WO2023016244A1 - Resin composition and application thereof - Google Patents

Abstract

Provided by the present invention a resin composition and an application thereof, the resin composition comprises the following components: (A) a thermosetting resin, the thermosetting resin comprising a combination of at least two among a thermosetting polyphenylene ether, a polyfunctional vinyl aromatic polymer, a thermosetting hydrocarbon resin, and an auxiliary crosslinking agent containing at least two unsaturated functional groups; and (B) silicon dioxide, the silicon dioxide being prepared by means of organosilicon hydrolysis, the purity of the silicon dioxide being ≥99.9%, the average particle size being 0.1-3 μm, and the diameter distance being <1; the mass percentage of the silicon dioxide in the resin composition is 20-70%. The described resin composition has a low dielectric constant and low dielectric loss, and the rate of change of the dielectric loss after moisture absorption is also low, the water absorption rate is low, and thermal stability is high; a prepreg prepared by the described resin composition can fully meet the performance requirements of a high-frequency, high-speed copper foil substrate.

Description

A kind of resin composition and its application technical field

The invention belongs to the technical field of copper clad laminates, and in particular relates to a resin composition and its application.

Background technique

Copper-clad laminate is a plate-shaped material made of insulating paper, glass fiber cloth or other fiber materials impregnated with resin, covered with copper foil on one or both sides, and hot-pressed. It is a printed circuit board (Printed Circuit Board, PCB) ) basic material. In the quartz glass currently used in copper-clad laminates, 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%, and 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%, and 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%, its dielectric constant>3.8, dielectric loss>0.001, is currently easy to obtain Among the fillers, the material with the lowest dielectric constant and dielectric loss. Used in copper clad laminates, it has the least impact on the dielectric properties of copper clad laminates, and at the same time can replace high-cost resins with low dielectric constant and low dielectric loss, so it is widely used in copper clad laminates with low dielectric constant and low dielectric loss Use quartz glass powder as filler. With the improvement of the requirements for the dielectric constant and dielectric loss of copper clad laminates, the dielectric constant Dk<3.8 and the dielectric loss Df<0.001 are required. The current quartz glass can no longer meet the needs of copper clad laminates.

CN112500608A discloses a preparation method of fused silicon micropowder for high-frequency high-speed copper-clad laminates, using high-purity fused silicon micropowder raw materials through crushing, grading and surface treatment with fluorosilane to obtain _D50 of 7.0-15.0 μm suitable for high-frequency high-speed copper-clad laminates Fused silica powder is used, but its diameter is 1.32, indicating that the particle size distribution of silica powder is relatively wide, resulting in more interfaces crossed during signal transmission, resulting in energy loss, resulting in high Df. CN105131527A discloses a low-dielectric constant copper-clad laminate and its manufacturing method. The cristobalite powder made of high-purity vein quartz ore is used as an inorganic filler to reduce the dielectric constant of the copper-clad laminate. The purity of silicon dioxide is reduced, which affects the Df of silicon dioxide; and also because the fused silica produced by the flame method has a wide particle size distribution, the rate of change of Df after the resin composition absorbs moisture is relatively large. CN103771423A discloses a spherical filler for electronic packaging and a manufacturing method thereof. The spherical filler is mainly composed of silicon dioxide, but its particle size distribution is wide, and the moisture absorption rate is still high, which will lead to a relatively low Df change rate after the composite material absorbs moisture. big. CN103450639A discloses a thermosetting resin composition and its use. The thermosetting resin composition contains silicon dioxide with closed surfaces and internal pores. It is produced by chemical method, and is obtained by hydrolysis of organic silicon to obtain the aggregation of chemical method spherical silicon. body, and then burnt to obtain porous silicon dioxide with a closed surface; since the aggregation of spherical silicon in the chemical method is directly burned during the production process, it is not depolymerized into single particles, and some impurities will be sealed on the surface during the burning process. Closing the interior of the interior porous silica results in a higher Df. CN1634763A discloses a method for making nano-level high-purity silica, adopts chemical direct synthesis method, and obtains a product with a particle size of 5-20nm, but because its particle size is about 10nm, the viscosity of the glue will be very high. Yes, it has a very large negative impact on the manufacturing process of the bonding sheet of the copper clad laminate (CCL), and it is impossible to make a qualified bonding sheet.

