TWI802482B - A resin composition and application thereof - Google Patents

Abstract

The present invention discloses a resin composition and application thereof. The resin composition includes the following components: (A) thermosetting resin including the combination of at least two of thermosetting polyphenylene ether, polyfunctional vinyl aromatic polymer, thermosetting hydrocarbon resin or co-agents comprising at least two unsaturated functional groups; (B) silica prepared by organosilicon hydrolysis and having a purity of 99.9% or more, an average particle size of 0.1~3 μm and a radial distance of less than 1. The silica in the resin composition has a mass percentage of 20~70%. The resin composition not only has low dielectric constant and low dielectric loss, but also shows a small change in dielectric loss after absorbing moisture, low water absorption rate and high thermal stability. A prepreg prepared from the resin composition can fully meet the performance requirements of high-frequency and high-speed copper clad laminate.

Description

A kind of resin composition and its application

Embodiments of the present invention relate to the technical field of copper clad laminates, such as a resin composition and its application.

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 silicon powder is used, but its diameter is 1.32, indicating that the particle size distribution of silicon 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 decreases, which affects the Df of silicon dioxide; moreover, the particle size distribution of fused silicon dioxide, which is also produced by the flame fusion method, is relatively wide, resulting in a large change rate of Df after the resin composition absorbs moisture. 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 cause the Df change rate of the composite material to be relatively low after moisture absorption. big. CN103450639A discloses a thermosetting resin composition and its application. The thermosetting resin composition contains silicon dioxide with a closed surface and internal pores. It is made of silicon dioxide by a chemical method, and is an aggregate of spherical silicon obtained by a chemical method by hydrolysis of organic silicon , and then burnt to obtain porous silicon dioxide with a closed surface; since the aggregates of spherical silicon in the chemical method are directly burned during the production process, they are not depolymerized into single particles. During the burning process, some impurities will be closed on the surface. The interior of the porous silica leads to a higher Df. CN1634763A discloses a method for preparing nanometer-grade high-purity silicon dioxide, adopts chemical direct synthesis method, and obtains a product with a particle size of 5-20 nm, but because its particle size is about 10 nm, the viscosity of the glue will Very, it has a very large negative impact on the bonding sheet manufacturing process of copper clad laminate (CCL), and it is impossible to make qualified bonding sheets.

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.

Aiming at the deficiencies of the prior art, the present invention provides a resin composition and its application. By compounding a low-dielectric thermosetting resin and specific silicon dioxide, the resin composition not only has a low dielectric constant and a low Dielectric loss, and the change rate of dielectric loss after moisture absorption is small, low water absorption, high thermal stability, and good reliability; the prepreg prepared by the resin composition can fully meet the performance of high-frequency and high-speed copper foil substrates Require.

In the first aspect, the embodiment of the present invention provides a resin composition, the resin composition includes the following components: (A) thermosetting resin, the thermosetting resin includes thermosetting polyphenylene ether, polyfunctional vinyl aromatic polymer, thermosetting A combination of at least two of hydrocarbon resins or auxiliary crosslinking agents containing at least two unsaturated functional groups; (B) silicon dioxide, which is prepared by hydrolysis of organosilicon, and the silicon dioxide is Purity≧99.9%, average particle size (D ₅₀ ) of 0.1~3 μm, and radial distance<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, a compound of low-dielectric thermosetting resin and silicon dioxide is used. The silicon dioxide is prepared by a chemical method (organic silicon hydrolysis method), has high purity, and has an average particle size (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 silicon dioxide is ≧99.9%, such as 99.92%, 99.95%, 99.97%, 99.99%, 99.991%, 99.993%, 99.995%, 99.997% or 99.999%.

The purity of 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 silicon dioxide 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 μm or 2.8 μm etc.

The diameter of the silicon dioxide is less than 1, such as 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, 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.

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

Ideally, the silicone is an alkoxysilane.

Ideally, the alkoxysilanes include tetraethoxysilane, tetramethoxysilane, tetraphenoxysilane, tetra-n-butoxysilane, tetraisobutyloxysilane, methyltriethoxysilane , any one or a combination of at least two of dimethyldiethoxysilane; Ideally, the firing temperature is 800-1300°C, for example, 850°C, 900°C, 950°C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C or 1250°C.

Ideally, the purity of the silicon dioxide is >99.95%, more ideally >99.99%.

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

Ideally, 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.

