CN113527818B

CN113527818B - Resin composition and application thereof

Info

Publication number: CN113527818B
Application number: CN202110923205.7A
Authority: CN
Inventors: 罗成; 柴颂刚; 颜善银
Original assignee: Shengyi Technology Co Ltd
Current assignee: Shengyi Technology Co Ltd
Priority date: 2021-08-12
Filing date: 2021-08-12
Publication date: 2022-11-29
Anticipated expiration: 2041-08-12
Also published as: TWI802482B; WO2023016244A1; CN113527818A; TW202307131A

Abstract

The invention provides a resin composition and application thereof, wherein the resin composition comprises the following components: (A) A thermosetting resin comprising a combination of at least two of a thermosetting polyphenylene ether, a polyfunctional vinyl aromatic polymer, a thermosetting hydrocarbon resin, or a co-crosslinking agent containing at least two unsaturated functional groups; (B) The silicon dioxide is prepared by an organic silicon hydrolysis method, the purity of the silicon dioxide is more than or equal to 99.9 percent, the average grain diameter is 0.1-3 mu m, and the radial distance is less than 1; the mass percentage of the silicon dioxide in the resin composition is 20-70%. The resin composition has low dielectric constant and low dielectric loss, and has small change rate of dielectric loss after moisture absorption, low water absorption and high thermal stability; the prepreg prepared from the resin composition can fully meet the performance requirements of a high-frequency high-speed copper foil substrate.

Description

Resin composition and application thereof

Technical Field

The invention belongs to the technical field of copper-clad plates, and particularly relates to a resin composition and application thereof.

Background

The copper-clad plate is a plate-shaped material which is formed by impregnating insulating paper, glass fiber cloth or other fiber materials with resin, coating copper foil on one surface or two surfaces and carrying out hot pressing, and is a basic material of a Printed Circuit Board (PCB). In the quartz glass currently used in the copper-clad plate, the mass content of silicon dioxide is 98.5-99.7%, the mass content of aluminum oxide is 0.1-0.3%, the mass content of water is 0.1-0.3%, the mass content of sodium oxide is 0.05-0.1%, the mass content of potassium oxide is 0.05-0.1%, the mass content of lithium oxide is 0.05-0.1%, the mass content of calcium oxide is 0.05-0.1%, the mass content of magnesium oxide is 0.05-0.1%, the mass content of barium oxide is 0.05-0.1%, the mass content of strontium oxide is 0.05-0.1%, the mass content of ferric oxide is 0.05-0.2%, the mass content of titanium dioxide is 0.05-0.1%, the dielectric constant is more than 3.8, the dielectric loss is more than 0.001, and the material with the lowest dielectric constant and dielectric loss in the currently easily obtained filler. The quartz glass powder is used in the copper-clad plate, has the minimum influence on the dielectric property of the copper-clad plate, and can replace high-cost resin with low dielectric constant and low dielectric loss, so that a large amount of quartz glass powder is used as a filler in the copper-clad plate with low dielectric constant and low dielectric loss. With the improvement of the requirements of the copper-clad plate on dielectric constant and dielectric loss, the dielectric constant Dk is required to be less than 3.8, the dielectric loss Df is required to be less than 0.001, and the current quartz glass can not meet the requirements of the copper-clad plate.

CN112500608A discloses a preparation method of fused silica micropowder for high-frequency high-speed copper-clad plate, which uses high-purity fused silica micropowder as raw material to obtain D through crushing, grading and surface treatment with fluorosilane ₅₀ The fused silica powder with the diameter of 7.0-15.0 microns is suitable for a high-frequency high-speed copper-clad plate, but the diameter distance is 1.32, which shows that the silica powder has wide particle size distribution, so that more interfaces are crossed in the signal transmission process, energy loss is caused, and the Df is higher. CN105131527A discloses a low dielectric constant copper-clad plate and a manufacturing method thereof, wherein cristobalite powder made of high-purity gangue quartz ore is adopted as an inorganic filler to reduce the dielectric constant of the copper-clad plate, and the purity of silicon dioxide is reduced in the grinding, crushing and pelletizing processes of the cristobalite powderAffecting Df of the silica; also, since the fused silica produced by the flame method has a wide particle size distribution, the Df change rate after moisture absorption of the resin composition is large. CN103771423A discloses a spherical filler for electronic packaging and a manufacturing method thereof, wherein the spherical filler takes silica as a main component, but the particle size distribution is wide, the moisture absorption rate is still high, and the Df change rate of the composite material after moisture absorption is large. CN103450639A discloses a thermosetting resin composition and its use, wherein the thermosetting resin composition contains silicon dioxide with a closed surface and a porous interior, the silicon dioxide is prepared by a chemical method, and is an aggregate of spherical silicon obtained by a chemical method for hydrolyzing organic silicon, and then the aggregate is burned to obtain the silicon dioxide with a closed surface and a porous interior; since the aggregate of the chemical spherical silicon is directly burned in the manufacturing process and is not depolymerized into single particles, part of impurities can be sealed in the silicon dioxide with closed surface and porous inside in the burning process, and Df is increased. CN1634763A discloses a method for preparing nano-grade high-purity silica, which adopts a chemical direct synthesis method to obtain a product with a particle size of 5-20 nm, but because the particle size is about 10nm, the viscosity of glue solution is very high, which brings a very large negative effect on the process for preparing a bonding sheet of a Copper Clad Laminate (CCL), and a qualified bonding sheet cannot be prepared.

