CN113527818A

CN113527818A - Resin composition and application thereof

Info

Publication number: CN113527818A
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: 2021-10-22
Anticipated expiration: 2041-08-12
Also published as: WO2023016244A1; CN113527818B; TW202307131A; TWI802482B

Abstract

The invention provides a resin composition and an 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%, the average particle size 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 currently used quartz glass 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 a high-frequency high-speed copper-clad plate, which comprises the steps of crushing, grading and carrying out surface treatment by using fluorosilane to obtain D₅₀The fused silica powder with the particle size of 7.0-15.0 microns is suitable for a high-frequency high-speed copper-clad plate, but the radial 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 used as an inorganic filler to reduce the dielectric constant of the copper-clad plate, and the purity of silicon dioxide is reduced and the Df of the silicon dioxide is influenced in the grinding, crushing and pelletizing processes of the cristobalite powder; 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 uses 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 surface closed and an internal porous structure, which is prepared by a chemical method, and is prepared by hydrolyzing organic silicon to obtain an aggregate of spherical silicon by a chemical method, and then burning to obtain silicon dioxide with a surface closed and an internal porous structure; 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 manufacturing nanoscale high-purity silicon dioxide, wherein a chemical direct synthesis method is adopted to obtain a product with a particle size of 5-20 nm, but due to the fact that the particle size is about 10nm, glue solution viscosity is very high, a manufacturing process of a bonding sheet of a Copper Clad Laminate (CCL) is greatly affected, and a qualified bonding sheet cannot be manufactured.

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 dioxide₅₀) 0.1-3 μm, and the radial distance is less than 1;

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

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 diameter pitch, a narrow particle size distribution of silica particles, a high uniformity of particle sizes of the respective particles, and a dielectric constant of the resin compositionLow dielectric loss factor (Dk), low hygroscopicity, low Df change after moisture absorption, high glass transition temperature, and 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 silica₅₀) The particle size is 0.1 to 3 μm, and may be, for example, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2 μm, 2.2 μm, 2.5 μm or 2.8 μm.

The silica may have a caliper of < 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 diameter₅₀、D₁₀、D₉₀Radial 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 (D)₉₀–D₁₀)/D₅₀。

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: the thermosetting resin composition comprises a thermosetting polyphenyl ether and multifunctional vinyl aromatic polymer, a thermosetting polyphenyl ether and thermosetting hydrocarbon resin, a thermosetting polyphenyl ether and auxiliary crosslinking agent, a multifunctional vinyl aromatic polymer and thermosetting hydrocarbon resin, a thermosetting polyphenyl ether, thermosetting hydrocarbon resin and auxiliary crosslinking agent, a multifunctional vinyl aromatic polymer, thermosetting hydrocarbon resin and auxiliary crosslinking agent, a thermosetting polyphenyl ether, multifunctional vinyl aromatic polymer and auxiliary crosslinking agent, and a thermosetting polyphenyl ether, multifunctional vinyl aromatic polymer, thermosetting hydrocarbon resin and auxiliary crosslinking agent.

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 ℃, and may be 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, or the like, for example.

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, the C6-C30 arylene group exemplarily includes but is not limited to: phenylene, biphenylene, terphenylene, naphthylene, or the like; the C1 to C10 linear or branched alkylene groups illustratively include, but are not limited to: methylene, ethylene, propylene or butylene, and the like.

R₁、R₂、R₃Each independently selected from any one of hydrogen, C1-C10 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched chain alkyl.

In the present invention, the C1-C10 linear or branched alkyl group includes C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10 linear or branched alkyl groups, which exemplarily 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 of 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.

R₄、R₆、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃、R₁₄、R₁₅Each 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.

R₅、R₇Each 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 a single bond, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched chain alkylene, -O-, -CO-, -CS-, C-O-C-,

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 a structural unit based on a 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%.

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^bEach independently selected from the group consisting of C6-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 comprises 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 divinyl naphthalene includes any one of 1, 3-divinyl naphthalene, 1, 4-divinyl naphthalene, 1, 5-divinyl naphthalene, 1, 8-divinyl naphthalene, 2, 3-divinyl naphthalene, 2, 6-divinyl naphthalene or 2, 7-divinyl naphthalene or a combination of at least two of the two.