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

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

。 Ideally, the thermosetting polyphenylene ether has the structure shown below:

.

或

；波浪線代表基團的連接位點。 Among them, Z is

or

; 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 examples include but are not limited to: methylene, ethylene, propylene or butylene wait.

R ₁ , R ₂ , R ₃ are each independently selected from hydrogen, C1~C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight chain or branched chain alkyl 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 to 10, for example, it can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

，X為

；波浪線代表基團的連接位點。 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.

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.

或

中的任意一種；所述「L為單鍵」意指兩個苯環通過單鍵相連、形成聯苯的結構。 L is selected from single bond, C1~C10 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) straight or branched chain alkylene, -O-, -CO-, -CS -,

or

Any one of them; the "L is a single bond" means that two benzene rings are connected 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. .

Ideally, 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.

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

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

、

；其中，基團兩側的短直線代表接入鍵，不代表甲基；下文中涉及到相同的表述方式時，均具有相同的含義。 Ideally, 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, R ^a 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 kinds; the divinylbiphenyl includes 4,4'-divinylbiphenyl, 4,3'-divinylbiphenyl, 4,2'-divinylbiphenyl, 3,2 Any one or a combination of at least two of '-divinylbiphenyl, 3,3'-divinylbiphenyl, 2,2'-divinylbiphenyl or 2,4-divinylbiphenyl; 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 naphthalene, 2,6-divinylnaphthalene or 2,7-divinylnaphthalene.

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

Ideally, the monovinyl aromatic compound includes styrene, and other monovinyl aromatic compounds except 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 or branched chain alkyl.

Ideally, 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, 10000 g/mol, 11000 g/mol, 13000 g/mol, 15000 g/mol, 17000 g/mol or 19000 g/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.

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

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

Ideally, the mass percentage of the thermosetting hydrocarbon resin in the resin composition is 0.1-40%, such as 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 at least two of B3000 from Japan Soda, R154 from American Craigville, RB810 from Japan JSR or R100 from American Crayville combination of species.

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

Ideally, the mass percentage of the auxiliary crosslinking agent in the resin composition is 0.1-30%, for example, it can be 0.3%, 0.5%, 1%, 3%, 5%, 8%, 10%, 12% , 15%, 18%, 20%, 22%, 25% or 28%, etc.

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

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

Ideally, 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.

Ideally, the resin composition further includes an initiator.

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

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

Ideally, the carbon-based free radical initiator includes bicumene and/or polylinketate.

Ideally, based on the mass of the thermosetting resin as 100%, 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.

Ideally, the resin composition further includes a flame retardant.

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

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

Ideally, 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.

Ideally, 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.

Ideally, the resin composition also includes low-dielectric fillers.

Ideally, 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.

Ideally, the mass percent content 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-mentioned resin composition, and the amount of solvent added is selected by a person with ordinary knowledge in the technical field based on experience and process requirements, so that the resin composition can reach a viscosity suitable for use, so that the resin composition can be impregnated, What is necessary is just to coat and the like. In 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. Ideally used are ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene.

In a second aspect, an embodiment of the present invention provides a resin film, and the material of the resin film includes the resin composition as described in the first aspect.

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

In a third aspect, an embodiment of 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, and the material of the resin layer includes the following The resin composition described in one aspect.

Ideally, 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, an embodiment of the present invention provides a prepreg (PP) sheet, the prepreg including a reinforcing material, and the resin composition according to the first aspect attached to the reinforcing material after impregnation and drying.

Ideally, 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 fabrics, etc., and low-dielectric reinforcing materials can also be selected according to needs. Such as NE fiberglass cloth, Q quartz cloth, QL cloth, etc.

In the fifth aspect, an embodiment of the present invention provides a copper-clad laminate, which includes 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. at least one.

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.

Ideally, 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.

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

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

In the sixth aspect, the embodiment of 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 prepreg as described in the fourth aspect Or at least one of the copper clad laminates as described in the fifth aspect.

Compared with the related prior art, the embodiments of the present invention have the following effects: In the resin composition provided by the embodiment of the present invention, the low-dielectric thermosetting resin is compounded with specific silicon dioxide, so that the resin composition and the board containing it have a lower dielectric constant and a lower dielectric constant. Electrical loss factor, Dk<3.5 at 10 GHz, 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, after 24 hours of treatment at 23°C and 50% humidity ΔDf<0.00013; at the same time, the glass transition temperature of the resin composition and the plate containing it is high, the thermal stability is good, the thermal expansion coefficient is low, the water absorption rate is 0.04~0.06%, the water absorption rate is low, the peel strength is high, and the overall performance Excellent, fully meeting the performance requirements of high-frequency high-speed copper foil substrates.

