by weight of acrylate monomers (having two or more unsaturated carbon-carbon double bonds) and / or their oligomers, when the amount of acrylate monomers (having two or more unsaturated carbon-carbon double bonds) and / or their oligomers used is not in the range of 20 to 100 parts by weight, the articles made from this resin composition show a significant deterioration in terms of Z-axis thermal expansion coefficient and tin-free crack rate.

[0205] Comparing Examples E1 to E19 with Comparative Example C5, it can be seen that when maleic anhydride-modified polyolefin is not added to the resin composition, the articles made from the resin composition show significant deterioration in terms of volatile organic matter, copper foil tensile strength, dielectric loss coefficient, and tin bleaching crack rate, compared to the addition of 100 parts by weight of maleic anhydride-modified polyolefin.

[0206] Examples E1 to E19 use maleic anhydride-modified polyolefins, siloxanes having two or more alicyclic epoxy groups, and acrylate monomers, their oligomers, or combinations thereof (acrylate monomers having two or more unsaturated carbon-carbon double bonds). Compared to Comparative Examples C6 and C7 (C6 with the addition of the non-alicyclic epoxy group-containing siloxane X-22-173BX, and C7 with the addition of the monofunctional alicyclic epoxy group-containing siloxane KBM-303) which use maleic anhydride-modified polyolefins, other siloxanes different from those having two or more alicyclic epoxy groups, and acrylate monomers, their oligomers, or combinations thereof (acrylate monomers having two or more unsaturated carbon-carbon double bonds), articles made from the resin compositions of Examples E1 to E19 show significant improvements in at least the following properties: volatile organic matter, tensile strength to copper foil, and Z-axis thermal expansion coefficient.

[0207] Examples E1-E19 used maleic anhydride-modified polyolefins, siloxanes having two or more alicyclic epoxy groups, and acrylate monomers, their oligomers, or combinations thereof (the acrylate monomers having two or more unsaturated carbon-carbon double bonds). Compared to Comparative Examples C8 and C10 (C8 with added polybutadiene Ricon 130, C10 with added styrene-butadiene-styrene triblock copolymer SBS-C) which used other polyolefins different from maleic anhydride-modified polyolefins, siloxanes having two or more alicyclic epoxy groups, and acrylate monomers, their oligomers, or combinations thereof (the acrylate monomers having two or more unsaturated carbon-carbon double bonds), the articles made from the resin compositions of Examples E1-E19 showed significant improvements in at least the following properties: volatile organic matter, tensile strength to copper foil, and Z-axis thermal expansion coefficient. Furthermore, Comparative Example C9 added hydrogenated styrene-butadiene-styrene block copolymer G1726. Because G1726 could not be completely dissolved in the absence of solvents, a homogeneous test sample could not be obtained.

Claims

1. A resin composition, characterized in that, The resin composition comprises: (A) 100 parts by weight of maleic anhydride modified polyolefin; (B) 1 to 30 parts by weight of an alicyclic epoxy-modified siloxane, wherein the alicyclic epoxy-modified siloxane has two or more alicyclic epoxy groups; and (C) 20 to 100 parts by weight of acrylate monomers, oligomers thereof, or combinations thereof, wherein the acrylate monomers have two or more unsaturated carbon-carbon double bonds.

2. The resin composition according to claim 1, characterized in that, The maleic anhydride-modified polyolefins include any one or a combination of 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.

3. The resin composition according to claim 1, characterized in that, The alicyclic epoxy-modified siloxane includes any one or a combination of the alicyclic epoxy-modified siloxane shown in formula (1) and the alicyclic epoxy-modified siloxane shown in formula (3): In equation (1): R 11 R 12 and R 13 Each is an alkyl group that is C1 to C3, and p is an integer from 1 to 15. There are a total of 2p R groups in formula (1). 12 , where each R 12 Each is independently the same or different; X is the group shown in formula (2): In equation (3), q represents an integer from 3 to 6, and there are a total of 2q R's in equation (3). 14 , where each R 14 Each is independently the same or different and each independently represents a C1 to C3 alkyl group. Where R 15 Each of the above represents an alkyl group from C1 to C3, and X is the group shown in formula (2); Furthermore, formula (3) contains at least two groups as shown in formula (2).

4. The resin composition according to claim 3, characterized in that, The alicyclic epoxy-modified siloxane includes the alicyclic epoxy-modified siloxane shown in formula (3).

5. The resin composition according to claim 1, characterized in that, The alicyclic epoxy-modified siloxane includes any one or a combination of the alicyclic epoxy-modified siloxane shown in formula (4), the alicyclic epoxy-modified siloxane shown in formula (5), the alicyclic epoxy-modified siloxane shown in formula (6), and the alicyclic epoxy-modified siloxane shown in formula (7):

6. The resin composition according to claim 1, characterized in that, The acrylate monomer has two or three acrylate groups.

7. The resin composition according to claim 1, characterized in that, The acrylate monomers include any one or a combination of tricyclodecanediethanol di(meth)acrylate, dioxanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

8. The resin composition according to claim 1, characterized in that, The acrylate monomer or its oligomer, after curing, has a glass transition temperature greater than or equal to 90°C.

9. The resin composition according to claim 1, characterized in that, The acrylate monomer or its oligomer, after curing, has a glass transition temperature greater than or equal to 150°C.

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

11. The resin composition according to claim 1, characterized in that, The resin composition further includes any one or a combination thereof of other polyolefins different from the maleic anhydride-modified polyolefin, polyphenylene ether resin containing unsaturated carbon-carbon double bonds, benzoxazine resin, epoxy resin different from component (B), reactive ester, phenolic resin, amine curing agent, polyamide, polyimide, and cyanate ester resin.

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

13. The resin composition according to claim 1, characterized in that, The volatile organic matter content of the resin composition, as determined by the method of IPC-TM-6502.4.24.6, is less than or equal to 0.63%.

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

15. An article made from the resin composition according to any one of claims 1 to 13, characterized in that, The article comprises a cured resin obtained by curing the resin composition.

16. The article of claim 15, characterized in that, The article has one or more of the following characteristics: The tensile force on the copper foil measured according to the method of IPC-TM-650 2.4.8 is greater than or equal to 4.0 lb / in; The dielectric loss coefficient measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0055; 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 1.60%.

17. Use of a resin composition according to any one of claims 1 to 13 in a resin filling process for printed circuit boards.

18. The use according to claim 17, 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, and printed circuit board circuit filling process.

19. The use according to claim 18, characterized in that, In the printed circuit board via-filling process, at least one via 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 recess 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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