TWI756037B - A kind of resin composition and its application - Google Patents

Abstract

The invention relates to a resin composition and an application thereof. The resin composition comprises the following components in parts by weight: thermosetting polyphenylene ether resin, cross-linking agent, epoxy silane oligomer and free radical initiator; the cross-linking agent The linking agent includes a polyolefin resin with unsaturated double bonds; the epoxy silane oligomer has the structure shown in formula I. In the present invention, epoxy silane oligomer is added to the polyphenylene ether+polyolefin resin system, which can not only effectively improve the peel strength and interlayer adhesion, but also because the epoxy silane oligomer is not easy to volatilize, the peel strength of the sheet and the interlayer adhesion Adhesion is not affected by temperature changes during processing, ensuring the stability of peel strength and interlayer adhesion without affecting the dielectric properties and heat resistance of the sheet.

Description

A kind of resin composition and its application

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

In recent years, with the development of high-performance, high-function and networking of computers and information communication equipment, in order to transmit and process large-capacity information at high speed, the operation signal tends to be high-frequency, so the material of the circuit substrate is required. , especially in those electronic devices that use broadband, such as mobile communication devices, there is a rapid development.

Among existing materials for printed circuit boards, epoxy resins having excellent adhesive properties are widely used. However, epoxy circuit substrates generally have high dielectric constant and dielectric loss tangent (dielectric constant Dk is greater than 4, dielectric loss tangent Df is about 0.02), and the high-frequency characteristics are insufficient, which cannot meet the requirements of high-frequency signals. . Therefore, it is necessary to develop resins with excellent dielectric properties, that is, resins with low dielectric constant and dielectric loss tangent. For a long time, those with ordinary knowledge in the technical field have conducted research on thermosetting polyphenylene ether resin, bismaleimide resin, vinylbenzyl ether resin, hydrocarbon resin, etc. with good dielectric properties; Cured and cross-linked hydrocarbon resin (polyolefin resin) has lower dielectric loss tangent Df (comparable to PTFE resin) and better fluidity, which attracts people with ordinary knowledge in the technical field. A lot of in-depth research has been done on it, but due to its insufficient peel strength and interlayer adhesion, it cannot meet the requirements of high multi-layer printed electronics. The process production requirements of the road board need to be used in conjunction with the selection of specific resins.

The application of the modified polyphenylene ether resin with active groups at the end of the molecular chain or side chain in the high-speed circuit substrate is generally to form a resin composition in combination with a cross-linking agent. The crosslinking agent has reactive groups that can react with the modified polyphenylene ether. According to literature research, for the modified polyphenylene ether with C=C double bond, the commonly used crosslinking agents are polybutadiene, butadiene-styrene copolymer, etc. For example, the CN 102807658A patent uses polybutadiene or butadiene-styrene copolymer as the crosslinking agent of the modified polyphenylene ether to prepare a high-speed circuit substrate. Although the comprehensive properties of the sheet are excellent, but polybutadiene or butadiene-styrene copolymer reduces the peel strength and interlayer adhesion of the sheet, adding a small molecule epoxy silane coupling agent KBM- 403 (Shin-Etsu Chemical Co., Ltd.) to improve the peel strength and interlayer adhesion of the system, but because the small molecule epoxy silane coupling agent is very easy to volatilize during the production of prepreg, it is not conducive to stable production of prepreg and laminate.

Therefore, there is an urgent need in the art to develop a resin composition based on a polyphenylene ether+polyolefin system, which has excellent and stable peel strength and interlayer adhesion, and has excellent Dk, Df, heat resistance and other properties.

【Prior technical literature】

【Patent Literature】

[Patent Document 1] CN 102807658A

One of the objectives of the present invention is to provide a resin composition, the copper clad laminate prepared from the resin composition has excellent and stable peel strength and interlayer adhesion, and also has Excellent Dk, Df and heat resistance properties.