The technical means of the present invention will be further described below through specific embodiments. It should be clear to those skilled in the art that the examples are only to help the understanding of the present invention, and should not be regarded as a specific limitation on 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 of Japan; MX9000: Saudi Sabek. (2) Multifunctional vinyl aromatic polymer ODV-XET: Japan Nippon Steel Chemical Industry Co., Ltd. (3) Thermosetting hydrocarbon resin B3000, Soda, Japan; R154, Crayville, USA; RB810, JSR, Japan; R100, Crayville, USA. (4) Auxiliary cross-linking agent TAIC, triallyl isocyanurate, American sandy; TAC, triallyl cyanurate, American sandy; TMAIC, trimethylallyl isocyanate, Hunan Fangruida; DVB, divinylbenzene, Nippon Steel Chemical Industry Co., Ltd.; BVPE, 1,2-di(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, American Kraton. (6) Flame retardant BT-93W, a brominated flame retardant, American Albemarle; ST8010, American Albemarle; XP7866, American Albemarle; HCP-804, China Kunshan Symphony. (7) Silica HM102, spherical silica prepared by organosilicon hydrolysis method, with a purity of 99.99%, average particle size (D ₅₀ ) of 0.95 μm, diameter distance of 0.426, Jiangsu Huimai; HM102YJ, organosilicon hydrolysis method The prepared spherical silica, the purity is 99.95%, the average particle size (D ₅₀ ) is 0.95 μm, the diameter is 0.500, Jiangsu Huimai; HM052, the spherical silica prepared by organosilicon hydrolysis, the purity is 99.90%, The average particle size (D ₅₀ ) is 0.55 μm, the diameter distance is 0.581, Jiangsu Huimai; YP-1, spherical silica prepared by flame fusion method, the purity is 99.90%, the average particle size (D ₅₀ ) is 2.63 μm, The diameter is 1.313, self-made by flame fusion method; FB-3SDC, spherical silica prepared by flame fusion method, the purity is 99.90%, the average particle size (D ₅₀ ) is 3.1 μm, the diameter is 1.364, Japan Denki Chemical; SFP -30M, spherical silica prepared by flame fusion method, with a purity of 99.90%, an average particle size (D ₅₀ ) of 1.2 μm, and a diameter of 0.934, Japan Denka Chemicals; YP-2, organosilicon hydrolysis method (tetraethoxy Spherical silica prepared by hydrolysis of base silane), with a purity of 99.95%, an average particle size (D ₅₀ ) of 1.0 μm, and a diameter of 1.253; YP-3, a spherical silica prepared by a chemical method, a purity of 98.15%, with an average The particle size (D ₅₀ ) is 1.0 μm, and the diameter distance is 0.85; the water glass is used as the raw material to prepare by the precipitation method, which is self-made. (8) Low dielectric filler CFP012, BN, American 3M; Polytetrafluoroethylene (PTFE) powder, Dongyue. [Example 1]

This embodiment provides a resin composition, which includes 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, silicon dioxide (HM102) 20 parts, brominated flame retardant (BT-93W) 10 parts.

This embodiment also provides a prepreg and copper clad laminate. The specific preparation method is as follows: (1) Mix thermosetting polyphenylene ether, polyfunctional vinyl aromatic polymer, SEBS resin and toluene, stir evenly at room temperature, and then add bromine-containing Flame retardant and silicon dioxide, mixed evenly to form a resin glue with a solid content of 65%; (2) impregnating the resin glue obtained in step (1) with glass fiber cloth (model 1078, Huber, Taiwan), at 130 ℃ in an impregnating machine oven for 5 minutes, so that the resin composition in the varnish state is transformed into a resin composition in a semi-cured state to obtain a prepreg; (3) stack 9 prepregs obtained in step (2) on two Between sheets of HOZ thick HVLP copper foil, solidify for 120 minutes at a pressure of 30 kg/ ^cm2 and a heating rate of 3.5°C/min at a temperature of 200°C, and then slowly cool to 50°C to obtain a thickness of 0.75mm CCL.

