resin composition

Abstract

The present invention relates to a resin composition. The resin composition comprises (1) a thermosetting resin including one or more of the following: thermosetting polyphenylene ether resin PPE, thermosetting hydrocarbon resin PCH, epoxy resin EP, polycyanate resin CE, polyimide resin PI, and modified resins thereof; and (2) a silicone-containing crosslinking component. This composition can be used in the field of metal-clad laminates, particularly high-frequency copper-clad laminates.

Description

Technical Field

[0001] The present invention relates to the technical field of metal-clad laminates, and specifically relates to a resin composition, and application thereof to metal-clad laminates and printed wiring boards.

Background Art

[0002] Polyphenylene ether resin (PPE) is known to be excellent in dielectric properties such as dielectric constant and dielectric loss tangent, and also excellent in dielectric properties in a high frequency band from MHz to GHz (high frequency region). Therefore, it is conceivable that a resin composition containing polyphenylene ether resin can be used, for example, as a molding material for high frequency applications. More specifically, it is conceivable that the resin composition can be used as a base material or the like for forming a base material for printed wiring boards used in electronic devices utilizing high frequency bands. When the resin composition is used as a molding material such as a base material, it is required to be excellent not only in dielectric properties, but also in low moisture absorption rate and low water absorption rate under heating.

[0003] CN105358595B discloses a polyphenylene ether resin composition comprising (A) a polyphenylene ether resin end-modified with a substituent having a carbon-carbon unsaturated double bond and (B) a crosslinking agent having a carbon-carbon unsaturated double bond, wherein the crosslinking agent as component (B) contains (B-1) divinylbenzene and (B-2) polybutadiene in a proportion of 50 to 100% by weight.

[0004] CN113527818B discloses a resin composition comprising the following components: (A) a thermosetting resin, wherein the thermosetting resin comprises a combination of at least two selected from the group consisting of thermosetting polyphenylene ether resin, polyfunctional vinyl aromatic polymer, thermosetting hydrocarbon resin, and a co-crosslinking agent containing at least two unsaturated functional groups; and (B) silicon dioxide obtained by hydrolysis of organosilicon, wherein the resin composition not only has low dielectric constant and dielectric loss tangent, but also has small change rate of dielectric loss tangent after moisture absorption under heating, low water absorption and high thermal stability.

[0005] CN103764697A discloses a curable composition for radical polymerization, to which another radical-reactive component C, preferably triallyl isocyanurate, selected from divinylbenzene, trivinylbenzene, 2,3-divinylnaphthalene, 1,4-bis(dimethylvinylmethylsilyl)benzene, may be added to lower the softening point, but does not mention the effect of this composition on the moisture absorption rate under heating. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Chinese Patent No. 105358595 Specification [Patent Document 2] Chinese Patent No. 113527818 Specification [Patent Document 3] Chinese Patent Application Publication No. 103764697 Specification [Overview of the project] [Problems that the invention aims to solve]

[0007] Metal laminates manufactured using resin compositions for metal laminates are known to have insufficient heat resistance and water resistance. The applicant has found that the silicone-containing crosslinking component shown in formula a significantly reduces the moisture absorption rate under heating for thermosetting resins used as substrates for metal-clad laminates, particularly printed circuit boards used in electronic equipment for high-frequency bands. Furthermore, the silicone-containing crosslinking component of the present application exhibits various synergistic effects when combined with various thermosetting resins. These effects include a reduction in water absorption rate when polymerized with thermosetting polyphenylene ether resins, optimization of dielectric constant when polymerized with thermosetting hydrocarbon resins, and overall optimization of peel strength, water absorption rate, dielectric constant, and dielectric loss tangent when polymerized with both thermosetting polyphenylene ether resins and thermosetting hydrocarbon resins.

[0008] [ka] a [Means for solving the problem]

[0009] In a first embodiment, the present invention provides a resin composition comprising: component (1): a thermosetting resin comprising one or more of thermosetting polyphenylene ether resins, thermosetting hydrocarbon resins, epoxy resins, polycyanate resins, polyimide resins, and modified resins thereof; and component (2): a silicone-containing crosslinking component shown in formula a. The aforementioned resin composition can be used to produce a metal-clad laminate with excellent moisture absorption rate under heating.