Therefore, it is an urgent problem to be solved in this field to develop a composite material with low dielectric constant, low dielectric loss, and low Df change rate after moisture absorption to meet the needs of high-frequency and high-speed copper foil substrates.

Contents of the invention

Aiming at the deficiencies in the prior art, the object of the present invention is to provide a resin composition and its application. By compounding a low-dielectric thermosetting resin and specific silica, the resin composition not only has a low The dielectric constant and low dielectric loss, and the change rate of dielectric loss after moisture absorption is small, the water absorption rate is low, the thermal stability is high, and the reliability is good; the prepreg prepared by the resin composition can fully meet the requirements of high frequency and high speed. Performance requirements for copper foil substrates.

For reaching this purpose, the present invention adopts 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 an auxiliary crosslinking agent containing at least two unsaturated functional groups;

(B) silicon dioxide, the silicon dioxide is prepared by organosilicon hydrolysis, the purity of the silicon dioxide is ≥99.9%, the average particle size (D ₅₀ ) is 0.1-3 μm, and the diameter distance is <1;

The mass percentage of silicon dioxide in the resin composition is 20-70%, for example, it can be 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65% or 68%, etc.

In the resin composition provided by the present invention, the compounding of low-dielectric thermosetting resin and silicon dioxide is adopted. The silicon dioxide is prepared by chemical method (organosilicon hydrolysis method), has high purity, and has an average particle size of ( D ₅₀ ) is 0.1-3 μm, the diameter distance is small, the particle size distribution of silica particles is narrow, and the particle size consistency of each particle is high, so that the dielectric constant (Dk) of the resin composition is small, and the dielectric loss factor (Df) is small, and the hygroscopicity is lower, the change rate of Df after moisture absorption is low, and it has a high glass transition temperature and excellent thermal stability. The non-adhesive prepreg prepared by the resin composition can be automatically processed into a copper clad laminate, so that the Dk<3.5 and Df<0.0020 of the copper clad laminate under the condition of 10 GHz fully meet the high frequency and high speed requirements.

In the present invention, the purity of the silica is ≥99.9%, for example, it can be 99.92%, 99.95%, 99.97%, 99.99%, 99.991%, 99.993%, 99.995%, 99.997% or 99.999%.

The purity of the silicon dioxide involved in the present invention is measured by an inductively coupled atomic emission spectrometer ICP-AES.

The average particle size (D ₅₀ ) of the silica is 0.1-3 μm, 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 μm etc.

The diameter of the silicon dioxide is <1, for example, it can be 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, parameters related to particle size (such as D ₅₀ , D ₁₀ , D ₉₀ , diameter distance, etc.) can be obtained by testing with a Malvern 3000 laser particle size analyzer; in addition, the diameter distance can also be obtained by the following calculation formula: diameter distance =(D ₉₀ -D ₁₀ )/D ₅₀ .

In the present invention, component (A) thermosetting resin includes a combination of at least two of thermosetting polyphenylene ether, polyfunctional vinyl aromatic polymer, thermosetting hydrocarbon resin or auxiliary crosslinking agent containing at least two unsaturated functional groups , Exemplary combinations include: combination of thermosetting polyphenylene ether and polyfunctional vinyl aromatic polymer, combination of thermosetting polyphenylene ether and thermosetting hydrocarbon resin, combination of thermosetting polyphenylene ether and co-crosslinking agent, multifunctional Combination of vinyl aromatic polymer and thermosetting hydrocarbon resin, combination of thermosetting polyphenylene ether, polyfunctional vinyl aromatic polymer and thermosetting hydrocarbon resin, thermosetting polyphenylene ether, thermosetting hydrocarbon resin and crosslinking aid The combination of the three agents, the combination of the multifunctional vinyl aromatic polymer, the thermosetting hydrocarbon resin and the co-crosslinking agent, the combination of the thermosetting polyphenylene ether, the multifunctional vinyl aromatic polymer and the co-crosslinking agent Combination, the combination of thermosetting polyphenylene ether, polyfunctional vinyl aromatic polymer, thermosetting hydrocarbon resin and co-crosslinking agent, etc.

