TWI869139B - Resin composition and article made therefrom - Google Patents

Abstract

A resin composition is disclosed, comprising: 100 parts by weight of an unsaturated carbon-carbon double bond-containing polyphenylene ether resin and 10 parts by weight to 60 parts by weight of a phosphorus-containing polyolefine resin. The phosphorus-containing polyolefine resin consists of (a) structural unit, (b) structural unit and (d) structural unit, and/or consists of (a) structural unit, (b) structural unit, (c) structural unit and (d) structural unit. The (a) structural unit comprises any one of (a1) structural unit and (a2) structural unit or a combination thereof. The (b) structural unit comprises any one of (b1) structural unit and (b2) structural unit or a combination thereof. The (d) structural unit comprises any one of (d1) structural unit and (d2) structural unit and (d3) structural unit or a combination thereof. An article made from the resin composition is also disclosed, that has an improvement in at least one of the following properties: stickiness resistance, glass transition temperature, dielectric properties, flame retardancy, thermal resistance after moisture absorption, appearance of the laminate, alkali resistance. (a1); (a2); (b1); (b2); (c); (d1); (d2);

Description

Resin composition and its products

The present invention relates to a resin composition and articles made therefrom, and in particular to a resin composition used for prepregs, resin films, laminates and printed circuit boards.

With the rapid development of electronic products such as mobile communication technology, servers, and cloud storage, resin materials suitable for high-speed information transmission have gradually become the main development direction of substrates. Copper foil substrate materials are required to have high glass transition temperature (or glass transition temperature), low dielectric properties, high flame retardancy, excellent moisture absorption and heat resistance, better substrate appearance, alkali resistance, and prepreg adhesion resistance to meet the use requirements of high-speed information transmission.

However, existing high-speed materials mainly use hydrocarbon resins such as ordinary polyolefins as the main body, combined with traditional additive flame retardants. The substrates made using this type of system resin composition cannot meet the above requirements at the same time. Therefore, it is necessary to develop materials suitable for printed circuit boards (PCBs) with better comprehensive properties.

In view of the above technical problems existing in the prior art, especially the problem that the existing materials cannot meet one or more of the above performance requirements, the main purpose of the present invention is to provide a resin composition that can solve at least one of the above technical problems, as well as prepregs, resin films, laminates, printed circuit boards and other products made therefrom.

The resin composition of the present invention comprises: (A) 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds; and (B) 10 to 60 parts by weight of a phosphorus-containing polyolefin resin, wherein the phosphorus-containing polyolefin resin is composed of (a) a structural unit, (b) a structural unit and (d) a structural unit, and/or (a) a structural unit, (b) a structural unit, (c) a structural unit and (d) a structural unit. The structure unit (a) comprises any one of the structure units (a1) and (a2) or a combination thereof, the structure unit (b) comprises any one of the structure units (b1) and (b2) or a combination thereof, the structure unit (d) comprises any one of the structure units (d1), (d2) and (d3) or a combination thereof, wherein R in (d3) is a hydrogen atom or a C ₁ to C ₃ alkyl group,

Among them, * represents the bonding position between structural units.

In an exemplary embodiment, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes any one of vinylbenzyl polyphenylene ether resin, (meth)acryl polyphenylene ether resin, vinyl polyphenylene ether resin or a combination thereof.

In an exemplary embodiment, the phosphorus content of the phosphorus-containing polyolefin resin is 2 to 10 weight percent (wt%).

In an exemplary embodiment, the phosphorus content of the phosphorus-containing polyolefin resin is 2.3 to 3.7 weight percent (wt%).

In an exemplary embodiment, the phosphorus-containing polyolefin resin includes any one of the phosphorus-containing polyolefin resins shown in formula (1), the phosphorus-containing polyolefin resins shown in formula (2), the phosphorus-containing polyolefin resins shown in formula (3), the phosphorus-containing polyolefin resins shown in formula (4), the phosphorus-containing polyolefin resins shown in formula (5), the phosphorus-containing polyolefin resins shown in formula (6), the phosphorus-containing polyolefin resins shown in formula (7), the phosphorus-containing polyolefin resins shown in formula (8), the phosphorus-containing polyolefin resins shown in formula (9), or the phosphorus-containing polyolefin resins shown in formula (10), or a combination thereof.

In formulae (1) to (10), * represents the bonding position between structural units, p, m, n, q, y or t are each independently p=1 to 200, m=2 to 200, n=10 to 400, q=1 to 100, y=1 to 50, t=1 to 50, and R is each independently a hydrogen atom or a C ₁ to C ₃ alkyl group.

In an exemplary embodiment, the resin composition further includes a crosslinking agent containing unsaturated carbon-carbon double bonds, and the crosslinking agent containing unsaturated carbon-carbon double bonds is any one of bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate (also known as triallyl isocyanurate), triallyl cyanurate (also known as triallyl cyanurate), trivinylcyclohexane, diallylbisphenol A, butadiene, decadiene, octadiene, and difunctional or higher acrylates or a combination thereof.

樹脂(又稱苯并噁嗪樹脂)、環氧樹脂、有機矽樹脂、氰酸酯樹脂、活性酯、酚樹脂、胺類固化劑、苯乙烯馬來酸酐、聚醯胺、聚醯亞胺中的任一種或其組合。 In an exemplary embodiment, the resin composition further includes a phosphorus-free polyolefin, a maleimide resin, a benzo

Any one of resin (also known as benzoxazine resin), epoxy resin, organic silicone resin, cyanate resin, active ester, phenol resin, amine curing agent, styrene maleic anhydride, polyamide, polyimide or a combination thereof.

In an exemplary embodiment, the resin composition further includes any one of a flame retardant, a hardening accelerator, a polymerization inhibitor, an inorganic filler, a solvent, a silane coupling agent, a surfactant, a dye, and a toughening agent, or a combination thereof.

The present invention also provides products made from the above-mentioned resin composition, wherein the products include prepregs, resin films, laminates or printed circuit boards.

In an exemplary embodiment, the product has one or more of the following characteristics: In an exemplary embodiment, after the semi-cured sheet is vacuum packaged, it is placed in a 40°C environment for 2 hours and then tested without sticking or powdering. The dielectric constant measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 3.40, the dielectric loss measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0040, the glass transition temperature measured according to the method of IPC-TM-650 2.4.24.4 is greater than or equal to 200°C, the flame retardancy level measured according to the method of UL94 specification is V0, and the flame retardancy level measured according to IPC-TM-650 2.6.16.1 and IPC-TM-650 The product was tested for moisture absorption and heat resistance using method 2.4.23, and no board bursting occurred. The alkali resistance of the substrate measured by the alkali resistance test was greater than or equal to 10 minutes. Visual inspection showed that the substrate had no streaks or yellow spots.

The product made of the resin composition in the present invention has improved properties in one or more of the following: anti-adhesion, glass transition temperature, dielectric properties, flame retardancy, moisture absorption and heat resistance, substrate appearance, alkali resistance, etc.

The terms used in this article (including technical and scientific terms) have the same meaning as those generally understood by people with ordinary knowledge in the relevant fields. If otherwise specified, the terms defined in this article shall prevail.

The words "include", "include", "contain", and "have" used in this article are all open conjunctions (i.e., they may also contain other elements not listed). The words "consisting of" and "consisting of" used in this article are all closed conjunctions.

The ranges of values used in this article include all possible subranges and all individual values (including fractions and integers) within the range.

The numerical values used in this article include all numerical ranges that are equal to the numerical value after rounding to the number of significant digits of the numerical value.

It should be understood that each member of the Markush group may be used to describe the present invention individually and/or in combination.

The polymer used in this article refers to the product formed by the polymerization reaction of monomers. The polymer may include homopolymers (also known as self-polymers), copolymers, prepolymers, etc., but the present invention is not limited thereto. Homopolymers refer to polymers polymerized from one monomer. Copolymers refer to polymers polymerized from two or more monomers. Copolymers include random copolymers (also known as random copolymers) (structures such as -AABABBBAAABBA-), alternating copolymers (structures such as -ABABABAB-), graft copolymers (structures such as -AA(A-BBBB)AA(A-BBBB)AAA-) and block copolymers (structures such as -AAAAA-BBBBBB-AAAAA-), etc. For example, the styrene-butadiene copolymer in this application may include styrene-butadiene random copolymers, styrene-butadiene alternating copolymers, styrene-butadiene graft copolymers or styrene-butadiene block copolymers. Prepolymer refers to a polymer with a lower molecular weight between the monomer and the final polymer, and the prepolymer contains reactive functional groups that can further undergo polymerization to obtain a completely cross-linked or hardened product with a higher molecular weight. Polymers of course include oligomers, but are not limited to them. Oligomers, also known as low polymers, are polymers composed of 2 to 20 repeating units, usually 2 to 5 repeating units.

The "resin" used in this article may include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and polymers thereof, and the present invention is not limited thereto.

The modified products used in this article include products obtained by modifying the reactive functional groups of each resin, products obtained by prepolymerization of each resin with other resins, products obtained by crosslinking each resin with other resins, products obtained by copolymerization of each resin with other resins, etc.

The unsaturated bond used in this article refers to a reactive unsaturated bond, such as an unsaturated carbon-carbon double bond that can undergo a cross-linking reaction with other functional groups, but the present invention is not limited thereto.