[0010] [ka] a [Modes for carrying out the invention]

[0011] The aforementioned thermosetting resin refers to a commercially available thermosetting resin with excellent dielectric properties used in clad metal laminates, and is selected from one or more of the following: thermosetting polyphenylene ether resin, thermosetting hydrocarbon resin, epoxy resin, cyanate ester resin, polyimide resin, and modified resins thereof.

[0012] The aforementioned thermosetting polyphenylene ether resins include epoxy-modified polyphenylene ether resins, vinyl-modified polyphenylene ether resins, or acylated polyphenylene ether resins, and preferably are polyphenylene ether resins containing unsaturated groups, and more preferably terminal groups containing unsaturated hydrocarbon groups.

[0013] Specifically, these are polyphenyl ether resins having vinylphenyl functional groups, such as vinylbenzyl ether polyphenyl ether resins or vinylphenyl ether polyphenyl ether resins. Specifically, these are polyphenyl ether resins having acrylate ester functional groups, such as (meth)acrylate-terminated polyphenylene ether resins or acrylate-terminated polyphenylene ether resins.

[0014] Polyphenylene ether resins having acrylates are preferred, and (meth)acrylate-terminated polyphenylene ether resins are more preferred.

[0015] The number-average molecular weight (Mn) of the thermosetting polyphenylene ether resin is not particularly limited and is selected from 1000 to 7000 g / mol, preferably 1000 to 5000 g / mol, and more preferably 1000 to 3000 g / mol. The number-average molecular weight used herein can be easily measured using general molecular weight measurement methods, specifically, by gel permeation chromatography (GPC).

[0016] In the present invention, the thermosetting polyphenylene ether resin can be purchased by market means, such as OPE-2ST manufactured by Mitsubishi Gas Chemical Company, Inc. and / or NORYL SA9000 manufactured by SABIC.

[0017] The mass percentage of thermosetting polyphenylene ether resin in the aforementioned thermosetting resin is 10 to 90% by weight, preferably 20 to 80% by weight, and more preferably 25 to 70% by weight, such as 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0018] The intrinsic viscosity of the thermosetting polyphenylene ether is preferably 0.03 to 0.12 dl / g, more preferably 0.04 to 0.11 dl / g, and still more preferably 0.06 to 0.10 dl / g. If the intrinsic viscosity is too low, the molecular weight tends to be low, and low dielectric properties such as low dielectric constant and low dielectric loss tangent tend to be difficult to obtain. In addition, if the intrinsic viscosity is too high, sufficient fluidity cannot be obtained due to the high viscosity, and the moldability of the cured product tends to decrease. Therefore, when the intrinsic viscosity of the modified polyphenylene ether is within the above range, the cured product exhibits excellent heat resistance and adhesion. The aforementioned intrinsic viscosity is measured according to the SABIC method.

[0019] The aforementioned thermosetting hydrocarbon resins include polybutadiene, styrene-butadiene copolymers, styrene-butadiene-divinylbenzene copolymers, styrene-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, maleimide-modified polybutadiene resins, epoxy-modified polybutadiene resins, styrene resins, methylene-styrene resins, ethylstyrene resins, divinylbenzene resins, isoprene resins, benzocyclobutene resins, and the like.

[0020] It is preferably polybutadiene and / or styrene-butadiene-styrene copolymer (butylbenzene resin), and more preferably polybutadiene.

[0021] Examples include 1,4-polybutadiene, 1,2-polybutadiene, terminal acrylate-modified polybutadiene, terminal urethane methacrylate-modified polybutadiene, and the like.

[0022] The number average molecular weight (Mn) of the thermosetting hydrocarbon resin is not particularly limited, and is selected from 100 to 5000 g / mol, preferably 500 to 4000 g / mol, more preferably 1000 to 3500 g / mol.

[0023] In the present invention, the thermosetting hydrocarbon resin can be purchased by market means, for example, B-3000 from Nippon Soda Co., Ltd., R154 from Cray Valley USA, RB810 from JSR Corporation of Japan, or R100 from Cray Valley USA.