Examples 2-8, Comparative Examples 1-8 A resin composition, the specific formula 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-650 2.4.24.4 (version 11/98), the test is carried out with a dynamic viscosity analyzer (DMA, Rheometric RSAIII); (2) Water absorption (%): the sample is heated in a pressure cooker at 120°C and 2 atm Calculate the weight change before and after heating after 120 minutes; (3) Peel strength of copper foil (PS, lb/in): according to the experimental conditions of "after thermal stress" in IPC-TM-650 2.4.8 method, test the peel strength of the plate; (4) Dielectric constant Dk (10 GHz): According to IPC-TM-650 2.5.5.13 test the dielectric constant Dk at a frequency of 10 GHz; (5) Dielectric loss factor Df (10 GHz): According to IPC-TM -650 2.5.5.13 Test the loss factor Df at a frequency of 10 GHz; (6) ΔDf: comparative test put the sample at 23°C, 50%RH, the change value of Df before and after the sample is placed for 48 hours, according to IPC-TM- 650 2.5.5.13 Test the loss factor Df at a frequency of 10 GHz, subtract the Df value of the sample before placing it for 48 hours with this value, and record it as ΔDf; (7) Coefficient of thermal expansion (CTE): use a thermomechanical analyzer (TMA instrument ), according to the CTE test standard stipulated in IPC-TM-650 2.4.24.1.

The test results are shown in Table 1 and Table 2. Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 thermosetting polyphenylene ether OPE-2ST 2200 20 10 10 10 MX9000 20 10 Multifunctional Vinyl Aromatic Polymer ODV-XET 49 30 20 10 10 Thermosetting Hydrocarbon Resin B3000 10 10 10 10 8 R154 10 4 RB810 10 10 R100 10 auxiliary crosslinking agent TAIC 5 TAC 5 TMAIC 2 DVB 8 BVPE 5 TVCH 10 SEBS resin G1652 1 0 KIC19-023 2 1 2 2 2 flame retardant BT-93W 10 ST8010 13 18 10 10 XP7866 20 25 PQ60 18 silicon dioxide HM102 20 45 40 HM102YJ 30 68 50 HM052 40 40 Low dielectric filler BN 5 PTFE powder 2 total 100 100 100 100 100 100 100 100 _g DMA 201 210 195 192 198 205 205 204 P.S. A 0.6 0.65 0.55 0.54 0.6 0.65 0.65 0.54 CTE 50~260℃ 2.5 2.4 2.3 2 1.5 2.2 2.2 1.4 d 10GHz 3.2 3.22 3.28 3.35 3.35 3.25 3.25 3.35 Df 10GHz 0.00150 0.00142 0.00131 0.00125 0.00120 0.00130 0.00130 0.00127 ΔDf 10GHz 0.00010 0.00010 0.00011 0.00011 0.00010 0.00011 0.00010 0.00012 water absorption % 0.06 0.05 0.04 0.05 0.04 0.05 0.05 0.06 Table 2 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 thermosetting polyphenylene ether OPE-2ST 2200 20 10 10 20 20 MX9000 20 10 Multifunctional Vinyl Aromatic Polymer ODV-XET 49 20 10 10 49 49 Thermosetting Hydrocarbon Resin B3000 10 10 10 10 8 R154 10 4 RB810 10 10 R100 auxiliary crosslinking agent TAIC TAC 5 TMAIC 2 DVB 8 BVPE 5 TVCH 10 SEBS resin G1652 1 0 1 1 KIC19-023 1 2 2 2 flame retardant BT-93W 10 10 10 ST8010 18 10 10 XP7866 20 25 PQ60 18 silicon dioxide YP-1 20 68 40 40 50 FB-3SDC 40 SFP-30M 45 YP-2 20 YP-3 20 Low dielectric filler BN 5 PTFE powder 2 total 100 100 100 100 100 100 100 100 100 _g DMA 201 195 192 198 205 205 204 201 201 P.S. A 0.61 0.53 0.51 0.58 0.63 0.63 0.52 0.52 0.51 CTE 50~260℃ 2.5 2.3 2 1.5 2.2 2.2 1.4 2.5 2.5 d 10GHz 3.21 3.28 3.35 3.35 3.25 3.25 3.35 3.20 3.20 Df 10GHz 0.00165 0.00141 0.00138 0.00133 0.00142 0.00145 0.00138 0.00150 0.00195 ΔDf 10GHz 0.00018 0.00023 0.00025 0.00032 0.00030 0.00028 0.00028 0.00023 0.00018 water absorption % 0.10 0.13 0.14 0.15 0.14 0.14 0.14 0.12 0.11

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 composition And the plate containing it has lower dielectric constant and lower dielectric loss factor, Dk at 10 GHz is 3.2~3.35, Df is 0.0012~0.00145, and the change rate of Df after moisture absorption is low, 23 ℃, 50 ΔDf≤0.00012 after 24 hours of humidity treatment; 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, sufficient It meets the performance requirements of high-frequency and high-speed copper foil substrates.