The unsaturated carbon-carbon double bond used in this article preferably includes vinyl, vinylbenzyl, (meth)acryl, allyl or a combination thereof, but the present invention is not limited thereto. Vinyl includes vinyl and vinylidene. (Meth)acryl includes acryl and methacryl.

The alkyl, alkenyl, and monomers used in this article include their various isomers. For example, propyl includes n-propyl and isopropyl.

The weight parts used in this article represent the number of parts by weight, which can be any weight unit, such as kilograms, grams, pounds, etc., but the present invention is not limited to this. For example, 100 weight parts of polyphenylene ether resin containing unsaturated carbon-carbon double bonds can represent 100 kilograms of polyphenylene ether resin containing unsaturated carbon-carbon double bonds or 100 pounds of polyphenylene ether resin containing unsaturated carbon-carbon double bonds.

The wt% used in this article refers to weight (or mass) percentage.

As mentioned above, the present invention mainly discloses a resin composition, which includes the following components: (A) 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds; and (B) 10 to 60 parts by weight of a phosphorus-containing polyolefin resin, wherein the phosphorus-containing polyolefin resin is composed of (a) a structural unit, (b) a structural unit and (d) a structural unit, and/or (a) a structural unit, (b) a structural unit, (c) a structural unit (a) structural unit comprises any one of (a1) structural unit and (a2) structural unit or a combination thereof, (b) structural unit comprises any one of (b1) structural unit and (b2) structural unit or a combination thereof, (d) structural unit comprises any one of (d1) structural unit, (d2) structural unit and (d3) structural unit or a combination thereof, in (d3) R is a hydrogen atom or a _C1 to C3 _alkyl group, (wherein * represents the bonding position between the structural units).

In the present invention, for example, in an exemplary embodiment, the resin composition of the present invention includes 10 to 60 parts by weight of phosphorus-containing polyolefin resin, such as 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight or 60 parts by weight of phosphorus-containing polyolefin resin, compared to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, but the present invention is not limited thereto.

In the present invention, the phosphorus-containing polyolefin resin may be composed of (a) structural units, (b) structural units and (d) structural units, or may be composed of (a) structural units, (b) structural units, (c) structural units and (d) structural units. The phosphorus-containing polyolefin resin may also be composed of (a) structural units, (b) structural units and (d) structural units and composed of (a) structural units, (b) structural units, (c) structural units and (d) structural units. The phosphorus-containing polyolefin resin is composed of (a) structural unit, (b) structural unit and (d) structural unit, and can be a single phosphorus-containing polyolefin resin composed of (a) structural unit, (b) structural unit and (d) structural unit, or a mixture of multiple phosphorus-containing polyolefin resins composed of (a) structural unit, (b) structural unit and (d) structural unit; the phosphorus-containing polyolefin resin is composed of (a) structural unit, (b) structural unit and (d) structural unit. The (a) structural unit, (b) structural unit, (c) structural unit and (d) structural unit can be a phosphorus-containing polyolefin resin composed of (a) structural unit, (b) structural unit, (c) structural unit and (d) structural unit, or a mixture of multiple phosphorus-containing polyolefin resins composed of (a) structural unit, (b) structural unit, (c) structural unit and (d) structural unit. The phosphorus-containing polyolefin resin may also be composed of (a) structural unit, (b) structural unit and (d) structural unit and composed of (a) structural unit, (b) structural unit, (c) structural unit and (d) structural unit, and may be a mixture of one or more phosphorus-containing polyolefin resins composed of (a) structural unit, (b) structural unit and (d) structural unit and one or more phosphorus-containing polyolefin resins composed of (a) structural unit, (b) structural unit, (c) structural unit and (d) structural unit.

The polyphenylene ether resin containing unsaturated carbon-carbon double bonds applicable to the present invention may be any one or more polyphenylene ether resins containing unsaturated carbon-carbon double bonds used for the production of prepregs, resin films, laminates or printed circuit boards, and may be any one or more commercially available products, self-made products or combinations thereof, but the present invention is not limited thereto. For example, vinylbenzyl polyphenylene ether resin, (meth)acrylic polyphenylene ether resin, vinyl polyphenylene ether resin or combinations thereof, but the present invention is not limited thereto.

The polyphenylene ether resin containing unsaturated carbon-carbon double bonds used in this article all have unsaturated carbon-carbon double bonds and phenylene ether skeletons, wherein the unsaturated carbon-carbon double bonds are reactive functional groups, which can self-polymerize after being heated, and can also undergo free radical polymerization with other unsaturated bond components in the resin composition and finally crosslink and cure. The cured product has the characteristics of high heat resistance and low dielectric properties. Preferably, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes a polyphenylene ether resin containing unsaturated carbon-carbon double bonds with 2,6-dimethyl substitution on the phenylene ether skeleton. After substitution, the methyl groups form stereo barriers, making it difficult for the oxygen atoms on the ether to generate hydrogen bonds or van der Waals forces and absorb moisture, thereby having lower dielectric properties.

In certain exemplary embodiments, the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes a vinylbenzyl polyphenylene ether resin having a number average molecular weight of about 1200 (e.g., OPE-2st 1200, available from Mitsubishi Gas Chemical Co., Ltd.), a vinylbenzyl polyphenylene ether resin having a number average molecular weight of about 2200 (e.g., OPE-2st 2200, available from Mitsubishi Gas Chemical Co., Ltd.), vinyl benzyl polyphenylene ether resin with a number average molecular weight of about 2400 to 2800 (e.g., vinyl benzyl bisphenol A polyphenylene ether resin), (meth) acryl polyphenylene ether resin with a number average molecular weight of about 1900 to 2300 (e.g., SA9000, available from Sabic), vinyl polyphenylene ether resin with a number average molecular weight of about 2200 to 3000, or a combination thereof, but the present invention is not limited thereto. The vinyl polyphenylene ether resin may include various types of polyphenylene ether resins disclosed in U.S. Patent Application US20160185904A1, all of which are incorporated herein by reference. Among them, the vinylbenzyl polyphenylene ether resin includes vinylbenzyl biphenyl polyphenylene ether resin, vinylbenzyl bisphenol A polyphenylene ether resin or a combination thereof, but the present invention is not limited thereto.

In the present invention, the phosphorus content of the phosphorus-containing polyolefin resin is 2 to 10wt%, preferably, the phosphorus content of the phosphorus-containing polyolefin resin is 2.3 to 3.7wt%, and the product prepared by using the resin composition including the phosphorus-containing polyolefin resin with a phosphorus content ranging from 2 to 10wt% and the polyphenylene ether resin containing unsaturated carbon-carbon double bonds has excellent anti-adhesion, high glass transition temperature, low dielectric property, flame retardancy, alkali resistance, moisture absorption and heat resistance, and good substrate appearance. Furthermore, when the phosphorus content of the phosphorus-containing polyolefin resin is preferably 2.3 to 3.7wt%, the above-mentioned properties are significantly improved, especially having a higher glass transition temperature, lower dielectric loss and better alkali resistance.

In the present invention, in the resin composition, the phosphorus-containing polyolefin resin includes any one of the phosphorus-containing polyolefin resins shown in formula (1), the phosphorus-containing polyolefin resins shown in formula (2), the phosphorus-containing polyolefin resins shown in formula (3), the phosphorus-containing polyolefin resins shown in formula (4), the phosphorus-containing polyolefin resins shown in formula (5), the phosphorus-containing polyolefin resins shown in formula (6), the phosphorus-containing polyolefin resins shown in formula (7), the phosphorus-containing polyolefin resins shown in formula (8), the phosphorus-containing polyolefin resins shown in formula (9), or the phosphorus-containing polyolefin resins shown in formula (10), or a combination thereof.

Wherein, in formula (1) to formula (10) (* represents the bonding position between structural units), p, m, n, q, y or t are each independently p=1 to 200, m=2 to 200, n=10 to 400, q=1 to 100, y=1 to 50, t=1 to 50, and R is each independently a hydrogen atom or a C ₁ to C ₃ alkyl group. Preferably, p, m, n, q, y or t are each independently p=1 to 100, m=2 to 100, n=10 to 200, q=1 to 50, y=1 to 40, t=1 to 40. More preferably, p, m, n, q, y or t are each independently p=1 to 40, m=2 to 30, n=10 to 80, q=1 to 30, y=1 to 30, t=1 to 30. In formula (1) to formula (10), each p, m, n, q, y or t may be the same or different, and each p, m, n, q, y or t, for example, p=1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 40, 60, 80, 100 or 200; m=2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 40, 60, 80, 100 or 200; n=10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27 ,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,5 3, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 100, 200, 300, or 400; q = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 40, 60, 80, or 100; y = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 40 or 50; t=1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 40 or 50, but the invention is not limited thereto.

The above formulas (1) to (10) merely exemplify that the phosphorus-containing polyolefin resin has m, n, q, p, t, and y structural units, and do not limit the specific bonding order of each structural unit. In other words, each structural unit can be bonded in various forms, including random bonding, alternating bonding, or block bonding, but the present invention is not limited thereto.