For this purpose, the present invention adopts the following technical means:

The invention provides a resin composition comprising the following components according to parts by weight: thermosetting polyphenylene ether resin, crosslinking agent, epoxy silane oligomer and free radical initiator;

The crosslinking agent includes a polyolefin resin with unsaturated double bonds;

The epoxy silane oligomer has the structure shown in formula I:

In formula I, described R ₁ , R ₂ are each independently selected from substituted or unsubstituted C1～C8 (such as C2, C3, C4, C5, C6, C7 etc.) straight-chain alkyl, substituted or unsubstituted C1 Any one of ~C8 (such as C2, C3, C4, C5, C6, C7, etc.) branched chain alkyl; in formula I, the n is an integer from 0 to 4, such as 1, 2, or 3, etc.

In the present invention, epoxy silane oligomer is added to the polyphenylene ether+polyolefin resin system, which can not only effectively improve the peel strength and interlayer adhesion, but also because the epoxy silane oligomer is not easy to volatilize, the peel strength of the sheet and the interlayer adhesion Adhesion is not affected by temperature changes during processing, resulting in high peel strength and interlayer adhesion even at higher processing temperatures. In addition, the inventor found in the research that the chain length of the epoxy silane oligomer is too long, which will also affect the board When n in formula I exceeds 4, although the peel strength and interlayer adhesion will be further improved, and the epoxy silane oligomer will not be easily volatilized, the dielectric properties of the board will be significantly worsened. The Dk and Df values increase, so the present invention defines that the main chain of the epoxysilane oligomer contains 2 to 6 siloxane units (that is, n is 0 to 4), and only the chain length is controlled within this specific range , so that the prepared sheet can have excellent Dk, Df and heat resistance while having excellent and stable peel strength and interlayer adhesion.

Ideally, the thermosetting polyphenylene ether resin has the structure shown in formula II:

In formula II, the a and b are each independently an integer from 1 to 30, such as 2, 3, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, etc. ;

In formula II, described Z has the structure shown in formula III or formula IV:

In formula IV, described A is selected from any one in C6～C30 arylene, C1～C10 alkylene or carbonyl, described R ₁ , R ₂ and R ₃ are each independently selected from hydrogen atom or C1～C10 Alkyl, the m is selected from an integer of 0 to 10, such as 2, 3, 4, 6, 8, 10, etc.;

In formula II, the -(-O-Y-)- has the structure shown in formula V:

In formula V, described R ₄ and R ₆ are each independently selected from any one of hydrogen atom, halogen atom, C1～C10 alkyl or phenyl, and described R ₅ and R ₇ are each independently selected from halogen atom, Any one of C1～C10 alkyl or phenyl;

In formula II, the -(-O-X-O-)- has the structure shown in formula VI:

、

、

、

、

或

中的任意一種，所述R₁₆選自氫原子或C1~C10烴基，所述r為0或1。所述烴基包括但不限於烷烴基或烯烴基。 In formula VI, described R ₈ ～R ₁₅ are each independently selected from any one in hydrogen atom, halogen atom, C1～C10 alkyl or phenyl, and described B is selected from C1～C20 alkylene,

,

,

,

,

or

In any one, the R ₁₆ is selected from a hydrogen atom or a C1-C10 hydrocarbon group, and the r is 0 or 1. The hydrocarbon group includes, but is not limited to, an alkane group or an alkene group.

In the present invention, the wavy line marks represent connecting keys.

Ideally, the number average molecular weight of the thermosetting polyphenylene ether resin is 500-10000g/mol, such as 600g/mol, 800g/mol, 1000g/mol, 1500g/mol, 2000g/mol, 3000g/mol, 4000g/mol, 5000g /mol, 6000g/mol, 7000g/mol, 8000g/mol, 9000g/mol, etc., 800-8000g/mol is desirable, and 1000-4000g/mol is more desirable. The test method of molecular weight in the present invention is GB/T 21863-2008, which is passed on the basis of polystyrene calibration determined by gel permeation chromatography.