Preferably, the silicon dioxide is prepared by the following method, which includes: performing a hydrolysis reaction on organosilicon to obtain a primary product; and firing the primary product to obtain the silicon dioxide.

Preferably, the silicone is an alkoxysilane.

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

Preferably, the firing temperature is 800-1300°C, such as 850°C, 900°C, 950°C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C or 1250°C.

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

Preferably, the diameter of the silicon dioxide is <0.85, more preferably <0.65.

Preferably, the mass percentage of the thermosetting resin in the resin composition is 10-80%, for example, it can be 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% etc.

Preferably, the number average molecular weight of the thermosetting polyphenylene ether is 500-10000 g/mol, for example, 600 g/mol, 800 g/mol, 1000 g/mol, 1500 g/mol, 2000 g/mol, 2500 g/mol, 3000 g/mol , 3500g/mol, 4000g/mol, 4500g/mol, 5000g/mol, 6000g/mol, 7000g/mol, 8000g/mol, 9000g/mol or 9500g/mol, etc.

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

Preferably, the thermosetting polyphenylene ether has the following structure:

Among them, Z is

The wavy line represents the attachment site of the group.

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

R ₁ , R ₂ , and R ₃ are each independently selected from hydrogen, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) any straight-chain or branched-chain alkyl group A sort of.

In the present invention, the C1～C10 straight chain or branched chain alkyl group includes C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10 straight chain or branched chain alkyl group, exemplarily including but Not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, or n-octyl Base etc. When referring to the same description below, they all have the same meaning.

m is an integer selected from 0-10, for example, may be 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 are each independently selected from 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) any one of straight-chain or branched-chain alkyl groups.

R ₅ and R ₇ are each independently selected from halogen (such as F, Cl, Br or I), phenyl, C1-C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) Any of straight-chain or branched-chain alkyl groups.

L is selected from single bond, C1～C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched alkylene, -O-, -CO-, -CS -,

Any one of them; the "L is a single bond" means that two benzene rings are linked by a single bond to form a biphenyl structure.

a and b represent the number of repeating units, each independently selected from an integer of 1 to 30, such as 2, 4, 5, 7, 9, 10, 12, 15, 18, 20, 22, 25 or 28, etc. .

Preferably, the mass percentage of thermosetting polyphenylene ether in the resin composition is 1-20%, for example, it can be 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 9% , 10%, 11%, 13%, 15%, 17% or 19%, etc.

In the present invention, the thermosetting polyphenylene ether can be purchased from the market, such as OPE-2ST from Mitsubishi Gas and/or MX9000 from Saudi Arabia.

Preferably, the polymerized monomers of the polyfunctional vinyl aromatic polymer include a combination of divinyl aromatic compounds and monovinyl aromatic compounds.

Preferably, the molar percentage of structural units based on divinyl aromatic compounds in the polyfunctional vinyl aromatic polymer is 2 to 95%, such as 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, etc.

Preferably, the divinyl aromatic compound includes any one or a combination of at least two of the following structural units:

Wherein, the short straight lines on both sides of the group represent the access bond, not the methyl group; when the same expressions are involved in the following, they all have the same meaning.

Wherein, Ra and R ^b are each independently selected from C6-C30 (C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) arylene groups, exemplarily including but not Limited to: phenylene, biphenylene, naphthylene or indenylene, etc.

Exemplarily, the divinyl aromatic compound includes any of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diisopropenylbenzene, diisopropenylnaphthalene or diisopropenylbiphenyl One or a combination of at least two. The divinyl aromatic compounds listed above include all their isomers, for example, the divinylbenzene is any one of o-divinylbenzene, m-divinylbenzene or p-divinylbenzene Or a combination of at least two; the divinylbiphenyl includes 4,4'-divinylbiphenyl, 4,3'-divinylbiphenyl, 4,2'-divinylbiphenyl, 3, Any one or at least two of 2'-divinylbiphenyl, 3,3'-divinylbiphenyl, 2,2'-divinylbiphenyl or 2,4-divinylbiphenyl combination; the divinylnaphthalene includes 1,3-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 1,8-divinylnaphthalene, 2,3-divinylnaphthalene Any one or a combination of at least two of vinylnaphthalene, 2,6-divinylnaphthalene or 2,7-divinylnaphthalene.