In the present invention, when the phosphorus-containing polyolefin resin contains two or more structural units, the bonding sequence of each structural unit is not particularly limited, and may be, for example, random bonding (structure such as -abbbaaabba-), alternating bonding (structure such as -abababab-) or block bonding (structure such as -aaaaa-bbbbbb-aaaaa-). For example, when the phosphorus-containing polyolefin resin contains four structural units a1, a2, b1, and d2, the structural formula -a1a2b1d2- (e.g., formula (1)) is used to represent it. This is only an exemplary representation that the phosphorus-containing polyolefin contains four structural units a1, a2, b1, and d2, and does not limit the bonding order of the four structural units. That is, the structural formula -a1a2b1d2- should include phosphorus-containing polyolefin resins in which the four structural units a1, a2, b1, and d2 are randomly bonded, phosphorus-containing polyolefin resins in which the four structural units a1, a2, b1, and d2 are alternately bonded, phosphorus-containing polyolefin resins in which the four structural units a1, a2, b1, and d2 are block bonded, or a combination thereof, but the present invention is not limited thereto. For example, when the phosphorus-containing polyolefin resin contains five structural units of c, a1, a2, b1, and d2, the structural formula -ca1a2b1d2- (e.g., formula (6)) is used to represent it. This is only an example to represent that the phosphorus-containing polyolefin resin contains five structural units of c, a1, a2, b1, and d2, and does not limit the bonding order of the five structural units. 2b1d2-, should include phosphorus-containing polyolefin resins with random bonding of five structural units c, a1, a2, b1, d2, phosphorus-containing polyolefin resins with alternating bonding of five structural units c, a1, a2, b1, d2, phosphorus-containing polyolefin resins with block bonding of five structural units c, a1, a2, b1, d2 or combinations thereof, but the present invention is not limited thereto.

In the present invention, the phosphorus-containing polyolefin resin in the resin composition can be prepared by various methods known to those skilled in the art. For example, the preparation method of the phosphorus-containing polyolefin resin comprises the following steps: adding a modified polybutadiene resin and a phosphorus-containing compound into a three-necked flask, stirring and reacting at a temperature of 130 to 165° C. for 3 to 10 hours under N ₂ protection conditions, and the modified polybutadiene resin and the phosphorus-containing compound undergo an addition reaction to generate a phosphorus-containing polyolefin resin.

For example, the modified polybutadiene resin may be a (meth)acrylate-terminated polybutadiene resin, which is commercially available, such as methacrylate-terminated polybutadiene resin EMA-3000 and acrylate-terminated polybutadiene resin EA-3000 from Soda Corporation. The modified polybutadiene resin may also be maleic anhydride-modified polybutadiene or maleic anhydride-modified butadiene-styrene copolymer, wherein the equivalent of maleic anhydride in the maleic anhydride-modified polybutadiene or maleic anhydride-modified butadiene-styrene copolymer is 400 to 2000 g/eq, and the maleic anhydride-modified polybutadiene is commercially available, such as Ricon 130MA8, Ricon 130MA13, Ricon 130MA14, Ricon 130MA15, Ricon 130MA16, Ricon 130MA17, Ricon 130MA18, Ricon 130MA19, Ricon 130MA20, Ricon 130MA30, Ricon 130MA40, Ricon 130MA50, Ricon 130MA60, Ricon 130MA70, Ricon 130MA80, Ricon 130MA19, Ricon 130MA20, Ricon 130MA11, Ricon 130MA21, Ricon 130MA13, Ricon 130MA15, Ricon 130MA21, Ricon 130MA30, Ricon 130MA80, Ricon 130MA16, Ricon 130MA17, Ricon 130MA20, Ricon 130MA18, Ricon 130MA20, Ricon 130MA30 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ricon 131MA20, Ricon 156MA17. Maleic anhydride-modified styrene-butadiene copolymers are commercially available, for example from Cray Valley under the trade name Ricon 184MA6.

For example, the phosphorus-containing compound includes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) compounds and their derivatives or resins, diphenylphosphine oxide (DPPO) compounds and their derivatives or resins, or a combination thereof.

For example, in an exemplary embodiment, the molar ratio of the polybutadiene resin and the phosphorus-containing compound is 1:2 to 1:20, preferably, the molar ratio of the polyolefin resin and the phosphorus-containing compound is 1:2 to 1:8.

For example, in an exemplary embodiment, the aforementioned resin composition may further include a crosslinking agent containing unsaturated carbon-carbon double bonds. The crosslinking agent containing unsaturated carbon-carbon double bonds of the present application refers to a small molecule compound containing unsaturated carbon-carbon double bonds with a molecular weight less than or equal to 1000, and its molecular weight is preferably between 100 and 900, and more preferably between 100 and 800. For example, in an exemplary embodiment, relative to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the added amount of the crosslinking agent containing unsaturated carbon-carbon double bonds of the present invention may be 1 part by weight to 50 parts by weight, preferably 1 part by weight to 10 parts by weight of the crosslinking agent containing unsaturated carbon-carbon double bonds, but the present invention is not limited thereto.

For example, the crosslinking agent containing unsaturated carbon-carbon double bonds can be bis(vinylphenyl)ethane (BVPE), divinylbenzyl ether, divinylbenzene (DVB), divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate (TAIC) (also known as triallyl isocyanurate), triallyl cyanurate (TAC) (also known as triallyl cyanurate), trivinylcyclohexane (TVCH), diallyl bisphenol A (DABPA), butadiene, decadiene, octadiene, difunctional or higher acrylates or combinations thereof, but the present invention is not limited thereto.

烷二醇二丙烯酸酯、三環癸烷二甲醇二丙烯酸酯、三環癸烷二甲醇二甲基丙烯酸酯中的任一種或其組合，但本發明並不受限於此。 The difunctional or higher-functional acrylates include various difunctional acrylates, trifunctional acrylates or tetrafunctional or higher-functional acrylates known in the art, which can be purchased from Shin-Nakamura Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd., Nippon Kayaku Co., Ltd. or Sartomer Co., Ltd. Specific examples include diallyl isophthalate (DAIP), di-

Any one of alkylene glycol diacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, or a combination thereof, but the present invention is not limited thereto.

For example, in an exemplary embodiment, the resin composition of the present invention may further include a phosphorus-free polyolefin. For example, in an exemplary embodiment, the amount of the phosphorus-free polyolefin of the present invention may be 1 to 50 parts by weight, preferably 1 to 10 parts by weight, relative to 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, but the present invention is not limited thereto. The phosphorus-free polyolefin applicable to the present invention may be any one or more polyolefins used to prepare prepregs, resin films, laminates or printed circuit boards, and may be any one or more commercially available products, self-made products or combinations thereof. For example, the phosphorus-free polyolefin of the present invention includes diene polymers, monoene polymers, hydrogenated diene polymers or combinations thereof, but the present invention is not limited thereto. The diene refers to a hydrocarbon compound containing two unsaturated carbon-carbon double bonds in the molecule, and the monoene refers to a hydrocarbon compound containing one unsaturated carbon-carbon double bond in the molecule. The phosphorus-free polyolefin of the present invention includes, for example, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-divinylbenzene terpolymer, maleic anhydride-added polybutadiene-styrene copolymer, vinyl-polybutadiene-urea polymer, maleic anhydride-added polybutadiene, polymethylstyrene, hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-butadiene-divinylbenzene terpolymer, hydrogenated maleic anhydride-added styrene-butadiene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, epoxy-containing polybutadiene, and multifunctional vinyl aromatic copolymers, or any one or a combination thereof, but the present invention is not limited thereto.

For example, the multifunctional vinyl aromatic copolymer used herein may include various types of multifunctional vinyl aromatic copolymers disclosed in U.S. Patent US20070129502A1, all of which are incorporated herein by reference.

樹脂、環氧樹脂、有機矽樹脂、氰酸酯樹脂、活性酯、酚樹脂、胺類固化劑、苯乙烯馬來酸酐、聚醯胺、聚醯亞胺或其組合。 For example, in an exemplary embodiment, the resin composition of the present invention may further contain maleimide resin, benzo[pi]

Resin, epoxy resin, organic silicone resin, cyanate resin, active ester, phenol resin, amine curing agent, styrene maleic anhydride, polyamide, polyimide or a combination thereof.

樹脂、環氧樹脂、有機矽樹脂、氰酸酯樹脂、聚酯樹脂、酚樹脂、苯乙烯馬來酸酐、聚醯胺、聚醯亞胺的用量並不特別限制，例如各成分可各自獨立為1重量份至100重量份，例如1重量份、10重量份、15重量份、20重量份、25重量份、50重量份或100重量份，但本發明並不受限於此。相對於100重量份的含不飽和碳碳雙鍵的聚苯醚樹脂，胺類固化劑的用量也不特別限制，例如可以是1 至15重量份，例如1重量份、4重量份、7.5重量份、12重量份或15重量份，但本發明並不受限於此。 In the resin composition of the present invention, relative to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, maleimide resin, benzo[pi]

The amount of resin, epoxy resin, organic silicone resin, cyanate resin, polyester resin, phenol resin, styrene maleic anhydride, polyamide, polyimide is not particularly limited, for example, each component can be independently 1 to 100 parts by weight, for example, 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, but the present invention is not limited thereto. The amount of amine curing agent relative to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds is also not particularly limited, for example, it can be 1 to 15 parts by weight, for example, 1 part by weight, 4 parts by weight, 7.5 parts by weight, 12 parts by weight or 15 parts by weight, but the present invention is not limited thereto.