Therefore, it is an urgent need in the art to develop a composite material with low dielectric constant, low dielectric loss and low Df change rate after moisture absorption to meet the use requirements of high-frequency and high-speed copper foil substrates.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a resin composition and application thereof, wherein the resin composition has low dielectric constant and low dielectric loss by compounding the thermosetting resin with low dielectric constant and specific silicon dioxide, and has the advantages of small change rate of dielectric loss after moisture absorption, low water absorption, high thermal stability and good reliability; the prepreg prepared from the resin composition can fully meet the performance requirements of a high-frequency high-speed copper foil substrate.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a resin composition comprising the following components:

(A) A thermosetting resin comprising a combination of at least two of a thermosetting polyphenylene ether, a polyfunctional vinyl aromatic polymer, a thermosetting hydrocarbon resin, or a co-crosslinking agent containing at least two unsaturated functional groups;

(B) Silicon dioxide, wherein the silicon dioxide is prepared by an organic silicon hydrolysis method, the purity of the silicon dioxide is more than or equal to 99.9 percent, and the average particle size (D) of the silicon dioxide ₅₀ ) 0.1-3 μm, and the radial distance is less than 1;

the content of silica in the resin composition may be, for example, 20 to 70% by mass, for example, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, or 68%.

The resin composition provided by the invention adopts the compounding of the thermosetting resin with low dielectric constant and the silicon dioxide, and the silicon dioxide is prepared by a chemical method (an organic silicon hydrolysis method), has high purity and average particle size (D) ₅₀ ) 0.1 to 3 μm, a small diametral distance, a narrow particle size distribution of the silica particles, a high uniformity of particle sizes of the respective particles, a low dielectric constant (Dk), a low dielectric dissipation factor (Df), a low hygroscopicity, a low rate of change of Df after moisture absorption, a high glass transition temperature, and an excellent thermal stability. The non-viscous prepreg prepared from the resin composition can be processed into a copper-clad plate by automation, so that the Dk and Df of the copper-clad plate are less than 3.5 and less than 0.0020 under the condition of 10GHz, and the requirements of high frequency and high speed are fully met.

In the present invention, the purity of the silica is not less than 99.9%, and may be, for example, 99.92%, 99.95%, 99.97%, 99.99%, 99.991%, 99.993%, 99.995%, 99.997%, 99.999%, or the like.

The purity of the silicon dioxide is measured by adopting an inductively coupled atomic emission spectrometer (ICP-AES).

Average particle diameter (D) of the silica ₅₀ ) 0.1 to 3 muThe m may be, for example, 0.2. Mu.m, 0.5. Mu.m, 0.8. Mu.m, 1. Mu.m, 1.2. Mu.m, 1.5. Mu.m, 1.8. Mu.m, 2. Mu.m, 2.2. Mu.m, 2.5. Mu.m, 2.8. Mu.m, or the like.

The silica may have a caliper < 1, and may be, for example, 0.95, 0.9, 0.85, 0.8, 0.75, 0.7, 0.65, 0.6, 0.55, 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, or 0.15.

In the present invention, the parameter (e.g., D) related to the particle diameter ₅₀ 、D ₁₀ 、D ₉₀ Radial distance, etc.) can be obtained by testing with a Malvern 3000 laser particle size analyzer; in addition, the radial distance can also be obtained by the following calculation formula: radius distance = (D) ₉₀ –D ₁₀ )/D ₅₀ 。

In the present invention, the thermosetting resin of component (a) includes a combination of at least two of a thermosetting polyphenylene ether, a polyfunctional vinyl aromatic polymer, a thermosetting hydrocarbon resin, or a co-crosslinking agent containing at least two unsaturated functional groups, and exemplary combinations include: a combination of a thermosetting polyphenylene ether and a polyfunctional vinyl aromatic polymer, a combination of a thermosetting polyphenylene ether and a thermosetting hydrocarbon resin, a combination of a thermosetting polyphenylene ether and an auxiliary crosslinking agent, a combination of a polyfunctional vinyl aromatic polymer and a thermosetting hydrocarbon resin, a combination of a thermosetting polyphenylene ether, a thermosetting hydrocarbon resin and an auxiliary crosslinking agent, a combination of a polyfunctional vinyl aromatic polymer, a thermosetting hydrocarbon resin and an auxiliary crosslinking agent, a combination of a thermosetting polyphenylene ether, a polyfunctional vinyl aromatic polymer, a thermosetting hydrocarbon resin and an auxiliary crosslinking agent, and the like.