Preferably, the molar percentage of structural units based on monovinyl aromatic compounds in the polyfunctional vinyl aromatic polymer is 5-98%, for example, it can be 6%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%, etc.

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

Preferably, the number average molecular weight of the polyfunctional vinyl aromatic polymer is 600-20000 g/mol, for example, it can be 800 g/mol, 1000 g/mol, 3000 g/mol, 5000 g/mol, 7000 g/mol, 9000 g/mol , 10000g/mol, 11000g/mol, 13000g/mol, 15000g/mol, 17000g/mol or 19000g/mol, etc.

In the present invention, the polyfunctional vinyl aromatic polymer can be purchased through market channels, such as ODV of Nippon Steel Corporation of Japan.

Preferably, the mass percent content of the polyfunctional vinyl aromatic polymer in the resin composition is 1-50%, for example, 2%, 3%, 5%, 8%, 10%, 12%, 15% %, 18%, 20%, 22%, 25%, 28%, 30%, 35%, 40%, 45% or 48%, etc.

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

Preferably, the mass percentage of the thermosetting hydrocarbon resin in the resin composition is 0.1-40%, for example, it can be 0.3%, 0.5%, 1%, 3%, 5%, 8%, 10%, 15% , 20%, 25%, 30%, 35% or 38%, etc.

In the present invention, the thermosetting hydrocarbon resin can be purchased through market channels, such as any one or A combination of at least two.

Preferably, the unsaturated functional groups in the auxiliary crosslinking agent include at least one of vinyl, phenylvinyl, allyl, isopropenyl, acrylic or methacrylic.

Preferably, the mass percentage of the auxiliary crosslinking agent in the resin composition is 0.1-30%, such as 0.3%, 0.5%, 1%, 3%, 5%, 8%, 10%, 12% , 15%, 18%, 20%, 22%, 25% or 28%, etc.

Preferably, the auxiliary crosslinking agent includes triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethallyl isocyanate (TMAIC), divinylbenzene ( DVB), 1,2-bis(p-vinylphenyl)ethane (BVPE) or 1,2,4-trivinylcyclohexane (TVCH) or a combination of at least two.

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

Preferably, the mass percentage of hydrogenated styrene-butadiene block copolymer in the resin composition is 0.1-10%, for example, it can be 0.3%, 0.5%, 1%, 2%, 3%, 4% %, 5%, 6%, 7%, 8% or 9%, etc.

In the present invention, the hydrogenated styrene-butadiene block copolymer (SEBS) can be purchased from the market, such as G1652 and/or KIC19-023 from Kraton, USA.

Preferably, the resin composition further includes an initiator.

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

Preferably, the organic peroxide initiator includes tert-butylcumyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl ylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne or 1,1-bis(tert-butylperoxy)-3,3, Any one or a combination of at least two of 5-dimethylcyclohexane.

Preferably, the carbon-based free radical initiator includes bicumene and/or polylinkum.

Preferably, based on 100% of the mass of the thermosetting resin, the mass of the initiator is 0.001-3%, such as 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%, etc.

Preferably, the resin composition further includes a flame retardant.

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

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

Preferably, the phosphorus-containing flame retardants include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide additive flame retardants and/or phosphonate additive flame retardants agent.

Preferably, the mass percentage of the flame retardant in the resin composition is 10-25%, for example, it can be 11%, 13%, 15%, 17%, 19%, 20%, 21%, 22%, 23% or 24% etc.

Preferably, the resin composition further includes low-dielectric fillers.

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

Preferably, the mass percentage of the low dielectric filler in the resin composition is 0.1-10%, such as 0.3%, 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%. , 6%, 7%, 8% or 9%, etc.

A solvent can also be added to the above resin composition, and the amount of solvent added is selected by those skilled in the art based on experience and process requirements, so that the resin composition can reach a suitable viscosity for impregnation and coating of the resin composition. . In the subsequent steps of drying, semi-curing or full curing, the solvent in the resin composition will be partially or completely volatilized.

As the solvent of the present invention, it is not particularly limited. Generally, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate can be used alone, or Can be used in combination of two or more. Preferable are ketones such as acetone, butanone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene.