20%，例如15%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%、85%、90%、95%等。 Ideally, the polyolefin resin with an unsaturated double bond contains butadiene units added at positions 1 and 2, and the butadiene units added at positions at positions 1 and 2 account for the weight of

20%, such as 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90 %, 95%, etc.

Ideally, the crosslinking agent also includes a co-crosslinking agent

Ideally, the co-crosslinking agent includes triallyl cyanurate, triallyl cyanurate, multifunctional acrylate compounds, bismaleimide resins, or divinylbenzene-polyfunctional ethylene Any one or a combination of at least two of the base aromatic compound copolymers, ideally triallyl cyanurate, triallyl isocyanate, multifunctional acrylate compound or divinylbenzene-polyfunctional ethylene Any one or a combination of at least two of the base aromatic compound copolymers.

In the present invention, "multifunctional group" refers to containing at least two functional groups.

Ideally, the free radical initiator includes a first initiator and/or a second initiator, and the 1-minute half-life temperature of the first initiator is 50-160°C, such as 60°C, 70°C, 80°C, 90°C ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, etc., the 1-minute half-life temperature of the second initiator is 161~300 ℃, such as 170 ℃, 180 ℃, 190 ℃, 200 ℃ , 220℃, 240℃, 260℃, 280℃, etc.

Ideally, the first initiator is selected from the group consisting of tert-butyl peroxyacetate, 2,2-bis(tert-butylperoxy)octane, tert-butylperoxyisopropyl carbonate, 1,1- Bis(tert-butylperoxy)cyclohexanone, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexanone, tert-butylperoxyoctanoate, tert-butylperoxycaprylate Butyl Peroxyisobutyrate, Disuccinic Acid Peroxide, Di-m-Toluene Peroxide, Xylyl Peroxide, Diacetyl Peroxide, Cumyl Peroxyoctanoate, Diklein Acetyl peroxide, dioctyl peroxide, didodecyl peroxide, bis(3,5,5-trimethylacetoxyperoxide) compound), tert-butyl peroxypivalate, tert-hexyl peroxytrimethyl acetate, tert-butyl peroxynecaproate, tert-hexyl peroxynecaproate, bis(3-methyl- 3-Methoxybutyl peroxybicarbonate), tert-hexyl peroxynecaproate, tert-butyl peroxynecaproate, cumyl peroxynecaproate, dimethoxyisopropyl base peroxybicarbonate, ditetradecyl peroxybicarbonate, bisallyl peroxybicarbonate, cumyl peroxynecaprate, di-n-propyl peroxybicarbonate, bis (2-Hydroxyethylhexylperoxybicarbonate), Bis(2-ethylhexylperoxybicarbonate), Di-n-butylperoxybicarbonate, Diisobutylperoxybicarbonate, Diisobutylene Any one or a combination of at least two of peroxide, diisopropyl peroxybicarbonate, or acetylcyclohexylsulfonyl peroxide.

Ideally, the second initiator comprises tert-butyl hydroperoxide, tetramethylbutane peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne, tert-Butyl peroxide, a,abis(tert-butylperoxy-m-cumyl), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butylperoxy Butylcumyl peroxide, tert-butylperoxyallyl bicarbonate, dicumyl peroxide (DCP), tert-butylperoxybenzoate, di-tert-butylperoxyiso Phthalate, n-butyl-4,4-bis(tert-butylperoxy)valerate, tert-butylperoxy(3,5,5-trimethylacetate), tert-butylperoxylauryl acid ester, 2,5-dimethyl-2,5-bis(dibenzoylperoxy)hexane or 2,2-bis(tert-butylperoxy)butane, or any one or a combination of at least two of them.

Ideally, based on the total mass of the thermosetting polyphenylene ether resin and the crosslinking agent as 100 parts by weight, the addition amount of the thermosetting polyphenylene ether resin is 20 to 90 parts by weight, such as 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, etc.

Ideally, based on the total mass of the thermosetting polyphenylene ether resin and the cross-linking agent as 100 parts by weight, the addition amount of the cross-linking agent is 10 to 80 parts by weight, such as 15 parts by weight, 20 parts by weight, 25 parts by weight parts, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight parts, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, etc.