Preferably, the silica is prepared by a process comprising: carrying out hydrolysis reaction on organic silicon to obtain a primary product; and firing the primary product to obtain the silicon dioxide.

Preferably, the silicone is an alkoxysilane.

Preferably, the alkoxy silane comprises any one or a combination of at least two of tetraethoxy silane, tetramethoxy silane, tetraphenoxy silane, tetra-n-butoxy silane, tetra-iso-butoxy silane, methyl triethoxy silane and dimethyl diethoxy silane;

preferably, the firing temperature is 800 to 1300 ℃, for example, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, or the like.

Preferably, the purity of the silica is > 99.95%, more preferably > 99.99%.

Preferably, the silica has a caliper of < 0.85, more preferably < 0.65.

The content of the thermosetting resin in the resin composition is preferably 10 to 80% by mass, and may be, for example, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, or 78%.

The thermosetting polyphenylene ether preferably has a number average molecular weight of 500 to 10000g/mol, and may be, for example, 600g/mol, 800g/mol, 1000g/mol, 1500g/mol, 2000g/mol, 2500g/mol, 3000g/mol, 3500g/mol, 4000g/mol, 4500g/mol, 5000g/mol, 6000g/mol, 7000g/mol, 8000g/mol, 9000g/mol or 9500 g/mol.

Preferably, the thermosetting polyphenylene ether is a polyphenylene ether containing an unsaturated group, and more preferably a polyphenylene ether having an unsaturated group as a terminal group.

Preferably, the thermosetting polyphenylene ether has a structure shown below:

wherein Z is

Or

The wavy line represents the attachment site of the group.

A is selected from any one of-CO-, C6-C30 (C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) arylene, C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched chain alkylene; wherein said C6-C30 arylene illustratively includes, but is not limited to: phenylene, biphenylene, terphenylene, naphthylene, or the like; the C1 to C10 linear or branched alkylene group illustratively includes, but is not limited to: methylene, ethylene, propylene or butylene, and the like.

R ₁ 、R ₂ 、R ₃ Each independently selected from any one of hydrogen, C1-C10 (e.g. C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched chain alkyl.

In the present invention, the C1 to C10 linear or branched alkyl group includes C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10 linear or branched alkyl groups, which illustratively include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, or n-octyl, and the like. The same meanings are given below in relation to the same descriptions.

m is an integer from 0 to 10, and may be, for example, 0, 1,2, 3, 4, 5, 6, 7, 8, 9 or 10.

Y is

X is

The wavy line represents the attachment site of the group.

R ₄ 、R ₆ 、R ₈ 、R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ Each independently selected from any one of hydrogen, halogen (such as F, cl, br or I), phenyl, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched chain alkyl.

R ₅ 、R ₇ Each independently selected from any one of halogen (such as F, cl, br or I), phenyl, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched chain alkyl.

L is selected from the group consisting of a single bond, C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C7C 8, C9 or C10) straight-chain or branched alkylene-O-, -CO-, -CS-),

Or

Any one of the above; the "L is a single bond" means a structure in which two benzene rings are connected through a single bond to form biphenyl.

a. b represents the number of repeating units, each independently selected from integers of 1 to 30, and may be, for example, 2,4, 5, 7, 9,10, 12, 15, 18, 20, 22, 25 or 28.

The thermosetting polyphenylene ether is preferably contained in the resin composition in an amount of 1 to 20% by mass, for example, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19% or the like.

In the present invention, the thermosetting polyphenylene ether is commercially available, for example, OPE-2ST of Mitsubishi gas, japan, and/or MX9000 of Saxabi, and the like.

Preferably, the polymerized monomer of the polyfunctional vinyl aromatic polymer includes a combination of a divinyl aromatic compound and a monovinyl aromatic compound.

Preferably, the polyfunctional vinyl aromatic polymer has a molar percentage of structural units based on the divinyl aromatic compound of 2 to 95%, and may be, for example, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%, and the like.

Preferably, the divinylaromatic compound comprises any one or a combination of at least two of the following structural units:

wherein, the short straight lines at both sides of the group represent access bonds and do not represent methyl; the same expressions are used hereinafter for the same meaning.

Wherein R is ^a 、R ^b Each independently selected from C6 to C30 (C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.) arylene, illustratively including but not limited to: phenylene, biphenylene, naphthylene, or indenylene, and the like.

Illustratively, the divinylaromatic compound includes any one of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diisopropenylbenzene, diisopropenylnaphthalene, or diisopropenylbiphenyl, or a combination of at least two thereof. The divinylaromatic compounds enumerated above include all isomers thereof, for example, the divinylbenzene is any one of o-divinylbenzene, m-divinylbenzene or p-divinylbenzene or a combination of at least two thereof; the divinylbiphenyl includes any one or a combination of at least two of 4,4' -divinylbiphenyl, 4,3' -divinylbiphenyl, 4,2' -divinylbiphenyl, 3' -divinylbiphenyl, 2' -divinylbiphenyl, or 2, 4-divinylbiphenyl; the divinylnaphthalene includes any one of 1, 3-divinylnaphthalene, 1, 4-divinylnaphthalene, 1, 5-divinylnaphthalene, 1, 8-divinylnaphthalene, 2, 3-divinylnaphthalene, 2, 6-divinylnaphthalene or 2, 7-divinylnaphthalene or a combination of at least two thereof.