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 compound includes styrene, and other monovinyl aromatic compounds than styrene, such as substituted styrene; the substituted substituent is selected from C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched chain alkyl.

Preferably, the polyfunctional vinyl aromatic polymer 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.

Preferably, the content of the polyfunctional vinyl aromatic polymer in the resin composition is 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).

Preferably, the content of the thermosetting hydrocarbon resin in the resin composition is 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 auxiliary 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%, or 9%.

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

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 tert-butyl cumyl peroxide, dicumyl peroxide, benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexyne, or 1, 1-di (tert-butylperoxy) -3,3, 5-dimethylcyclohexane, or a combination of at least two thereof.

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

Preferably, the initiator is 0.001 to 3% by mass, 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.

Preferably, the content of the flame retardant in the resin composition is 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.

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 present 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 150-250 ℃, 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 10-60 kg/cm²E.g. 15kg/cm²、20kg/cm²、25kg/cm²、30kg/cm²、35kg/cm²、40kg/cm²、45kg/cm²、50kg/cm²Or 55kg/cm²And the like.

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

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 and the specific silicon dioxide are compounded, 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 24-hour treatment at 23 ℃ and 50% humidity is less than 0.00013; meanwhile, the resin composition and the plate 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;

MX 9000: sauter sapick.

(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, Woodward, Germany.

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

1652, american kraton;

KIC19-023, USA 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 hydrolysis of organosilicon, purity of 99.99%, average particle diameter (D)₅₀) 0.95 μm, 0.426 radius distance, Jiangsu Huimei;

HM102YJ, spherical silica prepared by Silicone hydrolysis method, purity of 99.95%, average particle diameter (D)₅₀) 0.95 μm, 0.500 of radial 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 radial 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, radius 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 of raw materials and is prepared by self.

(8) Low dielectric filler

CFP012, BN, us 3M;

polytetrafluoroethylene (PTFE) powder, east yue.

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 (HM102) 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, 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 Hubeil, China), and heating and drying for 5min in a baking oven of a dipping machine at 130 ℃ to convert the resin composition in a varnish state into the resin composition in a semi-cured state to obtain a semi-cured sheet;

(3) laminating 9 prepregs obtained in the step (2) between two HVLP copper foils with the thickness of HOZ at the thickness of 30kg/cm²Solidifying 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 a 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 the following physical property evaluation tests were performed:

(1) glass transition temperature (T)_gAt deg.C): testing was carried out according to IPC-TM-6502.4.24.4 (version 11/98) with a dynamic viscosity analyzer (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-6502.4.8 method;

(4) dielectric constant Dk (10 GHz): the dielectric constant Dk at a frequency of 10GHz was measured according to IPC-TM-6502.5.5.13;

(5) dielectric loss factor Df (10 GHz): testing the loss factor Df at 10GHz according to IPC-TM-6502.5.5.13;

(6) Δ Df: comparative test the Df change value of the sample before and after 48 hours of standing at 23 ℃ and 50% RH, the loss factor Df at 10GHz frequency is tested according to IPC-TM-6502.5.5.13, and the Df value of the sample before 48 hours of standing is subtracted from the Df value and is recorded as delta 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 an organosilicon hydrolysis method, the silicon dioxide with 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 Df change rate after moisture absorption is low, and delta Df after 24-hour treatment at 23 ℃ and 50% humidity is less than or equal to 0.00012; the plate has the advantages of 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 provided by the invention adopt the chemical spherical silicon dioxide prepared by an alkoxysilane hydrolysis method, and the high purity of the spherical silicon dioxide ensures the characteristic of 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 a sodium silicate (water glass) hydrolytic precipitation method 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 modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, 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%, the average particle size 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%.