[0024] The mass percentage of thermosetting hydrocarbon resin in the aforementioned thermosetting resin is 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 25 to 70% by weight, and may be, for example, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0025] The aforementioned epoxy resins include bisphenol A type brominated epoxy resins, non-brominated bisphenol A type epoxy resins, phenolphenol resins, procresolphenol resins, bisphenol A type phenol epoxy resins, DCPC type epoxy resins, biphenyl type epoxy resins, naphthol type epoxy resins, alkylphenol type epoxy resins, aliphatic type epoxy resins, trifunctional epoxy resins, nitrogen-containing epoxy resins, and the like. Preferably, the epoxy resin contains unsaturated groups. For example, dicyclopentadiene type epoxy resin (XD-1000L, Nippon Chemicals).

[0026] In this invention, the epoxy resin can be purchased by market means, for example, XD-1000L from Nippon Corporation.

[0027] The mass percentage of epoxy resin in the aforementioned thermosetting resin is 10 to 90% by weight, preferably 20 to 80% by weight, and more preferably 25 to 70% by weight, such as 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0028] The aforementioned cyanate ester resins include bisphenol A type cyanate ester resin, DCPD type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol F type cyanate ester resin, phenol type cyanate ester resin, alkylphenol type cyanate ester resin, or naphthol type cyanate ester resin.

[0029] In the present invention, the cyanate ester resin can be purchased by market means, for example, LONZA's Primset HTL-300.

[0030] The mass percentage of cyanate ester resin in the aforementioned thermosetting resin is 10 to 90% by weight, preferably 20 to 80% by weight, and more preferably 25 to 70% by weight, such as 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0031] The aforementioned polyimide resin PI is preferably a bismaleimide-type polyimide resin, such as 4,4'-diphenylmethanebismaleimide, 4,4'-diphenylisopropylbismaleimide, or 4,4'-diphenylene etherbismaleimide, and the bismaleimide resin preferably includes one or more of diamine-modified bismaleimide resins or allyl-modified bismaleimide resins.

[0032] In this invention, the bismaleimide resin is commercially available, for example, XU292 manufactured by Ciby-Geigy.

[0033] The mass percentage of polyimide resin in the aforementioned thermosetting resin is 10 to 90% by weight, preferably 20 to 80% by weight, and more preferably 25 to 70% by weight, such as 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0034] Preferably, the aforementioned thermosetting resin includes one or more of the following: thermosetting polyphenylene ether resin, thermosetting hydrocarbon resin, and modified resins thereof.

[0035] Preferably, the mass ratio of the thermosetting polyphenylene ether resin to the thermosetting hydrocarbon resin is 0.01 to 100, more preferably 0.02 to 50, and even more preferably 0.1 to 10, such as 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, and 9.

[0036] Component (1): The mass percentage of the thermosetting resin is 20 to 80% by weight, preferably 30 to 70% by weight, and more preferably 45 to 65% by weight, with the total mass of the resin components being 100% by weight. Examples include 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, etc.

[0037] The term "resin component" refers to a mixture or monomer of polymers containing hydrocarbon structures, primarily comprising thermosetting resins, silicone-containing crosslinking components, cocrosslinking agents, and other organic components, but not containing fillers, initiators, flame retardants, solvents, reinforcing materials, etc.

[0038] The aforementioned component (2) is the silicone-containing crosslinking component shown in formula a.

[0039] [ka] a (wherein R is independently selected from a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably phenyl, methyl, or ethyl.) R* is a substituted and / or unsubstituted unsaturated hydrocarbon group having 1 to 16 carbon atoms and bonded to SiC, which may be interrupted by heteroatoms and / or carbonyl groups. Preferably, the aforementioned unsaturated hydrocarbon groups having 2 to 10 carbon atoms, such as vinyl, phenylvinyl, allyl, isopropenyl, acrylic acid or methacrylic acid, 4-vinylcyclohexyl and 3-norborneyl. (More preferably, it is independently selected from alkenyl groups having 2 to 10 carbon atoms.)

[0040] Specifically, the aforementioned silicone-containing crosslinking component is one or more of the following: bis(dimethylvinylmethylsilyl)benzene, bis(dimethylallylmethylsilyl)benzene, bis(dimethylphenylvinylmethylsilyl)benzene, bis(dimethylisopropenylmethylsilyl)benzene, bis(dimethylmethacrylatetomethylsilyl)benzene, and bis(dimethylmethylacrylatetomethylsilyl)benzene.

[0041] Preferably, one or more of 1,2-bis(dimethylvinylmethylsilyl)benzene, 1,3-bis(dimethylvinylmethylsilyl)benzene, and 1,4-bis(dimethylvinylmethylsilyl)benzene are selected, and more preferably, 1,4-bis(dimethylvinylmethylsilyl)benzene (formula b).