In a second aspect, the present invention provides a resin film, the material of which includes the resin composition as described in 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), the resin-coated copper foil includes a copper foil, and a resin layer disposed on one side of the copper foil, the material of the resin layer includes the first The resin composition described in the 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 invention provides a prepreg (PP) sheet, the prepreg comprising a reinforcing material, and the resin composition as described in the first aspect adhered to the reinforcing material after being impregnated and dried.

Preferably, the reinforcing material includes any one or a combination of at least two of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fibers; for example, glass fiber cloth, non-woven fabric, etc., and low-dielectric materials can also be selected according to needs. Reinforcement materials, such as NE glass fiber cloth, Q quartz cloth, QL cloth, etc.

In a fifth aspect, the present invention provides a copper-clad laminate, which includes at least one of the resin film as described in the second aspect, the resin-coated copper foil as described in the third aspect, or the prepreg as described in the fourth aspect A sort of.

Exemplarily, the copper-clad laminate is prepared by the following method, the method comprising: laminating copper foil on one or both sides of a prepreg and curing to obtain the metal-clad laminate; or, combining at least 2 The prepregs are laminated to form a laminate, and then copper foil is laminated on one or both sides of the laminate and cured to obtain the copper-clad laminate.

Preferably, the curing temperature is 150-250°C, such as 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 or 245°C, etc.

Preferably, the curing pressure is 10-60kg/cm ² , such as 15kg/cm ² , 20kg/cm ^{2 , 25 kg/cm 2} , 30kg/cm ² , 35kg/ ^{cm 2 ,} 40kg/cm ² , 45kg/cm 2 cm ² , 50kg/cm ² or 55kg/cm ² etc.

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

In a sixth aspect, the present invention provides a printed circuit board, which includes the resin film as described in the second aspect, the resin-coated copper foil as described in the third aspect, and the resin-coated copper foil as described in the fourth aspect. At least one of the prepreg or the copper clad laminate as described in the fifth aspect.

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

In the resin composition provided by the present invention, the low-dielectric thermosetting resin is compounded with specific silica, so that the resin composition and the board containing it have a lower dielectric constant and a lower dielectric Dissipation factor, Dk<3.5 at 10GHz, can be as low as 3.2~3.35, Df<0.0020, can be as low as 0.0012~0.00145, and the change rate of Df after moisture absorption is low, ΔDf<0.00013 after 24h treatment at 23°C and 50% humidity; At the same time, the resin composition and the plate containing it have high glass transition temperature, good thermal stability, low thermal expansion coefficient, low water absorption rate of 0.04-0.06%, high peel strength, excellent overall performance, and fully meet the requirements of The performance requirements of high-frequency and high-speed copper foil substrates are specified.

Detailed ways

The technical solutions of the present invention will be further described below through specific embodiments. It should be clear to those skilled in the art that the embodiments are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

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

(1) Thermosetting polyphenylene ether:

OPE-2ST 2200: Japan Mitsubishi gas;

MX9000: Saudi Sabek.

(2) Multifunctional vinyl aromatic polymer

ODV-XET: Nippon Steel Chemical Industry Co., Ltd., Japan.

(3) Thermosetting hydrocarbon resin

B3000, Japanese Soda;

R154, Crayville, USA;

RB810, Japan JSR;

R100, Crayville, USA.

(4) Auxiliary cross-linking agent

TAIC, triallyl isocyanurate, American Sartomer;

TAC, triallyl cyanurate, American Sartomer;

TMAIC, trimethylallyl isocyanate, Hunan Fangruida;

DVB, divinylbenzene, Nippon Steel Chemical Industry Co., Ltd., Japan;

BVPE, 1,2-bis(p-vinylphenyl)ethane, Jiangsu Linchuan Chemical Industry;

TVCH, 1,2,4-trivinylcyclohexane, Evonik, Germany.

(5) Hydrogenated styrene-butadiene block copolymer and its modification (SEBS resin)

G1652, American Kraton;

KIC19-023, Kraton, USA.

(6) Flame retardant

BT-93W, brominated flame retardant, American Albemarle;

ST8010, American Albemarle;

XP7866, American Albemarle;

HCP-804, Kunshan Symphony, China.