Ideally, based on the total mass of the thermosetting polyphenylene ether resin and the crosslinking agent as 100 parts by weight, the amount of the epoxy silane oligomer added is 0.1 to 5 parts by weight, such as 0.2 parts by weight, 0.4 parts by weight , 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 4.8 parts by weight, etc.

The present invention can further improve the peel strength and interlayer adhesion, as well as dielectric properties and heat resistance of the board prepared from the resin composition by further ideally adding an epoxy silane oligomer of 0.1 to 5 parts by weight. If the addition amount is too low, it is not enough to improve the peel strength and interlayer adhesion, but if the addition amount is too high, it will deteriorate the dielectric loss Df of the system.

Ideally, based on the total mass of the thermosetting polyphenylene ether resin and the crosslinking agent as 100 parts by weight, the amount of the free radical initiator added is 0.1 to 5 parts by weight, such as 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 4.8 parts by weight, etc.

Ideally, based on the mass of the thermosetting polyphenylene ether resin as 100 parts by weight, the addition amount of the co-crosslinking agent is 3 to 60 parts by weight, such as 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight parts, 50 parts by weight, 55 parts by weight, 60 parts by weight, etc.

Desirably, the resin composition further includes fillers.

Ideally, the fillers include organic fillers and/or inorganic fillers.

Ideally, the organic filler includes any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder, polyetherimide powder, polyphenylene ether powder or polyether titanate powder.

Desirably, the inorganic filler includes silica, glass frit, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talc, silicon Any one or a combination of at least two of calcium acid, calcium carbonate or mica.

Desirably, the silica comprises crystalline silica and/or fused silica.

Ideally, the silica comprises solid silica and/or hollow silica.

Ideally, the silica comprises spherical silica.

The present invention does not limit the shape and particle size of the inorganic filler, and the particle size usually used is 0.01 to 50 μm, such as 0.01 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.5 μm, 1 μm, 3 μm, 5 μm, 8 μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm or 50μm, etc., ideally 0.01~20μm, more ideally 0.01~10μm, inorganic fillers in this particle size range are more suitable for circuit substrates in resin solution. The particle size in the present invention is measured by a Malvern 2000 laser particle size analyzer.

Desirably, the resin composition further includes a flame retardant.

Desirably, the flame retardant includes a brominated flame retardant and/or a halogen-free flame retardant.

Ideally, the halogen-free flame retardant includes any one or a combination of at least two of phosphorus-containing flame retardants, nitrogen-containing flame retardants or silicon-containing flame retardants.

Ideally, the bromine-containing flame retardant comprises any one or at least two of decabromodiphenyl ether, decabromodiphenylethane, ethylenebistetrabromophthalimide or brominated polycarbonate combination. The optional commercial brominated flame retardants include BT-93, BT-93W, HP-8010 or HP-3010, but are not limited to the above types.

Ideally, the halogen-free flame retardant includes tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-Phosphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10-phosphine Any one or a combination of at least two of phenanthrene-10-oxide, phenoxyphosphine cyanide, phosphate or polyphosphate. Optional commercial halogen-free flame retardants are SPB-100, PX-200, PX-202, LR-202, LR-700, OP-930, OP-935, LP- 2200, XP-7866, but not limited to the above types.

The inclusion of a flame retardant in the thermosetting resin composition of the present invention is determined by the requirement of flame retardancy, so that the resin cured product has flame retardant properties and meets the requirements of UL 94 V-0. There is no particular limitation on the actual flame retardant that needs to be added, and it is preferred that it does not affect the dielectric properties.

Ideally, based on the total mass of the thermosetting polyphenylene ether resin and the crosslinking agent as 100 parts by weight, the filler is added in an amount of 10 to 300 parts by weight, such as 20 parts by weight, 50 parts by weight, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight, 280 parts by weight, etc.