[0042] [ka] b

[0043] Component (2): The mass percentage of the silicone-containing crosslinking component shown in formula a is 2 to 80% by weight, preferably 2 to 60% by weight, and more preferably 2 to 40% by weight, with the total mass of the resin components being 100% by weight. Examples include 5%, 8%, 10%, 15%, 18%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, etc.

[0044] Preferably, the aforementioned resin composition further comprises component (3): co-crosslinking agent, the co-crosslinking agent comprising one or more of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethylallyl isocyanate (TMAIC), divinylbenzene (DVB), 1,2-bis(p-vinylphenyl)ethane (BVPE), or 1,2,4-trivinylcyclohexane (TVCH).

[0045] The mass percentage of the cocrosslinking agent is 1 to 40% by weight, preferably 1 to 35% by weight, and more preferably 1 to 30%, with the total mass of the resin components being 100% by weight. Examples include 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%, etc.

[0046] Preferably, the aforementioned resin composition further comprises component (4): initiator, wherein the initiator comprises one or more of an organic peroxide initiator, an azo initiator, or a carbon-based radical initiator.

[0047] Preferably, the organic peroxide initiator comprises one or more of tert-butylisopropylphenyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexine, or 1,1-bis(tert-butylperoxy)-3,3,5-dimethylcyclohexane, and more preferably comprises 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane or dicumyl peroxide.

[0048] Preferably, the carbon-based radical initiator includes bicuculin and / or polybicucrin.

[0049] The mass percentage of the initiator is 0.001 to 3%, preferably 0.002 to 3%, with the total mass of the resin components being 100% by weight. Examples include 0.003%, 0.005%, 0.008%, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, or 2.8%.

[0050] A solvent may be added to the resin composition described above. The amount of solvent added should be selected by those skilled in the art based on experience and process requirements so that the resin composition reaches a viscosity suitable for use, thereby facilitating impregnation, coating, and the like of the resin composition. Subsequently, the solvent in the resin composition partially or completely evaporates during the drying, semi-curing, or fully curing process.

[0051] The choice of solvent is not particularly limited, and typically ketones, such as acetone, butanone, cyclohexanone, and other ketones, aromatic hydrocarbons, such as toluene, xylene, and other aromatic hydrocarbons, and esters, such as ethyl acetate, butyl acetate, and other esters, can be used alone or as a mixture of two or more solvents. Ketones, such as acetone, butanone, cyclohexanone, and other ketones, and aromatic hydrocarbons, such as toluene and xylene, are preferred.

[0052] Preferably, the aforementioned resin composition further comprises component (5): a flame retardant. The flame retardant is not particularly limited, but examples include halogenated flame retardants such as brominated flame retardants and phosphorus-based flame retardants.

[0053] Examples of halogenated flame retardants include brominated flame retardants such as pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, and hexabromocyclododecane; and chlorinated flame retardants such as chlorinated paraffins. These flame retardants may be used individually or in combination of two or more.

[0054] Examples of phosphorus-based flame retardants include phosphate esters, such as condensed phosphate esters and cyclic phosphate esters; phosphazene compounds, such as cyclic phosphazene compounds; phosphinic acid-based flame retardants, such as metal salts of phosphinic acid, such as aluminum dialkylphosphinate; and melamine-based flame retardants, such as melamine phosphate and melamine polyphosphate. These flame retardants may be used individually or in combination of two or more.

[0055] The mass percentage of the flame retardant is 1 to 50%, preferably 10 to 25%, based on the total mass of the resin components being 100% by weight, such as 11%, 13%, 15%, 17%, 19%, 20%, 21%, 22%, 23%, or 24%.

[0056] Preferably, the aforementioned resin composition further comprises component (6): an inorganic filler material, the inorganic filler material comprising one or more of silicon dioxide, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium dioxide, mica, aluminum borate, barium sulfate, and calcium carbonate.

[0057] When inorganic filler material is added, the amount added is not particularly limited. Specifically, the mass percentage of the inorganic filler is 10 to 300% by weight, preferably 50 to 150% by weight, with the total mass of the resin components being 100% by weight. Examples include 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140%, etc.