(7) Silica

HM102, spherical silica prepared by organosilicon hydrolysis, with a purity of 99.99%, an average particle size (D ₅₀ ) of 0.95 μm, and a diameter distance of 0.426, Jiangsu Huimai;

HM102YJ, spherical silica prepared by organosilicon hydrolysis, with a purity of 99.95%, an average particle size (D ₅₀ ) of 0.95 μm, and a diameter distance of 0.500, Jiangsu Huimai;

HM052, spherical silica prepared by organosilicon hydrolysis, with a purity of 99.90%, an average particle size (D ₅₀ ) of 0.55 μm, and a diameter distance of 0.581, Jiangsu Huimai;

YP-1, spherical silica prepared by the flame method, with a purity of 99.90%, an average particle size (D ₅₀ ) of 2.63 μm, and a diameter distance of 1.313, made by the flame method;

FB-3SDC, spherical silica prepared by the flame method, with a purity of 99.90%, an average particle size (D ₅₀ ) of 3.1 μm, and a diameter distance of 1.364, NEC;

SFP-30M, spherical silica prepared by the flame method, with a purity of 99.90%, an average particle size (D ₅₀ ) of 1.2 μm, and a diameter distance of 0.934, NEC;

YP-2, spherical silica prepared by organosilicon hydrolysis method (tetraethoxysilane hydrolysis method), with a purity of 99.95%, an average particle size (D ₅₀ ) of 1.0 μm, and a diameter distance of 1.253;

YP-3, spherical silica prepared by chemical method, with a purity of 98.15%, an average particle diameter (D ₅₀ ) of 1.0 μm, and a diameter distance of 0.85; prepared by precipitation method using water glass as raw material, self-made.

(8) Low dielectric filler

CFP012, BN, 3M USA;

Polytetrafluoroethylene (PTFE) powder, Dongyue.

Example 1

The present embodiment provides a resin composition, comprising the following components in parts by weight: 20 parts of thermosetting polyphenylene ether (OPE-2ST 2200), 49 parts of polyfunctional vinyl aromatic polymer (ODV-XET), SEBS resin (G1652) 1 part, silica (HM102) 20 parts, brominated flame retardant (BT-93W) 10 parts.

This embodiment also provides a prepreg and a copper clad laminate, the specific preparation method of which is as follows:

(1) Mix thermosetting polyphenylene ether, polyfunctional vinyl aromatic polymer, SEBS resin and toluene, stir evenly at room temperature, then add bromine-containing flame retardant and silicon dioxide, mix evenly, and form a solid content of 65 % resin glue;

(2) impregnate the resin glue solution obtained in step (1) with glass fiber cloth (model 1078, China Taiwan Huber), heat and dry it in an impregnating machine oven at 130°C for 5min, so that the resin composition in the varnish state is converted into semi-cured The resin composition of state, obtains prepreg;

(3) Lay 9 prepregs obtained in step (2) layer by layer between two HOZ thick HVLP copper foils, under a pressure of 30kg/ ^cm2 and a heating rate of 3.5°C/min and a temperature of 200°C, Solidify for 120 minutes, then slowly cool to 50°C to obtain a copper clad laminate with a thickness of 0.75mm.

Embodiment 2～8, comparative example 1～8

A resin composition, the specific formulation of which is shown in Table 1 and Table 2; the dosage unit of each component in Table 1 and Table 2 is "part".

The resin compositions of Examples 2-8 and Comparative Examples 1-8 were prepared into copper clad laminates by the method described in Example 1, and the following physical property evaluation tests were carried out:

(1) Glass transition temperature (T _g , °C): According to IPC-TM-6502.4.24.4 (version 11/98), it was tested with a dynamic viscosity analyzer (DMA, Rheometric RSAIII);

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

(3) Peel strength of copper foil (PS, lb/in): According to the experimental conditions of "after thermal stress" in the IPC-TM-6502.4.8 method, the peel strength of the plate is tested;

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

(5) Dielectric loss factor Df (10GHz): according to IPC-TM-6502.5.5.13 test the loss factor Df at a frequency of 10GHz;

(6) ΔDf: comparative test put the sample at 23℃, 50%RH, the change value of Df before and after the sample is placed for 48 hours, according to IPC-TM-6502.5.5.13 test the loss factor Df at a frequency of 10GHz, use this value Subtract the Df value of the sample before placing it for 48 hours, and record it as ΔDf;

(7) Coefficient of thermal expansion (CTE): The thermal mechanical analyzer (TMA instrument) is used to test according to the CTE test standard stipulated in IPC-TM-6502.4.24.1.