The maleimide resin suitable for the resin composition of the present invention can be any one or more maleimide resins used for making prepregs (or prepregs), resin films, laminates or printed circuit boards. In certain exemplary embodiments, the maleimide resin may be, for example, 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide (or oligomer of phenylmethane maleimide), bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bismaleimide), 3,3'-dimethyl-5,5'-dipropyl-4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, bismaleimide), 1,6-bismaleimide-(2,2,4-trimethyl)hexane, N-2,3-dimethylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-phenylmaleimide, vinyl benzylmaleimide The present invention can be selected from maleimide (VBM), biphenyl maleimide, maleimide resin with aliphatic structure having 10 to 50 carbon atoms, maleimide with indane structure, maleimide with meta-arylene structure, diallyl compound modified maleimide resin, diamine modified maleimide resin, multifunctional amine modified maleimide resin, acidic phenol compound modified maleimide resin, cyanate modified maleimide resin or a combination thereof, but the present invention is not limited thereto and should be understood to also include modified products of these components. Among them, the maleimide containing a meta-arylene structure refers to the maleimide resin produced by Nippon Kayaku Co., Ltd. under the trade name MIR-5000.

For example, maleimide resins 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 produced by Daiwakasei Industry, or BMI-70, BMI-80, etc. produced by K.I Chemical Co., Ltd., or MIR-3000 or MIR-5000, etc. produced by Nippon Kayaku Co., Ltd., but the present invention is not limited thereto.

For example, the maleimide resin having an aliphatic structure with 10 to 50 carbon atoms, or the maleimide resin extended with amide, may include various types of maleimide resin extended with amide disclosed in Taiwan Patent Application Publication No. TW200508284A, all of which are incorporated herein by reference. The maleimide resin of the present application having an aliphatic structure with 10 to 50 carbon atoms is, for example, a maleimide resin produced by the designer's subsidiary with trade names such as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000 and BMI-6000, but the present invention is not limited thereto.

樹脂可為本領域已知的各類苯并

樹脂。具體實例包括雙酚A型苯并

樹脂、雙酚F型苯并

樹脂、酚酞型苯并

樹脂、雙環戊二烯型苯并

樹脂、含磷苯并

樹脂、二胺型苯并

樹脂及苯基、乙烯基或烯丙基改質的苯并

樹脂，但本發明並不受限於此。適用的市售商品包括如Huntsman銷售的商品名LZ-8270(酚酞型苯并

樹脂)、LZ-8298(酚酞型苯并

樹脂)、LZ-8280(雙酚F型苯并

樹脂)、LZ-8290(雙酚A型苯并

樹脂)，或如韓國Kolon Industries銷售的商品名KZH-5031(乙烯基改質的苯并

樹脂)、KZH-5032(苯基改質的苯并

樹脂)。其中，二胺型苯并

樹脂可為二胺基二苯甲烷苯并

樹脂、二胺基二苯醚型苯并

樹脂、二胺基二苯碸苯并

樹脂、二胺基二苯硫醚苯并

樹脂或其組合，且不以此為限。 In the present invention, for example, the benzo

The resin can be any of various benzo

Specific examples include bisphenol A type benzo

Resin, bisphenol F type benzo

Resin, phenolphthalein type benzo

Resin, dicyclopentadiene benzophenone

Resins, phosphorus-containing benzoic acid

Resin, diamine type benzo

Resins and phenyl, vinyl or allyl modified benzo

Resins, but the present invention is not limited thereto. Suitable commercial products include, for example, Huntsman sold under the trade name LZ-8270 (phenolphthalein type benzophenone

Resin), LZ-8298 (phenolphthalein type benzo

Resin), LZ-8280 (Bisphenol F type benzo

Resin), LZ-8290 (Bisphenol A type benzo

resin), or KZH-5031 (vinyl-modified benzoic acid) sold by Kolon Industries of Korea

Resin), KZH-5032 (phenyl-modified benzoic acid

Resin). Among them, diamine type benzo

The resin can be diaminodiphenylmethane benzo

Resin, diaminodiphenyl ether type benzo

Resin, diaminodiphenyl sulfide benzo

Resin, diaminodiphenyl sulfide benzo

Resin or a combination thereof, but not limited thereto.

In the present invention, for example, the epoxy resin can be any epoxy resin known in the art. From the perspective of improving the heat resistance of the resin composition, the epoxy resin includes, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional novolac epoxy resin, dicyclopentadiene epoxy resin, and the like. (dicyclopentadiene, DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene epoxy resin (such as naphthol epoxy resin), benzofuran epoxy resin, isocyanate-modified epoxy resin or a combination thereof, but the present invention is not limited thereto. The phenolic epoxy resin may be phenol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenol benzaldehyde epoxy resin, phenol aralkyl novolac epoxy resin or o-cresol novolac epoxy resin; the phosphorus-containing epoxy resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin or a combination thereof. The DOPO epoxy resin may be selected from one or more of DOPO-containing phenol novolac epoxy resin, DOPO-containing o-cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin; the DOPO-HQ epoxy resin may be selected from DOPO-HQ-containing phenol novolac epoxy resin, DOPO-HQ-containing o-cresol novolac epoxy resin, and DOPO-HQ-containing bisphenol-A novolac epoxy resin. Novolac epoxy resin) One or more of them, but not limited to them.

In the present invention, for example, the organic silicon resin can be various organic silicon resins known in the art. Specific examples include polyalkyl organic silicon resins, polyaryl organic silicon resins, polyalkylaryl organic silicon resins, modified organic silicon resins or combinations thereof, but the present invention is not limited thereto. Preferably, the organic silicone resin of the present invention is an amine-modified organic silicone resin, for example, an amine-modified organic silicone resin produced by Shin-Etsu Chemical 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., an amine-modified organic silicone resin produced by Toray-Dow Corning Co., Ltd. under the trade names BY-16-853U, BY-16-853, BY-16-853B, etc., an amine-modified organic silicone resin produced by Momentive Performance Materials Co., Ltd. under the trade names XF42-C5742, XF42-C6252, XF42-C5379, etc. Amino-modified organic silicone resins or combinations thereof produced by JAPAN Corporation, but the present invention is not limited thereto.

In the present invention, for example, the cyanate ester may be any one or more cyanate resins used for making prepregs, resin films, laminates or printed circuit boards, such as compounds having an Ar-O-C≡N structure, wherein Ar may be a substituted or unsubstituted aromatic group. From the perspective of improving the heat resistance of the resin composition, specific examples of cyanate resins include phenolic cyanate resins, bisphenol A cyanate resins, bisphenol F cyanate resins, cyanate resins containing dicyclopentadiene structures, cyanate resins containing naphthalene ring structures, phenolphthalein cyanate resins, adamantane cyanate resins, fluorene cyanate resins or combinations thereof, but the present invention is not limited thereto. Among them, the phenolic cyanate resin can be bisphenol A phenolic cyanate resin, bisphenol F phenolic cyanate resin or a combination thereof. For example, the cyanate resin can be a cyanate resin produced by Lonza under the trade names of Primaset PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL950S, HTL-300, CE-320, LVT-50, LeCy, etc.

The active ester applicable to the resin composition of the present invention may be various types of active polyester resins known in the art, including various commercially available active polyester resin products, specific examples of which include polyester resins containing dicyclopentadiene structures and polyester resins containing naphthalene ring structures, such as active polyester resins with the trade names HPC-8000 and HPC-8150 produced by Dainippon Ink Chemicals, but the present invention is not limited thereto.

In the present invention, for example, the phenolic resin may be any phenolic resin known in the art, and specific examples include phenolic resin or phenoxy resin, wherein the phenolic resin includes phenolic resin, o-methylphenolic resin, bisphenol A resin, naphthol phenolic resin, biphenyl phenolic resin and dicyclopentadienol resin, but is not limited thereto.

In the present invention, for example, the amine curing agent can be any type of amine curing agent known in the art. Specific examples include at least one or a combination of diaminodiphenyl sulfone, diaminodiphenyl methane, diaminodiphenyl ether, diaminodiphenyl sulfide and dicyandiamide, but the present invention is not limited thereto.

In the present invention, for example, the styrene maleic anhydride may be any type of styrene maleic anhydride known in the art, wherein the ratio of styrene (St) to maleic anhydride (MA) may be 1/1, 2/1, 3/1, 4/1, 6/1, 8/1 or 12/1, and specific examples include styrene maleic anhydride 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 styrene maleic anhydride copolymers sold by Polyscope under the trade names C400, C500, C700, C900, and the like, and are not limited thereto.

In the present invention, for example, the polyamide can be various polyamides known in the art, including various commercially available polyamide resin products, but the present invention is not limited thereto.

In the present invention, for example, the polyimide can be various polyimides known in the art, including various commercially available polyimide resin products, but the present invention is not limited thereto.

In addition to the aforementioned components, the resin composition of the present invention may further include flame retardants, hardening accelerators, polymerization inhibitors, inorganic fillers, solvents, silane coupling agents, surfactants, dyes, toughening agents or combinations thereof as needed.

For example, the inorganic filler of the present invention can be any one or more inorganic fillers used in the manufacture of prepregs, resin films, laminates or printed circuit boards, and specific examples include: silicon dioxide (molten, non-molten, porous or hollow), aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, titanium dioxide, 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, perlite, calcined kaolin or a combination thereof, but the present invention is not limited thereto. In addition, the inorganic filler may be spherical (including solid sphere or hollow sphere), fibrous, plate-like, granular, flake or needle-like, and may be optionally pre-treated with a silane coupling agent. In addition, the inorganic filler may be prepared by a variety of methods, such as deflagration, chemical synthesis, etc., but the present invention is not limited thereto. For example, in an exemplary embodiment, compared to 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention may further include 10 to 300 parts by weight of an inorganic filler, preferably 100 to 250 parts by weight of an inorganic filler, but the present invention is not limited thereto.