Preferably, the polyfunctional vinyl aromatic polymer has a molar percentage of structural units based on the monovinyl aromatic compound of 5 to 98%, for example, 6%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%.

Preferably, the monovinyl aromatic compounds include styrene, as well as other monovinyl aromatic compounds than styrene, such as substituted styrenes; the substituted substituent is selected from C1 to C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight or branched chain alkyl.

The polyfunctional vinyl aromatic polymer preferably has a number average molecular weight of 600 to 20000g/mol, and may be, for example, 800g/mol, 1000g/mol, 3000g/mol, 5000g/mol, 7000g/mol, 9000g/mol, 10000g/mol, 11000g/mol, 13000g/mol, 15000g/mol, 17000g/mol or 19000 g/mol.

In the present invention, the polyfunctional vinyl aromatic polymer is commercially available, for example, ODV of Nippon iron.

The content of the polyfunctional vinyl aromatic polymer in the resin composition is preferably 1 to 50% by mass, and may be, for example, 2%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 35%, 40%, 45%, 48%, or the like.

Preferably, the thermosetting hydrocarbon resin includes polybutadiene and/or styrene-butadiene-styrene copolymer (styrene-butadiene resin).

The content of the thermosetting hydrocarbon resin in the resin composition is preferably 0.1 to 40% by mass, and may be, for example, 0.3%, 0.5%, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 38%, or the like.

In the present invention, the thermosetting hydrocarbon resin may be commercially available, for example, any one of or a combination of at least two of B3000 in Caoda, R154 in Krevili, japan, RB810 in JSR, or R100 in Krevili, USA.

Preferably, the unsaturated functional group in the co-crosslinking agent includes at least one of a vinyl group, a phenylvinyl group, an allyl group, an isopropenyl group, an acrylic group, or a methacrylic group.

Preferably, the content of the co-crosslinking agent in the resin composition is 0.1 to 30% by mass, and may be, for example, 0.3%, 0.5%, 1%, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, or the like.

Preferably, the co-crosslinking agent comprises any one of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethallyl allyl isocyanate (TMAIC), divinylbenzene (DVB), 1, 2-bis (p-vinylphenyl) ethane (BVPE), or 1,2, 4-Trivinylcyclohexane (TVCH), or a combination of at least two thereof.

Preferably, the resin composition further comprises a hydrogenated styrene-butadiene block copolymer (SEBS).

The content of the hydrogenated styrene-butadiene block copolymer in the resin composition is preferably 0.1 to 10% by mass, and may be, for example, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or the like.

In the present invention, the hydrogenated styrene-butadiene block copolymer (SEBS) is commercially available, for example, from G1652 and/or KIC19-023, koteng, USA.

Preferably, the resin composition further comprises an initiator.

Preferably, the initiator includes any one of an organic peroxide initiator, an azo-based initiator, or a carbon-based radical initiator, or a combination of at least two thereof.

Preferably, the organic peroxide initiator comprises any one of, or a combination of at least two of, t-butyl cumyl peroxide, dicumyl peroxide, benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne, or 1, 1-di (t-butylperoxy) -3, 5-dimethylcyclohexane.

Preferably, the carbon-based radical initiator comprises paraquat and/or polydioxanone.

Preferably, the mass of the initiator is 0.001 to 3%, for example, 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%, 2.8%, or the like, based on 100% by mass of the thermosetting resin.

Preferably, the resin composition further comprises a flame retardant.

Preferably, the flame retardant comprises a bromine-containing flame retardant and/or a phosphorus-containing flame retardant.

Preferably, the bromine-containing flame retardant comprises any one or at least two of ethylene bistetrabromophthalimide, decabromodiphenylethane or decabromodiphenyl ether.

Preferably, the phosphorus-containing flame retardant comprises 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide additive flame retardant and/or phosphonate additive flame retardant.

The content of the flame retardant in the resin composition is preferably 10 to 25% by mass, and may be, for example, 11%, 13%, 15%, 17%, 19%, 20%, 21%, 22%, 23%, 24%, or the like.

Preferably, the resin composition further includes a low dielectric filler.

Preferably, the low dielectric filler includes any one of boron nitride, polytetrafluoroethylene (PTFE) powder, or silica-coated Polytetrafluoroethylene (PTFE) powder, or a combination of at least two thereof.

Preferably, the content of the low dielectric filler in the resin composition is 0.1 to 10% by mass, and may be, for example, 0.3%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%.

The resin composition may further comprise a solvent, and the amount of the solvent is selected by a person skilled in the art according to experience and process requirements, so that the resin composition has a viscosity suitable for use, and the resin composition can be conveniently impregnated and coated. And in the subsequent drying, semi-curing or complete curing process, the solvent in the resin composition can be partially or completely volatilized.