Compared with Comparative Examples 1-7, the resin composition and the copper-clad laminate of the present invention adopt the chemical method spherical silica prepared by hydrolysis of alkoxysilane, and its high purity ensures its low dielectric loss. ; Its diameter is small, compared with the spherical silica of the flame fusion 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 relatively high water absorption. , 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 high dielectric loss Df value, high water absorption, and high water absorption. Df after wet changes greatly.

The applicant declares that the present invention illustrates the detailed methods of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed methods, that is, it does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented. Those with ordinary knowledge in the technical field should understand that any improvement of the present invention, the equal 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 (14)

A resin composition characterized by 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, which 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%. The resin composition as described in 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; firing the primary product to obtain the silicon dioxide. The resin composition as described in Claim 2, wherein the organosilicon is an alkoxysilane; The alkoxysilanes include tetraethoxysilane, tetramethoxysilane, tetraphenoxysilane, tetra-n-butoxysilane, tetraisobutyloxysilane, methyltriethoxysilane or dimethyl Any one or a combination of at least two of diethoxysilanes; The firing temperature is 800-1300°C. The resin composition according to claim 1, wherein the thermosetting polyphenylene ether has the following structure:

; Among them, Z is

or

; A is selected from any one of -CO-, C6~C30 arylene, C1~C10 straight chain or branched chain alkylene; R ₁ , R ₂ , R ₃ are each independently selected from hydrogen, C1~C10 straight chain Any one of chain or branched chain alkyl; m is an integer selected from 0 to 10; Y is

, X is

; The wavy line represents the connection 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, benzene any one of C1~C10 straight chain or branched chain alkyl; 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-,

or

any one of them; a and b are independently selected from an integer of 1 to 30; the mass percentage of thermosetting polyphenylene ether in the resin composition is 1 to 20%. The resin composition according to claim 1, wherein the polymerized monomer of the polyfunctional vinyl aromatic polymer includes a combination of divinyl aromatic compounds and monovinyl aromatic compounds; The number average molecular weight of the polyfunctional vinyl aromatic polymer is 600-20000 g/mol; The mass percent content of the polyfunctional vinyl aromatic polymer in the resin composition is 1-50%. The resin composition according to claim 1, wherein the thermosetting hydrocarbon resin comprises polybutadiene and/or styrene-butadiene-styrene copolymer; The mass percent content of the thermosetting hydrocarbon resin in the resin composition is 0.1-40%. The resin composition as claimed in item 1, wherein, the unsaturated functional group in the auxiliary crosslinking agent includes at least one of vinyl, phenylvinyl, allyl, isopropenyl, acrylic or methacrylic A sort of; The mass percent content of the auxiliary crosslinking agent in the resin composition is 0.1-30%. The resin composition as claimed in item 1, wherein, the resin composition also includes a hydrogenated styrene-butadiene block copolymer; The mass percent content of the hydrogenated styrene-butadiene block copolymer in the resin composition is 0.1-10%. The resin composition as claimed in item 1, wherein, the resin composition also includes an initiator; Based on the mass of the thermosetting resin being 100%, the mass of the initiator is 0.001-3%. The resin composition as described in claim 1, wherein, the resin composition also includes a flame retardant; The mass percent content of the flame retardant in the resin composition is 10-25%. The resin composition as claimed in claim 1, wherein the resin composition also includes low dielectric fillers; The mass percentage content of the low dielectric filler in the resin composition is 0.1-10%. A resin film, characterized in that the material of the resin film includes the resin composition described in any one of Claims 1 to 11; The resin film is prepared by coating the resin composition on the release material and drying and/or baking. A prepreg, characterized in that the prepreg includes a reinforcing material, and the resin composition as described in any one of Claims 1 to 11 adhered to the reinforcing material after being impregnated and dried. A copper clad laminate, characterized in that the copper clad laminate comprises at least one of the resin film as claimed in claim 12 or the prepreg as claimed in claim 13.