For example, the flame retardant of the present invention can be any one or more flame retardants used in the manufacture of prepregs, resin films, laminates or printed circuit boards, such as bromine-containing flame retardants or phosphorus-containing flame retardants, but the present invention is not limited thereto. Bromine-containing flame retardants preferably include decabromodiphenylethane, and phosphorus-containing flame retardants preferably include ammonium polyphosphate, p-hydroquinone bis-(diphenyl phosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), tri(chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methyl phosphate (dimethyl phosphate), and dimethyl methyl phosphate. phosphonate, DMMP), resorcinol bis (dixylenyl phosphate), RDXP (such as PX-200, PX-201, PX-202 and other commercial products), phosphazene compounds (such as SPB-100, SPH-100, SPV-100 and other commercial products), melamine polyphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, DOPO) compounds and their derivatives or resins, diphenylphosphine oxide (DPPO) compounds and their derivatives or resins, melamine cyanurate (melamine cyanurate) (also known as melamine cyanurate) and tri-hydroxy ethyl isocyanurate (also known as tri-hydroxyethyl isocyanurate), aluminum hypophosphite (such as OP-930, OP-935 and other products) or a combination thereof.

For example, the DPPO compound may be a bis-DPPO compound. The DOPO compound may be a bis-DOPO compound, DOPO-HQ, DOPO-NQ or a vinyl-containing DOPO compound. DOPO resins include DOPO-bonded phenolic resins or DOPO-bonded epoxy resins, but the present invention is not limited thereto. The DOPO-bonded phenolic resins include DOPO-phenol phenolic resins (DOPO-PN), DOPO-bisphenol A phenolic resins (DOPO-BPAN), DOPO-bisphenol F phenolic resins (DOPO-bisphenol F novolac, DOPO-BPFN) or DOPO-bisphenol S phenolic resins (DOPO-bisphenol S novolac, DOPO-BPSN) and other bisphenol phenolic resins, but the present invention is not limited thereto.

Preferably, the flame retardant is a DOPO compound and its derivatives or resins, a DPPO compound and its derivatives or resins, or a combination thereof.

For example, relative to 100 parts by weight of polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the amount of the flame retardant added can be 1 part by weight to 65 parts by weight, preferably, the amount of the flame retardant added can be 1 part by weight to 10 parts by weight.

The hardening accelerator (including hardening initiator) of the present invention may include a catalyst such as a Lewis base or a Lewis acid. The Lewis base may include one or more of imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP) and 4-dimethylaminopyridine (DMAP). The Lewis acid may include a metal salt compound such as a metal salt compound of manganese, iron, cobalt, nickel, copper, zinc, etc., such as a metal catalyst such as zinc octoate and cobalt octoate. The hardening accelerator also includes a hardening initiator, such as a peroxide that can generate free radicals. The hardening initiator includes: diisopropylbenzene peroxide, tertiary butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tertiary butyl peroxy)-3-hexyne (25B) and di(tertiary butyl peroxyisopropyl)benzene or a combination thereof, but the present invention is not limited thereto. For example, in an exemplary embodiment, compared to 100 parts by weight of a polyphenylene ether resin containing an unsaturated carbon-carbon double bond, the resin composition of the present invention may further include 0.001 parts by weight to 5 parts by weight of a hardening accelerator, preferably 0.5 parts by weight to 3 parts by weight of a hardening accelerator, but the present invention is not limited thereto.

、β-苯基萘胺、對三級丁基鄰苯二酚、亞甲基藍、4,4’-亞丁基雙(6-三級丁基-3-甲基苯酚)以及2,2’-亞甲基雙(4-乙基-6-三級丁基苯酚)或其組合，但本發明並不受限於此。例如，上述氮氧穩定自由基可包括2,2,6,6-四甲基-1-氧基-哌啶、2,2,6,6-取代-1-哌啶氧自由基或2,2,5,5-取代-1-吡咯烷氧自由基等來自環狀羥胺的氮氧自由基，但本發明並不受限於此。作為取代基，優選為甲基或乙基等碳數為四個以下的烷基。具體的氮氧自由基化合物並無限制，實例包括2,2,6,6-四甲基-1-哌啶氧自由基、2,2,6,6-四乙基-1-哌啶氧自由基、2,2,6,6-四甲基-4-氧代-1-哌啶氧自由基、2,2,5,5-四甲基-1-吡咯烷氧自由基、1,1,3,3-四甲基-2-異吲哚啉氧自由基、N,N-二(三級丁基)胺氧自由基等，但本發明並不受限於此。也可使用加爾萬氧基(galvinoxyl)自由基等穩定的自由基來代替氮氧自由基。本發明的樹脂組合物的聚合抑制劑也可以為所述聚合抑制劑中的氫原子或原子團被其他原子或原子團取代而衍生的產物。例如聚合抑制劑中的氫原子被胺基、羥基、酮羰基等原子團取代而衍生的產物。例如，在一示例性實施例中，相較於100重量份的含不飽和碳碳雙鍵的聚苯醚樹脂，本發明的樹脂組合物還可以進一步包括0.001重量份至20重量份的聚合抑制劑，優選為0.001重量份至10重 量份的聚合抑制劑，但本發明並不受限於此。 For example, the polymerization inhibitor of the present invention may include 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, nitrogen oxide stable free radicals, triphenylmethyl free radicals, metal ion free radicals, sulfur free radicals (such as dithioesters, but the present invention is not limited thereto), hydroquinone, p-methoxyphenol, p-benzoquinone, phenothiazine,

, β-phenylnaphthylamine, p-tert-butyl o-cyclopentylphenol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol) and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) or a combination thereof, but the present invention is not limited thereto. For example, the above-mentioned nitrogen oxide stable free radical may include a nitrogen oxide free radical from a cyclic hydroxyl amine such as 2,2,6,6-tetramethyl-1-oxy-piperidine, 2,2,6,6-substituted-1-piperidinyloxy free radical or 2,2,5,5-substituted-1-pyrrolidinyloxy free radical, but the present invention is not limited thereto. As a substituent, an alkyl group having four or less carbon atoms such as a methyl group or an ethyl group is preferred. The specific nitroxide free radical compound is not limited, and examples include 2,2,6,6-tetramethyl-1-piperidinyloxy free radical, 2,2,6,6-tetraethyl-1-piperidinyloxy free radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy free radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy free radical, 1,1,3,3-tetramethyl-2-isoindolinyloxy free radical, N,N-di(tertiary butyl)amineoxy free radical, etc., but the present invention is not limited thereto. Stable free radicals such as galvinoxyl free radicals can also be used to replace nitroxide free radicals. The polymerization inhibitor of the resin composition of the present invention can also be a product derived from the substitution of hydrogen atoms or atomic groups in the polymerization inhibitor by other atoms or atomic groups. For example, the hydrogen atoms in the polymerization inhibitor are replaced by atomic groups such as amino groups, hydroxyl groups, ketocarbonyl groups, etc. to derive products. For example, in an exemplary embodiment, compared with 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention can further include 0.001 parts by weight to 20 parts by weight of the polymerization inhibitor, preferably 0.001 parts by weight to 10 parts by weight of the polymerization inhibitor, but the present invention is not limited thereto.

For example, the solvent of the resin composition of the present invention can be any solvent suitable for dissolving the resin composition of the present invention, including: methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, nitrogen methyl pyrrolidone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether acetate and the like solvents or mixed solvents thereof, but the present invention is not limited thereto. The amount of solvent added is to be able to completely dissolve the resin and adjust to a specific overall solid content of the resin composition. For example, in an exemplary embodiment, the amount of solvent added is to adjust the overall solid content of the resin composition to 50% to 85%, but the present invention is not limited thereto.

For example, the silane coupling agent may include a silane compound (e.g., a siloxane compound, but the present invention is not limited thereto), which may be further divided into amino silane compounds, epoxide silane compounds, vinyl silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloxy silane compounds according to the type of functional groups. For example, in an exemplary embodiment, compared to 100 parts by weight of the polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention may further include 0.001 parts by weight to 20 parts by weight of a silane coupling agent, preferably 0.01 parts by weight to 10 parts by weight of a silane coupling agent, but the present invention is not limited thereto.

The type of surfactant in the resin composition of the present invention is not particularly limited. The main function of adding a surfactant in the present invention is to allow the filler to be evenly dispersed in the resin composition.

For example, the above-mentioned dye may include a dye or a pigment, but the present invention is not limited thereto.

In the present invention, the main function of adding a toughening agent is to improve the toughness of the resin composition. For example, the toughening agent may include carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, ethylene propylene rubber and other compounds or combinations thereof, but the present invention is not limited thereto. For example, in an exemplary embodiment, compared to 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds, the resin composition of the present invention may further include 1 to 20 parts by weight of a toughening agent, preferably 3 to 10 parts by weight of a toughening agent, but the present invention is not limited thereto.

The resin compositions of the aforementioned exemplary embodiments can be made into various products, such as components used in various electronic products, including prepregs, resin films, laminates or printed circuit boards, but the present invention is not limited thereto.