The solvent used in the present invention is not particularly limited, and generally ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate can be used alone or in combination of two or more. Ketones such as acetone, methyl ethyl ketone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are preferable.

In a second aspect, the present invention provides a resin film, a material of which comprises the resin composition according to the first aspect.

Preferably, the resin film is prepared by coating the resin composition on a release material and drying and/or baking.

In a third aspect, the present invention provides a resin-coated copper foil (RCC) comprising a copper foil, and a resin layer provided on one side of the copper foil, the material of the resin layer comprising the resin composition according to the first aspect.

Preferably, the resin-coated copper foil is prepared by coating the resin composition on a copper foil and drying and/or baking the coated copper foil.

In a fourth aspect, the present disclosure provides a prepreg (PP) comprising a reinforcing material, and the resin composition according to the first aspect attached to the reinforcing material after drying by immersion.

Preferably, the reinforcing material comprises any one or at least two of natural fibers, organic synthetic fibers, organic fabrics and inorganic fibers; for example, glass fiber cloth, nonwoven fabric, etc., and low dielectric reinforcing material such as NE glass fiber cloth, Q quartz cloth, QL cloth, etc., may be selected as necessary.

In a fifth aspect, the invention provides a copper-clad plate comprising at least one of the resin film according to the second aspect, the resin-coated copper foil according to the third aspect, or the prepreg according to the fourth aspect.

Illustratively, the copper-clad plate is prepared by adopting the following method, wherein the method comprises the following steps: overlapping copper foils on one side or two sides of 1 prepreg, and curing to obtain the metal foil-clad laminated board; or laminating at least 2 prepregs into a laminated board, then laminating copper foils on one side or two sides of the laminated board, and curing to obtain the copper-clad plate.

Preferably, the curing temperature is 150 to 250 ℃, such as 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 212 ℃, 215 ℃, 218 ℃, 220 ℃, 223 ℃, 225 ℃, 228 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃ and the like.

Preferably, the curing pressure is 10 to 60kg/cm ² E.g. 15kg/cm ² 、20kg/cm ² 、25kg/cm ² 、30kg/cm ² 、35kg/cm ² 、40kg/cm ² 、45kg/cm ² 、50kg/cm ² Or 55kg/cm ² And the like.

Preferably, the curing time is 60 to 360min, such as 80min, 90min, 100min, 120min, 140min, 150min, 160min, 180min, 200min, 220min, 240min, 260min, 280min, 300min, 320min, 340min, or the like.

In a sixth aspect, the present invention provides a printed circuit board comprising at least one of the resin film according to the second aspect, the resin-coated copper foil according to the third aspect, the prepreg according to the fourth aspect, or the copper clad laminate according to the fifth aspect.

Compared with the prior art, the invention has the following beneficial effects:

in the resin composition provided by the invention, the low-dielectric thermosetting resin is compounded with the specific silicon dioxide, so that the resin composition and the plate containing the resin composition have lower dielectric constant and lower dielectric loss factor, dk of 10GHz is less than 3.5 and can be as low as 3.2-3.35, df is less than 0.0020 and can be as low as 0.0012-0.00145, the Df change rate after moisture absorption is low, and delta Df after 24h treatment at 23 ℃ and 50% humidity is less than 0.00013; meanwhile, the resin composition and the board containing the same have the advantages of high glass transition temperature, good thermal stability, low thermal expansion coefficient, water absorption of 0.04-0.06%, low water absorption, high peel strength and excellent overall performance, and fully meet the performance requirements of the high-frequency and high-speed copper foil substrate.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The experimental materials involved in the following examples and comparative examples of the present invention are as follows:

(1) Thermosetting polyphenylene ether:

OPE-2ST 2200: mitsubishi gas;

MX9000: sautersapick.

(2) Polyfunctional vinyl aromatic polymers

ODV-XET: nippon Nissan iron chemical industry Co., ltd.

(3) Thermosetting hydrocarbon resins

B3000, japan caoda;

r154, kreviley, usa;

RB810, JSR, japan;

r100, kreviley, usa.

(4) Auxiliary crosslinking agent

TAIC, triallyl isocyanurate, sartomer usa;

TAC, triallyl cyanurate, sartomer usa;

TMAIC, trimethacrylisocyanate, badam in south of lake;

DVB, divinylbenzene, new day fe chemical industries, japan;

BVPE,1, 2-di (p-vinylphenyl) ethane, jiangsu Linchuan chemical industry;

TVCH,1,2, 4-trivinylcyclohexane, wolff in Germany.

(5) Hydrogenated styrene-butadiene Block copolymer and modified product thereof (SEBS resin)

1652, american kraton;

KIC19-023, american Keteng.

(6) Flame retardant

BT-93W, a bromine-containing flame retardant, american Yabao;

ST8010, american yabao;

XP7866, american yabao;

HCP-804, magic color Kunshan, china.