The test results are shown in Table 1 and Table 2.

Table 1

Table 2

According to the data in Table 1 and Table 2, it can be seen that in the resin composition provided by the present invention, silicon dioxide with a purity > 99.9% and a diameter < 1 prepared by hydrolysis of organosilicon is compounded with a thermosetting resin to make the resin combination The material and the plate containing it have a lower dielectric constant and a lower dielectric loss factor. The Dk at 10GHz is 3.2-3.35, and the Df is 0.0012-0.00145, and the Df change rate after moisture absorption is low. 23 ℃, 50% After 24 hours of humidity treatment, ΔDf≤0.00012; and the plate has high glass transition temperature, good thermal stability, low thermal expansion coefficient, low water absorption rate, water absorption rate is 0.04-0.06%, high peel strength, good reliability, fully satisfied Performance requirements for high-frequency high-speed copper foil substrates.

Compared with Comparative Examples 1-7, in the resin composition and copper clad laminate of the present invention, the chemical method spherical silica prepared by alkoxysilane hydrolysis method is used, and its high purity ensures its low dielectric loss. ; Its diameter is small, compared with the spherical silica of the flame method, it has the characteristics of small water absorption and small change of Df after moisture absorption. In Comparative Example 8, the chemical method spherical silica prepared by hydrolysis of alkoxysilane has a purity of 99.95%, which ensures a low dielectric loss Df value, but because the diameter distance is greater than 1, it shows a relatively high water absorption rate 1. The disadvantage of Df changes greatly after moisture absorption. In Comparative Example 9, the silicon dioxide prepared by sodium silicate (water glass) hydrolysis precipitation method has a purity of less than 99%, and it contains more ions, resulting in a very high dielectric loss Df value, high water absorption, and high water absorption. Df changes greatly after tide.

The applicant declares that the present invention illustrates the resin composition of the present invention and its application through the above examples, but the present invention is not limited to the above examples, that is, it does not mean that the present invention can only be implemented depending on the above examples. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (10)

1. A resin composition, characterized in that 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 an auxiliary crosslinking agent containing at least two unsaturated functional groups;

   (B) silicon dioxide, the silicon dioxide is prepared by organosilicon hydrolysis, the purity of the silicon dioxide is ≥99.9%, the average particle size is 0.1-3 μm, and the diameter distance is <1;

   The mass percentage of silicon dioxide in the resin composition is 20-70%.
2. The resin composition according to claim 1, wherein the silicon dioxide is prepared by the following method, the method comprising: performing a hydrolysis reaction on organosilicon to obtain a primary product; the primary product is fired to obtain said silicon dioxide;

   Preferably, the organosilicon is an alkoxysilane;

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

   Preferably, the firing temperature is 800-1300°C;

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

   Preferably, the diameter of the silicon dioxide is <0.85, more preferably <0.65.
3. The resin composition according to claim 1 or 2, characterized in that, the mass percentage of thermosetting resin in the resin composition is 20-80%;

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

   Preferably, the thermosetting polyphenylene ether has the following structure:

   

   Among them, Z is

   

   A is selected from any one of -CO-, C6~C30 arylene, C1~C10 linear or branched alkylene;

   R ₁ , R ₂ , R ₃ are each independently selected from any one of hydrogen, C1-C10 straight chain or branched chain alkyl;

   m is an integer selected from 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 , and R ₁₅ are each independently selected from hydrogen, halogen, phenyl, C1-C10 straight chain or branched chain alkane any of the bases;

   R ₅ and R ₇ are each 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 or branched chain alkylene, -O-, -CO-, -CS-,

   

   

   any of the

   a and b are each independently selected from an integer of 1 to 30;

   Preferably, the mass percentage of thermosetting polyphenylene ether in the resin composition is 1-20%;