For example, the resin composition of each exemplary embodiment 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 made by heating the 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 one of a fiber material, a woven fabric, and a non-woven fabric, and the woven fabric preferably includes a glass fiber cloth. Types of glass fiber cloth There is no particular limitation, and it can be various glass fiber cloths that can be used for printed circuit boards, such as E-type glass cloth, D-type glass cloth, S-type glass cloth, T-type glass cloth, L-type glass cloth, Q-type glass cloth or QL-type glass cloth (glass cloth with a mixed structure made of Q glass and L glass); types of glass fiber include yarn and coarse yarn, etc., and the form includes open fiber or non-open fiber, and the end face shape includes round or flat shape. The aforementioned non-woven fabric preferably includes liquid crystal resin non-woven fabric, such as polyester non-woven fabric, polyurethane non-woven fabric, etc., and is not limited to this. The aforementioned woven fabric may also include liquid crystal resin woven fabric, such as polyester woven fabric or polyurethane woven fabric, etc., and is not limited to this. This reinforcing material can increase the mechanical strength of the semi-cured sheet. In a preferred embodiment, the reinforcing material may also be selectively pre-treated with a silane coupling agent. The semi-cured sheet is subsequently heated and cured (C-stage) to form an insulating layer.

For example, the resin composition of each exemplary embodiment of the present invention can be made into a resin film, which is obtained by semi-curing the aforementioned resin composition after baking and heating. The resin composition can be selectively coated on a liquid crystal resin film, a polytetrafluoroethylene film, a polyethylene terephthalate film (PET film), a polyimide film (PI film), a copper foil or a backing copper foil, and then formed into a semi-cured state after baking and heating, so that the resin composition forms a resin film.

For example, the resin composition described in the present application can be made into various laminates, which include at least two metal foils and at least one insulating layer, wherein the insulating layer is disposed between the two metal foils, and the insulating layer can be formed by curing the resin composition under high temperature and high pressure (C-stage), and the applicable curing temperature is, for example, between 190°C and 220°C, preferably between 200°C and 210°C, the curing time is, for example, between 90 and 180 minutes, preferably between 120 and 150 minutes, and the applicable pressing pressure is, for example, between 300psi and 550psi, preferably between 400psi and 500psi. The aforementioned insulating layer can be obtained by curing the aforementioned prepreg or resin film. The material of the aforementioned metal foil may be copper, aluminum, nickel, platinum, silver, gold or their alloys, such as copper foil. In a preferred exemplary embodiment, the laminate is a copper foil substrate.

In an exemplary embodiment, the aforementioned laminate can be further processed into a printed circuit board after circuit processing.

One method of manufacturing the printed circuit board of the present application may be to use a double-sided copper-clad laminate (e.g., product EM-827, available from Taiwan Optoelectronics Materials) with a thickness of 28 mils and 1 ounce HTE (High Temperature Elongation) copper foil, and then perform electroplating after drilling holes to form electrical conduction between the upper copper foil and the bottom copper foil. Then, the upper copper foil and the bottom copper foil are etched to form an inner circuit. Then, the inner circuit is subjected to browning and roughening treatment to form a concave-convex structure on the surface to increase the roughness. Next, the copper foil, the aforementioned prepreg, the aforementioned inner circuit board, the aforementioned prepreg, and the copper foil are stacked in sequence, and then heated for 90 to 180 minutes in a vacuum lamination device at a temperature of 190°C to 220°C to cure the insulating layer material of the prepreg. Then, various circuit board process steps known in the art such as blackening, drilling, and copper plating are performed on the outermost surface of the copper foil to obtain a printed circuit board.

In one or more exemplary embodiments, the various types of products prepared from the resin composition disclosed in this application preferably have one or more of the following characteristics: In an exemplary embodiment, after the aforementioned semi-cured sheet is vacuum packaged, it is placed in a 40°C environment for 2 hours and tested without sticking or powdering.

The dielectric constant measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 3.40, for example, between 3.22 and 3.40.

The dielectric loss measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0040, for example, between 0.0026 and 0.0040.

The glass transition temperature measured according to the method of IPC-TM-650 2.4.24.4 is greater than or equal to 200°C, for example, between 200°C and 234°C.

The flame retardancy tested according to UL94 standard method is V0.

The products were tested for moisture absorption and heat resistance according to the methods of IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, and no board explosion occurred.

The alkali resistance of the substrate measured by the alkali resistance test is greater than or equal to 10 minutes, for example, between 10 minutes and 20 minutes.

Through visual inspection, it was observed that the substrate had no streaks or yellow spots.

In this application, the characteristic tests of the embodiments and comparative examples are performed by making the objects to be tested (samples) according to the following method and then performing the tests according to specific test conditions.

1. Precured sheet: The resin composition in the embodiment or the comparative example is selected and mixed uniformly to form a varnish, and the varnish is placed in an impregnation tank. Then, a glass fiber cloth (for example, L-glass fiber cloth with a specification of 2116 or L-glass fiber cloth with a specification of 1080, both purchased from Asahi) is immersed in the impregnation tank to make the resin composition adhere to the glass fiber cloth, and heated at 150°C to 170°C to a semi-cured state (B-Stage), to obtain a precured sheet with a resin content of 53%.

2. Copper-free substrate (8-ply, formed by pressing 8 prepregs): 2 ultra-low surface roughness (HVLP) copper foils with a thickness of 18 microns and 8 2116 L-glass fiber cloths were prepared to impregnate the prepregs made from each sample to be tested (each set of embodiments or comparative examples). The resin content of each prepreg was about 53%. One HVLP copper foil, eight prepregs and one HVLP copper foil were stacked in this order and pressed for 2 hours under vacuum conditions at a pressure of 500 psi and 200°C to form a copper-containing foil substrate (8-ply). The copper-containing foil substrate (8-ply) is etched to remove two copper foils to obtain a copper-free substrate (8-ply). The copper-free substrate is formed by pressing eight prepreg sheets together. The resin content of the copper-free substrate is about 53%.

3. Copper-free substrate (2-ply, formed by pressing two prepregs): Prepare two 18-micron-thick ultra-low surface roughness (HVLP) copper foils and two 1080 L-glass fiber cloths impregnated with the prepregs made from each sample to be tested (each set of embodiments or comparative examples), stack them in the order of copper foil, two prepregs and copper foil, and press them for 2 hours under vacuum conditions, a pressure of 500 psi, and 200°C to form a copper foil substrate (2-ply, formed by pressing two prepregs). Next, the copper foil on both sides of the copper-containing foil substrate (2-ply) is etched away to obtain a copper-free substrate (2-ply). The copper-free substrate is formed by pressing two prepreg sheets together. The resin content of the copper-free substrate (2-ply) is about 80%.

For the aforementioned samples to be tested, the test methods and their characteristic analysis items are described as follows:

1. Anti-adhesion property of semi-cured sheet

The prepregs made by impregnating each sample to be tested (each set of examples or comparative examples) with L-glass fiber cloth of 2116 are placed in an aluminum foil bag, and the aluminum foil bag is evacuated and packaged. They are placed in a 40°C environment for 2 hours, and then the prepregs are taken out and the surfaces between the prepregs and the adjacent prepregs are observed to see if there is any sticking or powdering. If there is no sticking or powdering on the surface of the prepreg, it is recorded as OK. If there is sticking or powdering on the surface of the prepreg, it is recorded as sticking or powdering. Sticking or powdering on the surface of the prepreg indicates that the prepreg has poor operability.

2. Glass transition temperature (Tg)

The aforementioned copper-free substrate (8-ply) was selected as the sample to be tested, and the dynamic mechanical analyzer (DMA) was used to measure the glass transition temperature of each sample to be tested according to the method described in IPC-TM-650 2.4.24.4 (2012), with the unit of °C. The measuring temperature range was 50 to 40 °C, and the temperature rise rate was 2 °C/min.

3. Dielectric constant (Dk) and dielectric loss (dissipation factor, Df)

The aforementioned copper-free substrate (2-ply) was selected as the sample to be tested, and a microwave dielectric analyzer (microwave dielectrometer, purchased from AET, Japan) was used to measure each sample at room temperature (about 25°C) and at a frequency of 10 GHz according to the method described in JIS C2565 (1992). The lower the dielectric constant and dielectric loss, the better the dielectric properties of the sample to be tested. At a measurement frequency of 10 GHz and within the range of Df values less than 0.005, a difference in Df values greater than or equal to 0.0001 indicates that there is a significant difference in dielectric loss between different substrates (there is a significant technical difficulty).

4. Flame retardancy

The aforementioned copper-free substrate (8-ply) (125mm×13mm) was selected as the sample to be tested and measured according to the UL94 standard method. The flame retardancy analysis results were expressed in V0, V1, and V2 grades, among which V0 flame retardancy was better than V1 flame retardancy, V1 flame retardancy was better than V2 flame retardancy, and the sample burned out was the worst.

5. Heat resistance test after moisture absorption (pressure cooking test, PCT)

The aforementioned copper-free substrate (8-ply) was selected and subjected to a pressure cooking test for 3 hours of moisture absorption (test temperature 121°C and relative humidity 100%) according to the method described in IPC-TM-650 2.6.16.1 (2012). Then, it was immersed in a tin furnace at a constant temperature of 288°C according to the method described in IPC-TM-650 2.4.23 (2012). After immersion for 20 seconds, it was taken out to observe whether there was any cracking (cracking means failure, and no cracking means passing the test. O means no cracking in the test, and X means cracking in the test). Three samples were tested in each group. One X means one sample failed in three PCT tests, two Xs mean two samples failed in three PCT tests, and three Xs mean three samples failed in three PCT tests. For example, interlayer peeling between insulating layers is called a failure. Interlayer peeling will cause blistering and separation between any layers of the substrate.