[0058] The aforementioned resin composition comprises, with a total mass of resin components of 100% by weight, 20 to 98% by weight of component (1): thermosetting resin, and 2 to 80% by weight of component (2): silicone-containing crosslinking component shown in formula a.

[0059] Preferably, with the total mass of the resin components being 100% by weight, the components consist of 30-98% by weight of component (1): thermosetting resin, 2-70% by weight of component (2): silicone-containing crosslinking component shown in formula a, and 0-40% by weight of cocrosslinking agent.

[0060] More preferably, with the total mass of the resin components being 100%, the components (1) consist of 45-98% by weight, for example, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 70%, 75%, 80%, 85%, 90%, and 95% by weight: thermosetting resin; Components (2) in amounts of 2-60% by weight, for example 5% by weight, 8% by weight, 10% by weight, 15% by weight, 18% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 58% by weight: Silicone-containing crosslinking components shown in formula a; and It contains 5 to 25% by weight of a cocrosslinking agent, for example, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, and 24% by weight.

[0061] With respect to the total mass of the resin components, the proportion of component (1): thermosetting resin, component (2): silicone-containing crosslinking component shown in formula a, and component (3): co-crosslinking agent is greater than 70% by weight, preferably 80% by weight, more preferably 90% by weight, and even more preferably 95% by weight.

[0062] The weight ratio of component (1): thermosetting resin to component (2): silicone-containing crosslinking component shown in formula a is in the range of 0.01 to 100, preferably 0.02 to 50, for example 0.04 to 40, 0.05 to 30, 0.06 to 20, 0.07 to 15, and more preferably 0.1 to 10, for example 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9.

[0063] With respect to the total mass of the resin components, the proportion of component (1): thermosetting resin and component (2): silicone-containing crosslinking component shown in formula a is greater than 50%, preferably greater than 60% by weight, more preferably greater than 70%, for example, 75% by weight, 80% by weight, 85% by weight, 90% by weight, or 95% by weight.

[0064] In a second embodiment, the present invention provides a prepreg comprising a reinforcing material and a resin composition that partially hardens by drying after impregnation and coating.

[0065] Preferably, the reinforcing material includes one or more of the following: natural fibers, organic synthetic fibers, organic fabrics, inorganic fibers; for example, glass cloth, aramid cloth, polyester cloth, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and cotton tufted paper. Low dielectric reinforcing materials such as NE glass fiber cloth can also be selected as desired.

[0066] In a third embodiment, the present invention provides a metal-clad laminate.

[0067] Metal-clad laminates are produced by a method that includes laminating metal foil onto one or both sides of a single prepreg and curing it to obtain a metal-clad laminate, or by a method that includes laminating at least two prepregs to form a laminate, then laminating metal foil onto one or both sides of the laminate and curing it to obtain a metal-clad laminate.

[0068] Preferably, the metal foil is copper foil.

[0069] Preferably, the curing temperature is 150-300°C, for example, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 212°C, 215°C, 218°C, 220°C, 223°C, 225°C, 228°C, 230°C, 235°C, 240°C, 245°C, 250°C, 255°C, 260°C, 265°C, 270°C, 275°C, 280°C, 285°C, or 290°C.

[0070] Preferably, the curing pressure is 1.2 to 5 MPa, more preferably 1.2 to 4 MPa, such as 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2.0 MPa, 2.1 MPa, 2.2 MPa, 2.3 MPa, 2.4 MPa, 2.5 MPa, 2.6 MPa, 2.7 MPa, 2.8 MPa, 2.9 MPa, 3.0 MPa, 3.1 MPa, 3.2 MPa, 3.3 MPa, 3.4 MPa, 3.5 MPa, 3.6 MPa, 3.7 MPa, 3.8 MPa, 3.9 MPa, etc.

[0071] Preferably, the curing time is 60 to 360 minutes, for example, 80, 90, 100, 120, 140, 150, 160, 180, 200, 220, 240, 260, 280, 300, 320, or 340 minutes.

[0072] In a fourth aspect, the present invention provides a printed circuit board comprising one or more of the aforementioned prepregs or metal-clad laminates.

[0073] Compared to prior art, the present invention has the following beneficial effects.