(7) Silicon dioxide

HM102, spherical silica prepared by organosilicon hydrolysis method, purity of 99.99%, average particle diameter (D) ₅₀ ) 0.95 μm, 0.426 radius distance, jiangsu Huimei;

HM102YJ, silicone WaterSpherical silica prepared by the decomposition method, the purity is 99.95%, and the average particle diameter (D) ₅₀ ) 0.95 μm, 0.500 of radius distance, jiangsu Huimei;

HM052, spherical silica prepared by hydrolysis of organosilicon, purity 99.90%, average particle diameter (D) ₅₀ ) 0.55 μm, 0.581 of radius distance, jiangsu Huimei;

YP-1, flame-prepared spherical silica, purity 99.90%, average particle diameter (D) ₅₀ ) 2.63 mu m, the radius distance is 1.313, and the material is self-made by a flame method;

FB-3SDC, spherical silica prepared by flame method, purity of 99.90%, average particle diameter (D) ₅₀ ) 3.1 μm, a caliper of 1.364, japan electrochemistry;

SFP-30M, flame-prepared spherical silica, purity 99.90%, average particle diameter (D) ₅₀ ) 1.2 μm, 0.934 on radial basis, japan electrochemistry;

YP-2, spherical silica prepared by Silicone hydrolysis (tetraethoxysilane hydrolysis), purity 99.95%, average particle diameter (D) ₅₀ ) 1.0 μm, and the radial distance is 1.253;

YP-3, chemically prepared spherical silica, purity 98.15%, average particle diameter (D) ₅₀ ) 1.0 μm, and a radial distance of 0.85; the water glass is prepared by a precipitation method and is self-made.

(8) Low dielectric filler

CFP012, BN, us 3M;

polytetrafluoroethylene (PTFE) powder, yue Dong.

Example 1

The embodiment provides a resin composition, which comprises the following components in parts by weight: 20 parts of thermosetting polyphenylene ether (OPE-2ST 2200), 49 parts of multifunctional vinyl aromatic polymer (ODV-XET), 1 part of SEBS resin (G1652), 20 parts of silicon dioxide (HM 102) and 10 parts of bromine-containing flame retardant (BT-93W).

The embodiment also provides a prepreg and a copper-clad plate, and the specific preparation method comprises the following steps:

(1) Mixing thermosetting polyphenyl ether, polyfunctional vinyl aromatic polymer, SEBS resin and toluene, stirring uniformly at normal temperature, then adding bromine-containing flame retardant and silicon dioxide, and mixing uniformly to form resin glue solution with solid content of 65%;

(2) Dipping the resin glue solution obtained in the step (1) by using glass fiber cloth (model 1078, taiwan Hubeier, china), and heating and drying for 5min in a baking oven of a dipping machine at the temperature of 130 ℃ to convert the resin composition in a varnish state into the resin composition in a semi-cured state to obtain a prepreg;

(3) Laminating 9 prepregs obtained in the step (2) between two HVLP copper foils with the thickness of HOZ at the concentration of 30kg/cm ² Solidifying for 120 minutes under the pressure and at the heating rate of 3.5 ℃/min and the temperature of 200 ℃, and then slowly cooling to 50 ℃ to obtain the copper-clad plate with the thickness of 0.75 mm.

Examples 2 to 8, comparative examples 1 to 8

A resin composition having the specific formulation shown in tables 1 and 2; the units of the amounts of the components in tables 1 and 2 are "parts".

The resin compositions of examples 2 to 8 and comparative examples 1 to 8 were prepared into copper-clad plates by the method described in example 1, and subjected to the following physical property evaluation tests:

(1) Glass transition temperature (T) _g At deg.C): testing was carried out according to IPC-TM-650.2.4.24.4 (version 11/98) with a dynamic viscosity analyser (DMA, rheometric RSAIII);

(2) Water absorption (%): heating the sample in a pressure cooker at 120 ℃ and 2atm for 120 minutes, and calculating the weight change before and after heating;

(3) Copper foil peel strength (PS, lb/in): testing the peel strength of the plate according to the experimental conditions of 'after thermal stress' in the IPC-TM-650.4.8 method;

(4) Dielectric constant Dk (10 GHz): the dielectric constant Dk at a frequency of 10GHz was measured according to IPC-TM-650.5.5.13;

(5) Dielectric loss factor Df (10 GHz): the loss factor Df at frequency 10GHz was tested according to IPC-TM-650.5.5.13;

(6) Δ Df: comparative test the change in Df of a sample before and after leaving it for 48 hours under conditions of 23 ℃ and 50% RH was measured, the loss factor Df at a frequency of 10GHz was measured according to IPC-TM-650 2.5.5.13, and the Df of the sample before leaving it for 48 hours was subtracted from this value and was designated as Δ Df;

(7) Coefficient of Thermal Expansion (CTE): the test was carried out using a thermomechanical analyzer (TMA) according to the CTE test standard specified by IPC-TM-6502.4.24.1.

The test results are shown in tables 1 and 2.