   Preferably, the polymerized monomers of the polyfunctional vinyl aromatic polymer include a combination of divinyl aromatic compounds and monovinyl aromatic compounds;

   Preferably, the molar percentage of structural units based on divinyl aromatic compounds in the polyfunctional vinyl aromatic polymer is 2-95%;

   Preferably, the divinyl aromatic compound includes any one or a combination of at least two of the following structural units:

   

   Wherein, R ^a and R ^b are independently selected from C6-C30 arylene groups;

   Preferably, the molar percentage of structural units based on monovinyl aromatic compounds in the polyfunctional vinyl aromatic polymer is 5-98%;

   Preferably, the number average molecular weight of the polyfunctional vinyl aromatic polymer is 600-20000 g/mol;

   Preferably, the mass percentage of the polyfunctional vinyl aromatic polymer in the resin composition is 1-50%;

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

   Preferably, the mass percentage of the thermosetting hydrocarbon resin in the resin composition is 0.1-40%.
4. The resin composition according to any one of claims 1 to 3, wherein the unsaturated functional groups in the co-crosslinking agent include vinyl, phenylvinyl, allyl, isopropenyl, acrylic or at least one of methacrylic;

   Preferably, the mass percent content of the auxiliary crosslinking agent in the resin composition is 0.1-30%;

   Preferably, the auxiliary crosslinking agent includes triallyl isocyanurate, triallyl cyanurate, trimethallyl isocyanate, divinylbenzene, 1,2-di(p-vinyl Any one or a combination of at least two of phenyl)ethane or 1,2,4-trivinylcyclohexane.
5. The resin composition according to any one of claims 1 to 4, wherein the resin composition further comprises a hydrogenated styrene-butadiene block copolymer;

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

   Preferably, an initiator is also included in the resin composition;

   Preferably, the initiator includes any one or a combination of at least two of organic peroxide initiators, azo initiators or carbon-based free radical initiators;

   Preferably, the organic peroxide initiator includes tert-butylcumyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl ylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne or 1,1-bis(tert-butylperoxy)-3,3, Any one or a combination of at least two of 5-dimethylcyclohexane;

   Preferably, the carbon-based free radical initiator includes bicumene and/or polylinkum;

   Preferably, based on 100% of the mass of the thermosetting resin, the mass of the initiator is 0.001-3%;

   Preferably, the resin composition also includes a flame retardant;

   Preferably, the flame retardant includes a bromine-containing flame retardant and/or a phosphorus-containing flame retardant;

   Preferably, the bromine-containing flame retardant includes any one or a combination of at least two of ethylene bis-tetrabromophthalimide, decabromodiphenylethane or decabromodiphenyl ether;

   Preferably, the phosphorus-containing flame retardants include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide additive flame retardants and/or phosphonate additive flame retardants agent;

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

   Preferably, the resin composition also includes low dielectric fillers;

   Preferably, the low dielectric filler includes any one or a combination of at least two of boron nitride, polytetrafluoroethylene powder or silica-coated polytetrafluoroethylene powder;

   Preferably, the mass percent content of the low-dielectric filler in the resin composition is 0.1-10%.
6. A resin film, characterized in that the material of the resin film comprises the resin composition according to any one of claims 1-5;

   Preferably, the resin film is prepared by coating the resin composition on a release material and drying and/or baking.
7. A resin-coated copper foil, characterized in that the resin-coated copper foil includes copper foil, and a resin layer arranged on one side of the copper foil, and the material of the resin layer includes any one of claims 1-5. The resin composition;

   Preferably, the resin-coated copper foil is prepared by coating the resin composition on a copper foil and drying and/or baking.
8. A prepreg, characterized in that the prepreg includes a reinforcing material, and the resin composition according to any one of claims 1 to 5 attached to the reinforcing material after being impregnated and dried.
9. A copper-clad laminate, characterized in that the copper-clad laminate comprises at least one of the resin film as claimed in claim 6, the resin-coated copper foil as claimed in claim 7, or the prepreg as claimed in claim 8.
10. A printed circuit board, characterized in that the printed circuit board comprises the resin film as claimed in claim 6, the resin-coated copper foil as claimed in claim 7, the prepreg as claimed in claim 8 or the At least one of the copper clad laminates according to claim 9.