[0074] The silicone-containing crosslinking component of this application significantly reduces the moisture absorption rate under heating for thermosetting resins used as substrates for metal-clad laminates, particularly printed circuit boards used in high-frequency electronic equipment. The resin composition and metal laminate of this application exhibit excellent moisture absorption under heating, solving the problem of reduced dielectric properties caused by water absorption due to high-frequency heat generation. Furthermore, the silicone-containing crosslinking component of this application shows various synergistic effects when combined with various thermosetting resins. These effects include a reduction in water absorption rate when polymerized with thermosetting polyphenylene ether resins, optimization of dielectric constant when polymerized with thermosetting hydrocarbon resins, and overall optimization of peel strength, water absorption rate, relative properties, and dielectric properties when polymerized with both thermosetting polyphenylene ether resins and thermosetting hydrocarbon resins. [Examples]

[0075] Thermosetting polyphenylene ether resin: NORYL SA9000 (manufactured by SABIC) Thermosetting hydrocarbon resin: Polybutadiene B-3000 (manufactured by Nippon Soda Co., Ltd.) Silicone-containing crosslinking component: 1,4-bis(dimethylvinylmethylsilyl)benzene (manufactured by Wacker Chemie AG) Co-crosslinking agent: Triallyl isocyanurate (TAIC) (manufactured by Sigma-Aldrich Co., LLC) Initiator: Dicumyl peroxide (DCP) (commercial product) Solvent: Xylene (XYL) (commercial product) Filler: Silicon dioxide (manufactured by Suzhou Ginet material) Reinforcement material: NE glass fiber cloth 1080 (commercially available product) Metal foil: 35μm thick copper foil (manufactured by Jiangxi Copper Group Co., Ltd.)

[0076] Method for adjusting copper-clad laminates: The resin composition was adjusted to the appropriate amount shown in Tables 1 and 2, and dissolved with xylene XYL to obtain varnish. Glass cloth cut into 25cm x 25cm squares was immersed in the varnish and dried in a 150°C oven for 5 minutes to prepare a prepreg. Six of these prepregs were laminated together, and 35μm thick copper foil was placed on both sides of the laminate to form a pressure-bearing body. The copper foil was then bonded to both sides by heating and pressurizing at a temperature of 280°C and a pressure of 1.5MPa (megapascals) for 180 minutes to obtain a copper-clad laminate.

[0077] The copper foil peel strength of the copper-clad laminate was tested, and the water absorption rate (%), PCT moisture absorption rate (%), dielectric constant Dk (10 GHz), and dielectric loss tangent Df (10 GHz) of the copper-clad laminate after etching were tested and recorded in Tables 1 and 2.

[0078] Peel strength (PS, pounds / inch): Test the peel strength of the copper foil according to IPC-TM-650 2.4.8.

[0079] Water absorption rate (%): Test the water absorption rate according to IPC-TM-650 2.6.2.1.

[0080] PCT moisture absorption rate (%): After treating the test specimen at 121°C, 105 kPa, and 100% relative humidity for 180 minutes, the change in weight before and after treatment was calculated.

[0081] Dielectric constant Dk (10 GHz): Test Dk at a frequency of 10 GHz according to IPC-TM-650 2.5.5.13.

[0082] Dielectric loss tangent Df (10 GHz): Test Df at a frequency of 10 GHz according to IPC-TM-650 2.5.5.13.

[0083] [Table 1]

[0084] As shown in Table 1, compared to the copper-clad laminate obtained from the silicone-containing resin without crosslinking in Comparative Example 1, both Examples 2 and 3 exhibit superior PCT moisture absorption rates. Furthermore, Example 2 shows a reduction in water absorption rate, and Example 3 shows an optimized Df value.

[0085] [Table 2]

[0086] As shown in Table 2, compared to Comparative Example 4, a copper-clad laminate made from B3000 and SA9000 resin components without silicone-containing crosslinking, Example 5, which contains thermosetting hydrocarbon resin B3000, thermosetting polyphenylene ether resin SA9000, and silicone-containing crosslinking component 1,4-bis(dimethylvinylmethylsilyl)benzene in its resin components, not only exhibited excellent PCT moisture absorption rate, but also showed well-optimized peel strength, water absorption rate, Dk, and Df.