TABLE 1

TABLE 2

According to the data in tables 1 and 2, the resin composition provided by the invention is prepared by the organosilicon hydrolysis method, the silicon dioxide with the purity of more than 99.9% and the radial distance of less than 1 is compounded with the thermosetting resin, so that the resin composition and the plate containing the resin composition have lower dielectric constant and lower dielectric loss factor, dk at 10GHz is 3.2-3.35, df is 0.0012-0.00145, the change rate of Df after moisture absorption is low, and delta Df after 24h treatment at 23 ℃ and 50% humidity is less than or equal to 0.00012; the plate has high glass transition temperature, good thermal stability, low thermal expansion coefficient, low water absorption rate of 0.04-0.06%, high peel strength and good reliability, and fully meets the performance requirements of the high-frequency high-speed copper foil substrate.

Compared with comparative examples 1-7, the resin composition and the copper-clad plate of the invention adopt the spherical silicon dioxide prepared by the alkoxysilane hydrolysis method, and the high purity of the spherical silicon dioxide ensures the low dielectric loss; the method has small diameter distance, and has the characteristics of small water absorption and small Df change after moisture absorption compared with the spherical silicon dioxide prepared by a flame method. In comparative example 8, the chemically spherical silica prepared by hydrolysis of alkoxysilane had a purity of 99.95% and ensured a low value of dielectric loss Df, but exhibited disadvantages of relatively large water absorption and large change in Df after moisture absorption due to a radial distance of more than 1. In comparative example 9, silica prepared by hydrolytic precipitation of sodium silicate (water glass) has a purity of less than 99% and contains a large amount of ions, resulting in a high dielectric loss Df value, a high water absorption rate, and a large change in Df after moisture absorption.

The applicant states that the present invention is illustrated by the above examples of the resin composition and the application thereof, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. A resin composition, characterized in that the resin composition comprises the following components:

(B) The silicon dioxide is prepared by an organic silicon hydrolysis method, the purity of the silicon dioxide is more than or equal to 99.9 percent, the average grain diameter is 0.1-3 mu m, and the radial distance is less than 0.65;

the mass percentage of the thermosetting resin in the resin composition is 20-80%, and the mass percentage of the silicon dioxide is 20-70%.

2. The resin composition of claim 1, wherein the silica is prepared by a process comprising: carrying out hydrolysis reaction on organic silicon to obtain a primary product; and firing the primary product to obtain the silicon dioxide.

3. Resin composition according to claim 1 or 2, characterized in that the silicone is an alkoxysilane.

4. The resin composition of claim 3, wherein the alkoxysilane comprises any one or a combination of at least two of tetraethoxysilane, tetramethoxysilane, tetraphenoxysilane, tetra-n-butoxysilane, tetra-iso-butoxysilane, methyltriethoxysilane, or dimethyldiethoxysilane.

5. The resin composition according to claim 2, wherein the firing temperature is 800 to 1300 ℃.

6. Resin composition according to claim 1, characterized in that the purity of the silica is > 99.95%.

7. Resin composition according to claim 6, characterized in that the silica has a purity > 99.99%.

8. The resin composition according to claim 1, wherein the thermosetting polyphenylene ether has a number average molecular weight of 500 to 10000g/mol.

9. The resin composition according to claim 1, wherein the thermosetting polyphenylene ether has a structure shown as follows:

wherein Z is

A is selected from any one of-CO-, C6-C30 arylene and C1-C10 straight chain or branched chain alkylene;

R ₁ 、R ₂ 、R ₃ each independently selected from hydrogen, C1-C10 straight chain or branched chain alkylAny one of the above;

m is an integer of 0 to 10;

y is

X is

The wavy line represents the attachment site of the group;

R ₄ 、R ₆ 、R ₈ 、R ₉ 、R ₁₀ 、R ₁₁ 、R ₁₂ 、R ₁₃ 、R ₁₄ 、R ₁₅ each independently selected from any one of hydrogen, halogen, phenyl, C1-C10 straight chain or branched chain alkyl;

R ₅ 、R ₇ each independently selected from any one of halogen, phenyl, C1-C10 straight chain or branched chain alkyl;

l is selected from a single bond, C1-C10 linear or branched alkylene, -O-, -CO-, -CS-,

any one of the above;

a. each b is independently selected from an integer of 1 to 30.

10. The resin composition according to claim 1, wherein the thermosetting polyphenylene ether is contained in the resin composition in an amount of 1 to 20% by mass.

11. Resin composition according to claim 1, characterized in that the polymerized monomers of the polyfunctional vinyl aromatic polymer comprise a combination of divinyl aromatic compound and monovinyl aromatic compound.

12. Resin composition according to claim 11, characterized in that the multifunctional vinyl aromatic polymer has a content of structural units based on divinyl aromatic compound of from 2 to 95% in molar percentage.

13. The resin composition according to claim 11, wherein the polyfunctional vinyl aromatic polymer has a content of 5 to 98% by mole of a structural unit based on a monovinyl aromatic compound.