Ideally, based on the total mass of the thermosetting polyphenylene ether resin and the crosslinking agent as 100 parts by weight, the addition amount of the flame retardant is 5 to 80 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, etc., ideally 10 ~60 parts by weight, more preferably 15 to 40 parts by weight. When the amount of flame retardant added is insufficient, a good flame retardant effect cannot be achieved; when the amount of flame retardant added is more than 80 parts, it will bring the risk of a decrease in the heat resistance of the system, an increase in water absorption, and the dielectric properties of the system. will also be deteriorated.

Ideally, the resin composition further includes additives, ideally including antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, anti-drip agents, anti-blocking agents, anti-blocking agents Any one or a combination of at least two of static agents, flow enhancers, processing aids, substrate adhesives, mold release agents, toughening agents, low shrinkage additives, or stress relief additives.

Ideally, the total mass of the thermosetting polyphenylene ether resin and the crosslinking agent is 100 parts by weight, and the amount of the additive is 0.1 to 10 parts by weight, such as 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight , 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, etc., preferably 0.5 to 8 parts by weight, and more preferably 1 to 5 parts by weight.

The preparation method of the resin composition provided by the present invention can adopt conventional methods to compound, stir, and mix the components such as the thermosetting polyphenylene ether resin, crosslinking agent, epoxy silane oligomer, free radical initiator, etc. Prepare.

The second object of the present invention is to provide a resin glue solution obtained by dissolving or dispersing the thermosetting resin composition described in the first object in a solvent.

The solvent in the present invention is not particularly limited, and alcohols such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, butyl carbitol, etc. can be selected. , acetone, methyl ethyl ketone, methyl ethyl ketone, cyclohexanone and other ketones, toluene, xylene and other aromatic hydrocarbons, ethyl acetate, ethoxyethyl acetate and other esters, N,N-diol Nitrogen-containing solvents such as methylformamide and N,N-dimethylacetamide. The above solvents may be used alone or in combination of two or more. Ideally, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, and cyclohexanone are used. The added amount of the solvent can be selected by those with ordinary knowledge in the technical field according to their own experience, so that the resin glue can reach a suitable viscosity for use.

During the process of dissolving or dispersing the resin composition in the solvent as described above, an emulsifier may be added. By dispersing with an emulsifier, powder fillers and the like can be uniformly dispersed in the glue solution.

A third object of the present invention is to provide a prepreg comprising a reinforcing material and the resin composition described in one of the objects attached to it after being impregnated and dried.

In the present invention, the reinforcing material can be a woven or non-woven fabric made of organic fibers, carbon fibers or inorganic fibers; for a woven or non-woven fabric made of inorganic fibers, the main component contains a weight ratio of 50%. ~99.9% (eg 50%, 55%, 58%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 90%, 95% or 99%, etc.) _SiO2 , by weight 0~30% (eg 0%, 5%, 10%, 15%, 20%, 25% or 30%, etc.) of CaO, 0~20% by weight (eg 0%, 5%, 10%, 15%) % or 20%, etc.) Al ₂ O ₃ , weight ratio 0~25% (for example, 0%, 5%, 10%, 15%, 20% or 25%, etc.) B ₂ O ₃ and weight ratio 0~5 % (eg 0%, 0.5%, 1%, 2%, 3%, 4% or 5%, etc.) of MgO.

Ideally, the organic fibers include aramid fibers, such as Kevlar fibers from DuPont.

Ideally, the reinforcing material is ideally woven fiber cloth, which may be E-Glass, T-Glass, NE-Glass, L-Glass, L2-Glass or Q-Glass.

The prepreg provided by the present invention can be obtained by impregnating the above-mentioned resin glue into the reinforcing material, then heating and drying it to remove the organic solvent and partially curing the resin composition in the reinforcing material.

Ideally, the resin content used to impregnate the above reinforcement material is ideally such that the resin content in the prepreg is 30wt.% or higher, such as 30wt.%, 35wt.%, 40wt.%, 50wt.%, 60wt.% %, 70wt.% or more. Since the dielectric constant of the reinforcing material is often higher than that of the resin composition, in order to reduce the dielectric constant of the laminates made from these prepregs, the content of the resin composition component in the prepreg is desirably the above-mentioned content.