Claims

1. A resin composition, Component (1): A thermosetting resin comprising one or more of the following: thermosetting polyphenylene ether resin, thermosetting hydrocarbon resin, epoxy resin, polycyanate resin, polyimide resin, and modified resins thereof, and Component (2): Silicone-containing crosslinking component shown in formula a 【Chemistry 1】 a (In the formula, R is independently selected from a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably phenyl, methyl, or ethyl.) A resin composition comprising a C1-C16 SiC-bonded substituted and / or unsubstituted unsaturated hydrocarbon group, preferably a C2-C10 unsaturated hydrocarbon group, such as vinyl, phenylvinyl, allyl, isopropenyl, acrylic acid, or methacrylic acid, which may be interrupted by heteroatoms and / or carbonyls, and more preferably an alkenyl group with C2-C10.

2. The resin composition according to claim 1, wherein the thermosetting resin comprises one or more of a thermosetting polyphenylene ether resin and a thermosetting hydrocarbon resin, and preferably the mass ratio of the thermosetting polyphenylene ether resin to the thermosetting hydrocarbon resin is 0.01 to 100, more preferably 0.02 to 50, and even more preferably 0.1 to 10, for example 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9.

3. The resin composition according to claim 1 or 2, further comprising component (3): a co-crosslinking agent, wherein the crosslinking agent comprises one or more of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethylallyl isocyanate (TMAIC), divinylbenzene (DVB), 1,2-bis(p-vinylphenyl)ethane (BVPE), or 1,2,4-trivinylcyclohexane (TVCH).

4. The resin composition according to any one of claims 1 to 3, wherein the number average molecular weight of the thermosetting polyphenylene ether resin is selected from 1,000 to 7,000 g / mol, preferably 1,000 to 5,000 g / mol, and more preferably 1,000 to 3,000 g / mol.

5. The resin composition according to any one of claims 1 to 4, wherein the thermosetting hydrocarbon resin comprises polybutadiene and / or styrene-butadiene-styrene copolymer, preferably polybutadiene.

6. The resin composition according to any one of claims 1 to 5, wherein the thermosetting hydrocarbon resin has a number average molecular weight of 100 to 5000 g / mol, preferably 500 to 4000 g / mol, and more preferably 1000 to 3500 g / mol.

7. Component (2): The resin composition according to any one of claims 1 to 6, wherein the silicone-containing crosslinking component is bis(dimethylvinylmethylsilyl)benzene, preferably 1,4-bis(dimethylvinylmethylsilyl)benzene.

8. With the total mass of the resin components being 100%, the product comprises: Component (1): 20 to 98% by weight of thermosetting resin and Component (2): 2 to 80% by weight of the silicone-containing crosslinking component shown in formula a. Preferably, with the total mass of the resin components being 100%, the component (1) comprises 30 to 98% by weight of thermosetting resin, and component (2) comprises 2 to 70% by weight of the silicone-containing crosslinking component shown in formula a and 0 to 40% by weight of the cocrosslinking agent. More preferably, the resin composition according to any one of claims 1 to 7, wherein the total mass of the resin components is 100%, and comprises: component (1): 45 to 98% by weight of thermosetting resin, component (2): 2 to 60% by weight of silicone-containing crosslinking component shown in formula a, and component (3): 5 to 25% by weight of cocrosslinking agent.

9. The resin composition according to any one of claims 1 to 8, wherein the proportion of component (1): thermosetting resin, component (2): silicone-containing crosslinking component shown in formula a, and component (3): co-crosslinking agent, relative to the total mass of the resin components, is greater than 70% by weight, preferably 80% by weight, more preferably 90% by weight, and even more preferably 95% by weight.

10. The weight ratio of component (1): thermosetting resin to component (2): silicone-containing crosslinking component shown in formula a is in the range of 0.01 to 100, preferably in the range of 0.02 to 50, more preferably in the range of 0.1 to 10, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and / or The resin composition according to any one of claims 1 to 9, wherein the proportion of component (1): thermosetting resin and component (2): silicone-containing crosslinking component shown in formula a, relative to the total mass of the resin components, is greater than 70%, preferably greater than 75% by weight, more preferably greater than 80%, for example, 85% by weight, 90% by weight, or 95% by weight.

11. Use of the resin composition according to any one of claims 1 to 10 as a substrate for metal-clad laminates.

12. A prepreg comprising a reinforcing material and a resin composition according to any one of claims 1 to 10.

13. A metal-clad laminate manufactured from the prepreg described in claim 12.

14. A printed circuit board comprising the prepreg described in claim 12 or the metal-clad laminate described in claim 13.

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