14. The resin composition according to claim 1, wherein the number average molecular weight of the polyfunctional vinyl aromatic polymer is 600 to 20000g/mol.

15. The resin composition according to claim 1, wherein the mass percentage of the polyfunctional vinyl aromatic polymer in the resin composition is 1 to 50%.

16. The resin composition of claim 1, wherein the thermosetting hydrocarbon resin comprises polybutadiene and/or styrene-butadiene-styrene copolymer.

17. The resin composition according to claim 1, wherein the content of the thermosetting hydrocarbon resin in the resin composition is 0.1 to 40% by mass.

18. The resin composition of claim 1, wherein the unsaturated functional group of the auxiliary crosslinking agent comprises at least one of vinyl, phenyl vinyl, allyl, isopropenyl, acrylic or methacrylic groups.

19. The resin composition according to claim 1, wherein the content of the co-crosslinking agent in the resin composition is 0.1 to 30% by mass.

20. The resin composition of claim 1, wherein the co-crosslinking agent comprises any one of triallyl isocyanurate, triallyl cyanurate, trimethallyl isocyanate, divinylbenzene, 1, 2-bis (p-vinylphenyl) ethane, or 1,2, 4-trivinylcyclohexane, or a combination of at least two thereof.

21. The resin composition according to claim 1, wherein the resin composition further comprises a hydrogenated styrene-butadiene block copolymer, wherein the mass percent of the thermosetting resin is 20 to 70%, and the mass percent of the silica is 20 to 70%.

22. The resin composition according to claim 21, wherein the hydrogenated styrene-butadiene block copolymer is contained in the resin composition in an amount of 0.1 to 10% by mass.

23. The resin composition according to claim 1, wherein the resin composition comprises 20 to 70% by mass of the thermosetting resin and 20 to 70% by mass of the silica, and further comprises an initiator.

24. The resin composition according to claim 23, wherein the initiator comprises any one of an organic peroxide initiator, an azo-based initiator, or a carbon-based radical initiator, or a combination of at least two of them.

25. The resin composition of claim 24, wherein the organic peroxide initiator comprises any one of, or a combination of at least two of, t-butylcumyl peroxide, dicumyl peroxide, benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne, or 1, 1-di (t-butylperoxy) -3, 5-dimethylcyclohexane.

26. The resin composition of claim 24, wherein the carbon-based radical initiator comprises paraquat and/or polydioxanone.

27. The resin composition according to claim 23, wherein the mass of the initiator is 0.001 to 3% based on 100% by mass of the thermosetting resin.

28. The resin composition according to claim 1, wherein the resin composition further comprises a flame retardant, wherein the thermosetting resin is 20 to 70% by mass, the silica is 20 to 70% by mass, and the resin composition further comprises a flame retardant.

29. The resin composition of claim 28, wherein the flame retardant comprises a bromine-containing flame retardant and/or a phosphorus-containing flame retardant.

30. The resin composition as claimed in claim 29, wherein the bromine-containing flame retardant comprises any one or a combination of at least two of ethylenebistetrabromophthalimide, decabromodiphenylethane, or decabromodiphenylether.

31. The resin composition as claimed in claim 29, wherein the phosphorus-containing flame retardant comprises 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-based additive flame retardant and/or phosphonate-based additive flame retardant.

32. The resin composition according to claim 28, wherein the flame retardant is contained in an amount of 10 to 25% by mass.

33. The resin composition according to claim 1, wherein the resin composition comprises 20 to 70% by mass of the thermosetting resin and 20 to 70% by mass of the silica, and the resin composition further comprises a low dielectric filler.

34. The resin composition of claim 33, wherein the low dielectric filler comprises any one of boron nitride, polytetrafluoroethylene powder or silica-coated polytetrafluoroethylene powder or a combination of at least two thereof.

35. The resin composition of claim 33, wherein the low dielectric filler is present in the resin composition in an amount of 0.1 to 10% by mass.

36. A resin film characterized in that a material of the resin film comprises the resin composition according to any one of claims 1 to 35.

37. The resin film according to claim 36, wherein the resin film is obtained by applying the resin composition onto a release material and drying and/or baking the resin composition.

38. A resin-coated copper foil comprising a copper foil, and a resin layer provided on one side of the copper foil, wherein a material of the resin layer comprises the resin composition according to any one of claims 1 to 35.

39. The resin-coated copper foil as claimed in claim 38, wherein the resin-coated copper foil is obtained by applying the resin composition to a copper foil and drying and/or baking the resin composition.

40. Prepreg comprising a reinforcement and a resin composition according to any one of claims 1 to 35 attached to the reinforcement by dip drying.

41. A copper-clad plate comprising at least one of the resin film according to claim 36 or 37, the resin-coated copper foil according to claim 38 or 39, or the prepreg according to claim 40.

42. A printed circuit board comprising at least one of the resin film of claim 36 or 37, the resin-coated copper foil of claim 38 or 39, the prepreg of claim 40, or the copper-clad plate of claim 41.