Ideally, the drying temperature of the prepreg mentioned above is 80~200°C, such as 80°C, 90°C, 110°C, 120°C, 130°C, 140°C, 150°C, 170°C, 190°C or 200°C, etc. ; The drying time is 1 to 30 minutes, such as 1 minute, 5 minutes, 8 minutes, 13 minutes, 17 minutes, 21 minutes, 24 minutes, 28 minutes or 30 minutes, etc.

The fourth object of the present invention is to provide a laminate comprising at least one prepreg according to the third object.

The fifth object of the present invention is to provide a copper clad laminate, the copper clad laminate containing at least one of the prepregs described in the third object and copper foils covered on one or both sides of the laminated prepregs.

Ideally, the copper foil is electrolytic copper foil or rolled copper foil, and its surface roughness is less than 5 microns; it can improve and improve the signal loss of laminate materials used in high-frequency and high-speed printed circuit boards. lose.

Ideally, the copper foil is chemically treated with a silane coupling agent, which is a methacrylate-based silane coupling agent, an epoxy-based silane coupling agent, a vinyl silane coupling agent, an amine-based coupling agent Any one or a combination of at least two silane coupling agents, phenyl silane coupling agents, anilino silane coupling agents or oligomeric silane coupling agents. The purpose of chemical treatment is to improve the bonding force between the copper foil and the substrate, and prevent the risk of dropped wires and pads during the use of the printed circuit board.

The sixth object of the present invention is to provide a printed circuit board, which includes the laminate described in the fourth object or the copper clad laminate described in the fifth object.

Ideally, the preparation method of the printed circuit board includes the following steps:

It is prepared by overlapping at least one prepreg as described above, placing copper foil on the upper and lower sides of the overlapping prepreg, and performing lamination molding. The overlapping ideally adopts an automatic stacking operation, thereby making the process operation easier.

The lamination molding is ideally vacuum lamination molding, and vacuum lamination molding can be realized by a vacuum laminator. The lamination time is 70 to 130 minutes, such as 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, 105 minutes, 110 minutes, 115 minutes, 120 minutes, 125 minutes or 130 minutes. minutes, etc.; the lamination temperature is 180~220°C, such as 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C or 220°C; the lamination pressure is 20~60kg/cm ² , such as 20kg/cm ² , 25kg/cm ² , 30kg/cm ² , 35kg/cm ² , 40kg/cm ² , 45kg/cm ² , 50kg/cm ² , 55kg/cm ² , 58kg/ cm ² or 60kg/cm ² etc.

The printed circuit board prepared by the above preparation method has low dielectric constant Dk and low dielectric loss Df, excellent and stable heat resistance, interlayer adhesion and peel strength, and satisfies the requirements of high-speed circuit substrates for dielectric constant, dielectric loss, heat resistance. performance, peel strength and interlayer adhesion, etc., can be used to prepare high-speed circuit substrates.

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

In the present invention, the epoxy silane oligomer with a specific chain length in the polyphenylene ether+polyolefin resin system can not only effectively improve the peeling strength and the interlayer adhesion, but also because the epoxy silane oligomer is not easy to volatilize, the board's Peel strength and interlayer adhesion are not affected by temperature changes during processing, ensuring the stability of peel strength and interlayer adhesion without affecting the dielectric properties and heat resistance of the sheet.

The technical means of the present invention will be further described below through specific embodiments. It should be understood by those with ordinary knowledge in the technical field that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.

The details of the raw materials used in the following examples and comparative examples are shown in Table 1 below:

【Example】

Embodiment 1～8, comparative example 1～2

(1) each component in the resin composition is mixed according to the formula amount (refer to Table 2 for details), and is dissolved in the toluene solvent to obtain the resin glue;

(2) Infiltrate the above-mentioned resin glue with glass fiber cloth (Asahi, model 2116L), control the appropriate single weight through the clamping shaft, and dry it in an oven (see Table 2 for the drying temperature and time), remove the toluene solvent, and obtain 2116 prepreg. Laminate 6 sheets of 2116 prepregs, with copper foils with HOZ thickness on the upper and lower sides, vacuum lamination and curing in a press for 120 minutes, curing pressure is 50kg/cm ² , curing temperature is 210 ℃, and the size of 0.76mm is obtained. of copper clad laminate.