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; firing the primary product to obtain the silicon dioxide;

preferably, the silicone is an alkoxysilane;

preferably, the alkoxysilane includes any one or a combination of at least two of tetraethoxysilane, tetramethoxysilane, tetraphenoxysilane, tetra-n-butoxysilane, tetra-iso-butoxysilane, methyltriethoxysilane, or dimethyldiethoxysilane;

preferably, the firing temperature is 800-1300 ℃;

preferably, the purity of the silica is > 99.95%, preferably > 99.99%;

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

3. The resin composition according to claim 1 or 2, wherein the mass percentage of the thermosetting resin in the resin composition is 20 to 80%;

preferably, the number average molecular weight of the thermosetting polyphenyl ether is 500-10000 g/mol;

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

wherein Z is

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

R₁、R₂、R₃each independently selected from any one of hydrogen and C1-C10 straight chain or branched chain alkyl;

m is an integer of 0-10;

y is

X is

The wavy line represents the attachment site of the group;

R₄、R₆、R₈、R₉、R₁₀、R₁₁、R₁₂、R₁₃、R₁₄、R₁₅each independently selected from any one of hydrogen, halogen, phenyl, C1-C10 straight chain or branched chain alkyl;

R₅、R₇each independently selected from any one of halogen, phenyl, C1-C10 straight chain or branched chain alkyl;

l is selected from single bond, C1-C10 straight chain or branched chain alkylene, -O-, -CO-, -CS-, C-O-, -CO-, -C-O-or-C-O-C-,

Any one of the above;

a. b is independently selected from an integer of 1-30;

preferably, the mass percentage content of the thermosetting polyphenyl ether in the resin composition is 1-20%;

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 multifunctional vinyl aromatic polymer has a mol% content of 2 to 95% of a structural unit based on a divinyl aromatic compound;

wherein R is^a、R^bEach independently selected from C6-C30 arylene;

preferably, the polyfunctional vinyl aromatic polymer has a structural unit based on a monovinyl aromatic compound in a molar percentage of 5 to 98%;

preferably, the polyfunctional vinyl aromatic polymer has a number average molecular weight of 600 to 20000 g/mol;

preferably, the mass percentage of the polyfunctional vinyl aromatic polymer in the resin composition is 1 to 50 percent;

preferably, the thermosetting hydrocarbon resin comprises polybutadiene and/or styrene-butadiene-styrene copolymer;

preferably, the mass percentage content of the thermosetting hydrocarbon resin in the resin composition is 0.1-40%.

4. The resin composition as claimed in any one of claims 1 to 3, wherein the unsaturated functional group in the co-crosslinking agent comprises at least one of vinyl group, phenyl vinyl group, allyl group, isopropenyl group, acrylic group or methacrylic group;

preferably, the mass percentage of the auxiliary crosslinking agent in the resin composition is 0.1-30%;

preferably, 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.

5. The resin composition according to any one of claims 1 to 4, further comprising a hydrogenated styrene-butadiene block copolymer;

preferably, the mass percentage content of the hydrogenated styrene-butadiene block copolymer in the resin composition is 0.1-10%;

preferably, the resin composition further comprises an initiator;

preferably, the initiator comprises any one or a combination of at least two of an organic peroxide initiator, an azo initiator or a carbon-based radical initiator;

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

preferably, the carbon-based radical initiator comprises paraquat and/or polydioxanone;

preferably, the mass of the initiator is 0.001-3% based on 100% of the 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;

preferably, the mass percentage of the flame retardant in the resin composition is 10-25%;

preferably, the resin composition further comprises a low dielectric filler;

preferably, the low dielectric filler comprises any one of boron nitride, polytetrafluoroethylene powder or silicon dioxide-coated polytetrafluoroethylene powder or a combination of at least two of the boron nitride, the polytetrafluoroethylene powder or the silicon dioxide-coated polytetrafluoroethylene powder;

preferably, the mass percentage content of the low dielectric filler in the resin composition is 0.1-10%.

6. A resin film characterized in that a material of the resin film comprises the resin composition according to any one of claims 1 to 5;

7. 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 5;

8. A prepreg comprising a reinforcing material and the resin composition according to any one of claims 1 to 5 attached to the reinforcing material by dip drying.

9. A copper-clad plate characterized by comprising at least one of the resin film according to claim 6, the resin-coated copper foil according to claim 7, or the prepreg according to claim 8.

10. A printed circuit board comprising at least one of the resin film according to claim 6, the resin-coated copper foil according to claim 7, the prepreg according to claim 8, or the copper-clad plate according to claim 9.