6. Alkali resistance

The aforementioned copper-free substrate (8-ply) was selected as the sample to be tested, and three 4mm×2mm test specimens were cut out and placed in a 105℃ oven for 2 hours, and then immersed in a 90℃ 20% NaOH solution. The specimens were taken out every 5 minutes, and visually observed whether the substrate surface was whitish or the weave was exposed, and the sample immersion time was recorded. If no whitish or weave was exposed, it means that the substrate alkali resistance passed within this time range; if whitish or weave was exposed, it means that the substrate alkali resistance did not pass within this time range, and the sample needs to be re-prepared, and the specimens were taken out every 1 minute, and visually observed when the substrate would be whitish or the weave was exposed, and the sample immersion time was recorded in minutes (min). The longer the time, the better the alkali resistance.

7. Appearance of substrate

Take the above copper-free substrate (8-ply, 8 prepreg sheets pressed together) and visually observe whether there are tree-like stripes (abbreviated as stripes) and yellow spots on the surface edge of the board. If there are no tree-like stripes and yellow spots on the board edge, record it as OK. If there are tree-like stripes and yellow spots on the board edge, record it as stripes or yellow spots.

Using various raw materials from the following sources, the resin compositions of the embodiments of the present invention and the comparative examples of the present invention are respectively prepared according to the dosages in Tables 1 to 4, and further prepared into various test samples.

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

SA9000: Methacrylic polyphenylene ether resin, purchased from Sabic.

OPE-2st 2200: vinyl benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

OPE-2st 1200: vinyl benzyl polyphenylene ether resin, purchased from Mitsubishi Gas Chemical.

Self-made phosphorus-containing polyolefin resins P1 to P9 are described in detail below.

Self-made D1 to D4, details are as follows.

Ricon 184MA6: Maleic anhydride modified styrene-butadiene copolymer, anhydride equivalent weight 1651g/eq, purchased from Cray Valley.

Ricon 130MA8: Maleic anhydride modified polybutadiene, anhydride equivalent weight 1238g/eq, purchased from Cray Valley.

Ricon 156MA17: Maleic anhydride modified polybutadiene, anhydride equivalent weight 583g/eq, purchased from Cray Valley.

Ricon 131MA5: Maleic anhydride modified polybutadiene, anhydride equivalent weight 1981g/eq, purchased from Cray Valley.

EMA-3000: methacrylate-terminated polybutadiene, purchased from Soda Corporation.

EA-3000: Acrylate-terminated polybutadiene, purchased from Soda Corporation.

DPPO: diphenylphosphine oxide, purchased from Beijing Bailingwei Technology Co., Ltd.

DOPO: 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide, purchased from Zhengzhou Alpha Company.

Di-DOPO: bis(9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide), the structural formula is as follows.

Di-DPPO: Di-DPPO flame retardant, the structure is as follows.

BVPE: Bis(vinylphenyl)ethane, purchased from Linchuan Chemical.

Multifunctional vinyl aromatic copolymer, commercially available.

SC-2500 SVJ: Spherical silica made by deflagration method, purchased from Admatechs.

99.8%，市售或自製。 Synthetic spherical silica: Spherical silicon dioxide is made by chemical synthesis.

99.8%, commercially available or homemade.

25B: 2,5-dimethyl-2,5-di(tertiary butylperoxy)-3-hexyne, purchased from NOF Corporation.

Toluene: purchased from Sinopec. The toluene content is expressed as "appropriate amount", which means that the toluene content is adjusted to the overall solid content of the resin composition of 55% to 70% (solid content, S/C = 60% to 68%).

Homemade compound P1:

Into a three-necked flask, 100 g of maleic anhydride-modified polybutadiene (Ricon 130MA8) and 32 g of 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide (DOPO) were added in sequence (the molar ratio of Ricon 130MA8 to DOPO in the reaction raw material was 1:4), and the mixture was stirred at a high speed at 140°C for 4 hours under _N2 protection to obtain a phosphorus-containing polyolefin resin with a phosphorus content of 3.5 wt%. Its structure is shown in formula (1).

Homemade compound P2:

100 g of maleic anhydride-modified polybutadiene (Ricon 130MA8) and 30 g of diphenylphosphine oxide (DPPO) (the molar ratio of Ricon 130MA8 to DPPO in the reaction raw material is 1:4) were added to a three-necked flask in sequence, and the mixture was stirred at a high speed at 145°C for 3.5 hours under _N2 protection to obtain a phosphorus-containing polyolefin resin with a phosphorus content of 3.5 wt%. Its structure is shown in formula (2).

Homemade compound P3:

Into a three-necked flask, 100 g of maleic anhydride-modified polybutadiene (Ricon 131MA5) and 27.6 g of 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide (DOPO) were added in sequence (the molar ratio of Ricon 131MA5 to DOPO in the reaction raw material was 1:6), and the mixture was stirred at a high speed at 150°C for 5 hours under _N2 protection to obtain a phosphorus-containing polyolefin resin with a phosphorus content of 3.1 wt%. Its structure is shown in formula (1).

Homemade compound P4:

Into a three-necked flask, 100 g of maleic anhydride-modified styrene-butadiene copolymer (Ricon 184MA6) and 17.8 g of diphenylphosphine oxide (DPPO) (the molar ratio of Ricon 184MA6 to DPPO in the reaction raw material is 1:8) were added in sequence, and the mixture was stirred at high speed at 155°C for 6 hours under _N2 protection to obtain a phosphorus-containing polyolefin resin with a phosphorus content of 2.3 wt%. Its structure is shown in formula (5).

Homemade compound P5:

Into a three-necked flask, 100 g of maleic anhydride-modified polybutadiene (Ricon 156MA17) and 32.3 g of diphenylphosphine oxide (DPPO) (the molar ratio of Ricon 156 MA17 to DPPO in the reaction raw material is 1:4) are added in sequence, and the mixture is stirred at high speed at 140°C for 4 hours under _N2 protection to obtain a phosphorus-containing polyolefin resin with a phosphorus content of 3.7 wt%. Its structure is shown in formula (2).

Homemade compound P6:

Into a three-necked flask, 100 g of methacrylate-terminated polybutadiene (EMA-3000) and 27.9 g of 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide (DOPO) were added in sequence (the molar ratio of EMA-3000 to DOPO in the reaction raw materials was 1:4). Under _N2 protection conditions, the mixture was stirred at a high speed at 140°C for 4.5 hours to obtain a phosphorus-containing polyolefin resin with a phosphorus content of 3.1 wt%. Its structure is shown in formula (9), wherein R is methyl.

Homemade compound P7:

Into a three-necked flask, 100 g of acrylate-terminated polybutadiene (EA-3000) and 26.1 g of diphenylphosphine oxide (DPPO) (the molar ratio of EA-3000 to DPPO in the reaction raw material is 1:4) are added in sequence, and the mixture is stirred at a high speed at 140°C for 4.5 hours under _N2 protection conditions to obtain a phosphorus-containing polyolefin resin with a phosphorus content of 3.2 wt%. Its structure is shown in formula (10), wherein R is a hydrogen atom.

Homemade compound P8:

100 g of maleic anhydride-modified polybutadiene (Ricon 130MA8) and 74.9 g of diphenylphosphine oxide (DPPO) (the molar ratio of Ricon 130MA8 to DPPO in the reaction raw materials is 1:10) were added to a three-necked flask in sequence, and the mixture was stirred at high speed at 160°C for 7 hours under _N2 protection to obtain a phosphorus-containing polyolefin resin with a phosphorus content of 6.6 wt%. Its structure is shown in formula (2).

Homemade compound P9:

Into a three-necked flask, 100 g of methacrylate-terminated polybutadiene (EMA-3000) and 139.4 g of 9,10-dihydro-9-oxo-10-phosphophenanthrene-10-oxide (DOPO) were added in sequence (the molar ratio of EMA-3000 to DOPO in the reaction raw materials was 1:20), and the mixture was stirred at high speed at 165°C for 10 hours under _N2 protection to obtain a phosphorus-containing polyolefin resin with a phosphorus content of 8.4 wt%. Its structure is shown in formula (9), wherein R is methyl.

Homemade compound D1:

65 g of Krasol LBH 3000 (hydroxyl-terminated polybutadiene resin) and 34 g of DOPO were placed in a flat-mouthed flask and homogenized at 150°C. Then 1 g of di(tertiary)butyl peroxide was added, and the reaction temperature was raised to 160°C. The reaction mixture was cooled to 150°C and stirred at this temperature for 4 hours to prepare a white product with a softening point of 105°C. The content of free unreacted DOPO in the white product was 1wt%, and the phosphorus content was 5wt%.

Homemade compound D2:

Dissolve the following compound of formula D2-1 in a hydrogen peroxide solution with a concentration of 85wt%, wherein the mass ratio of the compound of formula D2-1 to the hydrogen peroxide solution is 1:3.

The solution was heated to 60°C and stirred for 1 hour, then filtered and washed with pure water until neutral, and dried to obtain the intermediate product D2-2:

26 parts by weight of the intermediate product D2-2 were added to 100 parts by weight of POLYVEST@MA75 (maleic anhydride modified butadiene), heated to 120°C and stirred for 8 hours, cooled to room temperature and filtered to remove impurities, and a light yellow liquid flame retardant product was obtained. The mass ratio of the butadiene main chain and the grafted group formed by D2-2 in the product was 1:0.208.