Performance Testing

The following performance tests are carried out for the copper clad laminates prepared by the above-mentioned embodiments and comparative examples:

(1) Glass transition temperature (Tg): According to dynamic thermomechanical analysis (DMA), the Tg of the laminate was measured according to the DMA method specified in IPC-TM-650 2.4.24.4.

(2) Glass transition temperature (Tg): According to dynamic thermomechanical analysis (DSC), the Tg of the laminate was measured according to the DSC method specified in IPC-TM-650 2.4.25D (two scans were performed).

(3) Dielectric constant Dk and dielectric loss factor Df: Tested according to the method of Split Post Dielectric Resonator (Split Post Dielectric Resonator), and the test frequency is 10 GHz.

(4) Test method for peel strength (state A): refers to the tensile force required to peel off each millimeter of copper foil from the copper clad laminate at room temperature.

(5) Test method for peel strength (thermal stress): refers to the tensile force required to peel off the copper clad laminate per millimeter of copper foil after immersion in tin at 288°C for 10 minutes.

(6) Test method for interlayer adhesion: refers to the tensile force required to peel off the two-layer sheet per millimeter at room temperature, and records the range of the minimum tensile force and the maximum tensile force required during the separation process.

The above performance test results are shown in Table 2.

As can be seen from Table 2, the resin composition provided by the present invention to which the epoxy silane oligomer represented by formula I is added is dried in an oven at 170 ° C for 5 minutes, the copper clad laminate still has high peel strength and Interlayer adhesion with excellent Dk, Df and heat resistance. The results of Example 1 and Example 6 prove that the peel strength and interlayer adhesion of the substrate are basically the same under the conditions of drying in an oven at 170°C for 5 minutes or in an oven at 155°C for 5 minutes. After the epoxy silane oligomer shown, the process stability of the resin composition is excellent, and the stability of the sheet is better.

Specifically, the Dk (10G) of the copper clad laminate obtained by the present invention is below 3.51, the Df (10G) is below 0.0027, the Tg-DMA is above 205° C., and the Tg-DSC is above 189° C. After baking at 170° C./5 minutes After that, the peel strength (state A) is above 0.65N/mm, the peel strength (thermal stress) is above 0.55N/mm, and the interlayer adhesion is above 0.62~1.00N/mm.

The difference between Comparative Example 1 and Example 5 is only that the epoxy silane oligomer was replaced with a small molecule epoxy silane coupling agent KBM-403, and the peel strength of the sheet was 5 minutes after drying in an oven at 170 °C. Compared with Example 5, the interlayer adhesion is obviously deteriorated, mainly because a large amount of its components have been volatilized, which is not enough to meet the requirement of the epoxysilane coupling dosage in the system.

As mentioned above, compared with the general copper clad laminate, the copper clad laminate prepared with the resin composition of the present invention has low dielectric constant (Dk) and low dielectric loss (Df), heat resistance, interlayer adhesion and peel strength. Excellent and stable performance, meeting the requirements of high-speed circuit substrate to dielectric constant, The performance requirements of dielectric loss, heat resistance, peel strength and interlayer adhesion can be used to prepare high-speed circuit substrates.

The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method 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 protection scope and disclosure scope of the present invention. .