Homemade Compound D3:

The structure of D3 is as follows:

，其中，k=600至7000；x/k=0.01至0.85；o/k=0.05至0.30。 Z is:

, where k=600 to 7000; x/k=0.01 to 0.85; o/k=0.05 to 0.30.

Homemade Compound D4:

其中，s的取值為15至50。 The structure of D4 is as follows:

The value of s is between 15 and 50.

The resin composition compositions (all in parts by weight) and property test results of the embodiments and comparative examples are shown in the following table:

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

By referring to the test results in Tables 1 to 4, we can see that:

1. Examples E1 to E14 use phosphorus-containing polyolefins (DOPO, DPPO addition modified polybutadiene resins) and add polyphenylene ether resins containing unsaturated carbon-carbon double bonds. Compared with the phosphorus-containing flame retardant prepared by using DOPO addition hydroxyl-terminated polybutadiene resin and adding polyphenylene ether resins containing unsaturated carbon-carbon double bonds, the flame retardant prepared by non-DOPO or DPPO phosphorus-containing compounds grafted on anhydride-modified butadiene is Comparative Example C2, a flame retardant obtained by reacting DOPO with epoxidized polybutadiene and adding a polyphenylene ether resin containing an unsaturated carbon-carbon double bond; Comparative Example C3, a flame retardant obtained by reacting DOPO with acrylic acid and then reacting with terminal hydroxyl polybutadiene and adding a polyphenylene ether resin containing an unsaturated carbon-carbon double bond; Comparative Example C4, a flame retardant obtained by reacting DOPO with acrylic acid and then reacting with terminal hydroxyl polybutadiene and adding a polyphenylene ether resin containing an unsaturated carbon-carbon double bond, the following properties were significantly improved: Tg, PCT and alkali resistance. Among them, the Tg of samples of Examples E1 to E14 is greater than or equal to 200℃, the Tg of samples of Comparative Examples C1 to C4 is less than 200℃, the PCT of samples of Comparative Examples C1 to C4 exploded, while the PCT of samples of Examples E1 to E14 did not explode, the alkali resistance of samples of Examples E1 to E14 is greater than or equal to 10 minutes, and the alkali resistance of samples of Comparative Examples C1 to C4 is less than 10 minutes.

2. Examples E1 to E14 use phosphorus-containing polyolefins (DOPO, DPPO addition-modified polybutadiene resins) and add polyphenylene ether resins containing unsaturated carbon-carbon double bonds. Compared with Comparative Examples C5 to C9 (the phosphorus-containing polyolefins used in Examples E1 to E14 are replaced with DOPO, DPPO and maleic anhydride-modified polybutadiene, maleic anhydride-modified styrene-butadiene copolymer, (meth)acrylate-terminated polybutadiene, which are directly added without reaction and compounded with polyphenylene ether resins containing unsaturated carbon-carbon double bonds), the following properties are significantly improved: anti-adhesion, Tg, Dk, Df, flame retardancy, PCT, substrate appearance and alkali resistance. Compared to Comparative Examples C10 to C11 (Examples E1 to E14 using phosphorus-containing polyolefins instead of phosphorus-free polyolefins and using conventional additive flame retardants (Di-DOPO, Di-DPPO) in combination with polyphenylene ether resins containing unsaturated carbon-carbon double bonds), the following properties were significantly improved: anti-adhesion, flame retardancy, PCT and alkali resistance. Among them, the samples of Examples E1 to E14 are not sticky and do not shed powder, while the samples of Comparative Examples C10 to C11 shed powder. The flame retardancy of the samples of Examples E1 to E14 is V-0, and the flame retardancy of Comparative Examples C10 to C11 is V-1. The PCT of the samples of Comparative Examples C10 to C11 explodes, while the PCT of the samples of Examples E1 to E14 does not explode. The alkali resistance of the samples of Examples E1 to E14 is greater than or equal to 10 minutes, and the alkali resistance of the samples of Comparative Examples C10 to C11 is less than 10 minutes.

3. Comparative Example C12 uses phosphorus-free polyolefin, traditional additive flame retardant and polyphenylene ether resin containing unsaturated carbon-carbon double bonds. In order to meet the flame retardancy requirements, Comparative Example C12 increases the amount of flame retardant Di-DOPO added compared to Comparative Example C10, but other properties are still not improved compared to Comparative Example C10. In addition, Examples E1 to E14 using phosphorus-containing polyolefin and polyphenylene ether containing unsaturated carbon-carbon double bonds have achieved significant improvements in the following properties compared to Comparative Example C12: anti-adhesion, PCT, substrate appearance and alkali resistance. Among them, the samples of Examples E1 to E14 were not sticky and did not shed powder, while the sample of Comparative Example C12 shed powder, and the PCT of the sample of Comparative Example C12 exploded, while the PCT of the samples of Examples E1 to E14 did not explode, the substrates of the samples of Examples E1 to E14 had no stripes or yellow spots, while the substrate of the sample of Comparative Example C12 had stripes, and the alkali resistance of the samples of Examples E1 to E14 was greater than or equal to 10 minutes, while the alkali resistance of the sample of Comparative Example C12 was less than 10 minutes.

4. In the above-mentioned embodiments E1 to E14, E1 to E10 and E13 to E14 respectively have significantly improved properties of products prepared from the resin composition compared to E11 to E12, especially having a higher glass transition temperature, lower dielectric loss and better alkali resistance.

without.

Claims (9)

A resin composition comprises the following components: (A) 100 parts by weight of a polyphenylene ether resin containing unsaturated carbon-carbon double bonds; and (B) 10 to 60 parts by weight of a phosphorus-containing polyolefin resin, wherein the phosphorus-containing polyolefin resin is composed of (a) a structural unit, (b) a structural unit and (d) a structural unit, and/or (a) a structural unit, (b) a structural unit, (c) a structural unit and (d) a structural unit. The structure unit (a) comprises any one of the structure units (a1) and (a2) or a combination thereof, the structure unit (b) comprises any one of the structure units (b1) and (b2) or a combination thereof, the structure unit (d) comprises any one of the structure units (d1), (d2) and (d3) or a combination thereof, wherein R in (d3) is a hydrogen atom or a C ₁ to C ₃ alkyl group,

Wherein, * represents the bonding position between structural units, wherein the phosphorus content of the phosphorus-containing polyolefin resin is 2 to 10 weight percent (wt%). The resin composition as described in claim 1, wherein the polyphenylene ether resin containing unsaturated carbon-carbon double bonds includes any one of vinylbenzyl polyphenylene ether resin, (meth)acryl polyphenylene ether resin, vinyl polyphenylene ether resin or a combination thereof. The resin composition as described in claim 1, wherein the phosphorus content of the phosphorus-containing polyolefin resin is 2.3 to 3.7 weight percent (wt%). The resin composition as described in claim 1, wherein the phosphorus-containing polyolefin resin comprises any one of the phosphorus-containing polyolefin resin represented by formula (1), the phosphorus-containing polyolefin resin represented by formula (2), the phosphorus-containing polyolefin resin represented by formula (3), the phosphorus-containing polyolefin resin represented by formula (4), the phosphorus-containing polyolefin resin represented by formula (5), the phosphorus-containing polyolefin resin represented by formula (6), the phosphorus-containing polyolefin resin represented by formula (7), the phosphorus-containing polyolefin resin represented by formula (8), the phosphorus-containing polyolefin resin represented by formula (9), or the phosphorus-containing polyolefin resin represented by formula (10), or a combination thereof;

In formulae (1) to (10), * represents the bonding position between structural units, p, m, n, q, y or t are each independently p=1 to 200, m=2 to 200, n=10 to 400, q=1 to 100, y=1 to 50, t=1 to 50, and R is each independently a hydrogen atom or a C ₁ to C ₃ alkyl group. The resin composition as described in claim 1, wherein the resin composition further comprises a crosslinking agent containing unsaturated carbon-carbon double bonds, and the crosslinking agent containing unsaturated carbon-carbon double bonds is any one of bis(vinylphenyl)ethane, divinylbenzyl ether, divinylbenzene, divinylnaphthalene, divinylbiphenyl, triallyl isocyanurate, triallyl cyanurate, trivinylcyclohexane, diallylbisphenol A, butadiene, decadiene, octadiene, difunctional or higher acrylates or a combination thereof. The resin composition as claimed in claim 1, wherein the resin composition further comprises a phosphorus-free polyolefin, a maleimide resin, a benzo

Any one of resin, epoxy resin, organic silicone resin, cyanate resin, active ester, phenol resin, amine curing agent, styrene maleic anhydride, polyamide, polyimide or a combination thereof. The resin composition as described in claim 1, wherein the resin composition further includes any one or a combination of flame retardants, hardening accelerators, polymerization inhibitors, inorganic fillers, solvents, silane coupling agents, surfactants, dyes, and toughening agents. A product made from the resin composition described in any one of claims 1 to 7, wherein the product includes a prepreg, a resin film, a laminate or a printed circuit board. The product as described in claim 8, wherein the product has one, more or all of the following characteristics: the dielectric constant measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 3.40, the dielectric loss measured at a frequency of 10 GHz according to the method of JIS C2565 is less than or equal to 0.0040, the glass transition temperature measured according to the method of IPC-TM-650 2.4.24.4 is greater than or equal to 200°C, the flame retardancy level tested according to the method of UL94 is V0, The product is tested for moisture absorption and heat resistance according to the methods of IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, and no board explosion occurs.