Claims (14)

A resin composition is characterized in that the resin composition comprises the following components in parts by weight: thermosetting polyphenylene ether resin, cross-linking agent, epoxy silane oligomer and free radical initiator; the cross-linking agent comprises a Polyolefin resin with unsaturated double bond; the epoxy silane oligomer has the structure shown in formula I:

In formula I, the R ₁ and R ₂ are each independently selected from any one of substituted or unsubstituted C1 to C8 straight-chain alkyl, substituted or unsubstituted C1 to C8 branched alkyl; in formula I, the n is an integer from 0 to 4; based on the total mass of the thermosetting polyphenylene ether resin and the crosslinking agent as 100 parts by weight, the addition amount of the thermosetting polyphenylene ether resin is 20 to 90 parts by weight, and the addition of the crosslinking agent The amount is 10 to 80 parts by weight, the addition amount of the epoxy silane oligomer is 0.1 to 5 parts by weight, and the addition amount of the free radical initiator is 0.1 to 5 parts by weight. The resin composition according to claim 1, wherein the thermosetting polyphenylene ether resin has the structure shown in formula II:

In formula II, the a and b are each independently an integer from 1 to 30; in formula II, this Z has the structure shown in formula III or formula IV:

In formula IV, this A is selected from any one of C6 to C30 arylene group, C1 to C10 alkylene group or carbonyl group, and each of R ₁ , R ₂ and R ₃ is independently selected from hydrogen atom or C1 to C10 alkyl group , the m is selected from an integer from 0 to 10; in formula II, the -(-OY-)- has the structure shown in formula V:

In formula V, this R ₄ and R ₆ are each independently selected from any one of hydrogen atom, halogen atom, C1 to C10 alkyl or phenyl, and this R ₅ and R ₇ are each independently selected from halogen atom, C1 to C10 Any one of C10 alkyl or phenyl; in formula II, the -(-OXO-)- has the structure shown in formula VI:

In formula VI, this R ₈ to R ₁₅ are each independently selected from any one of hydrogen atom, halogen atom, C1 to C10 alkyl or phenyl, and this B is selected from C1 to C20 alkylene,

,

,

,

,

or

In any one, the R ₁₆ is selected from a hydrogen atom or a C1 to C10 hydrocarbon group, and the r is 0 or 1. The resin composition according to claim 1, wherein the thermosetting polyphenylene ether resin has a number average molecular weight of 500 to 10000 g/mol. The resin composition according to claim 1, wherein the polyolefin resin with an unsaturated double bond contains a butadiene unit added at the 1,2 position, and the butadiene added at the 1,2 position unit weight

20%. The resin composition according to claim 1, wherein the crosslinking agent further comprises a co-crosslinking agent. The resin composition according to claim 5, wherein the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanate, polyfunctional acrylate compound, bismaleimide resin Or any one or a combination of at least two of the divinylbenzene-polyfunctional vinyl aromatic compound copolymers. The resin composition according to claim 1, wherein the radical initiator comprises a first initiator and/or a second initiator, the 1-minute half-life temperature of the first initiator is 50 to 160°C, and the second initiator The 1 minute half-life temperature of the initiator is 161 to 300°C. The resin composition according to claim 5, wherein the co-crosslinking agent is added in an amount of 3 to 60 parts by weight based on 100 parts by weight of the thermosetting polyphenylene ether resin. The resin composition according to claim 1, wherein the resin composition further includes a filler, the total mass of the thermosetting polyphenylene ether resin and the crosslinking agent is 100 parts by weight, and the filler is added in an amount of 10 to 300 parts by weight. parts by weight. The resin composition according to claim 1, wherein the resin composition further comprises a flame retardant, based on the total mass of the thermosetting polyphenylene ether resin and the crosslinking agent being 100 parts by weight, the flame retardant The added amount is 5 to 80 parts by weight. A prepreg, characterized in that the prepreg comprises a reinforcing material and the resin composition according to any one of claims 1 to 10 attached to it after being impregnated and dried. A laminate, characterized in that the laminate comprises at least one prepreg as claimed in claim 11. A copper clad laminate is characterized in that the copper clad laminate contains at least one piece of the prepreg described in claim 11 and copper foils covered on one or both sides of the laminated prepreg. A printed circuit board is characterized in that the printed circuit board comprises the laminate described in claim 12 or the copper clad laminate described in claim 13.