TWI704185B - Resin composition, prepreg for printed circuit and metal-clad laminate - Google Patents

Abstract

The present invention provides resin compositions, prepreg sheets for printed circuits, and metal-clad laminates. The resin composition includes: a silyl acetylene resin; an unsaturated bond-containing polyphenylene ether resin; and a butadiene polymer. By using the resin composition, the metal-clad laminate produced can have at least one of low dielectric loss factor, high heat resistance, and low thermal expansion coefficient.

Description

Resin composition, prepreg for printed circuit and metal-clad laminate

The invention relates to the technical field of printed circuit boards. Specifically, the present invention relates to a resin composition, a prepreg for printed circuit, and a metal-clad laminate.

Metal-clad laminate is a plate-shaped material made by immersing electronic glass fiber cloth or other reinforcing materials with resin liquid, covering one or both sides with metal foil and hot pressing. It is called metal-clad laminate, abbreviated as It is a metal clad laminate or a metal clad laminate, such as a copper clad laminate or a copper clad laminate (Copper Clad Laminate, CCL). Metal-clad laminates, such as copper-clad laminates, are the base laminate materials used to manufacture printed circuit boards (PCBs), and PCBs are one of the important components in the electronics industry. Almost every kind of electronic equipment, from electronic watches, calculators, to computers, communication electronic equipment, military weapon systems, as long as there are electronic components such as integrated circuits, printed boards are used for electrical interconnection between them. . The metal-clad laminate is mainly responsible for the three functions of conduction, insulation and support on the entire printed circuit board.

With the rapid development of electronic equipment towards miniaturization, multi-function, high performance and high reliability, printed circuit boards are required to develop in the direction of high precision, high density, high performance, microporation and thinness. Faster. The CCL determines the performance of the PCB to a large extent.

The development trend of high-precision, high-density, high-performance, microporous, thin and multilayer printed circuit boards requires metal clad laminates such as copper clad laminates to have higher thermal and mechanical properties. For example, more and more multi-layer boards are used in electronic products. In order to ensure the stable and reliable performance of multi-layer circuit boards, it is necessary to laminate with characteristics such as low dielectric loss factor, high heat resistance, and low thermal expansion coefficient.

An object of the present invention is to provide a resin composition, a prepreg for printed circuits obtained by impregnating the resin composition with a reinforcing material such as glass fiber cloth (abbreviated as glass fiber cloth), and a prepreg containing the printed circuit The sheet metal-clad laminate makes the metal-clad laminate at least have one of low dielectric loss factor, high heat resistance, and low thermal expansion coefficient.

Another object of the present invention is to provide an insulating board including the printed circuit prepreg and a printed circuit board including the printed circuit prepreg, the insulating board, or the metal-clad laminate, wherein The insulating board or metal-clad laminate has one of the characteristics of low dielectric loss factor, high heat resistance, and low thermal expansion coefficient.

Therefore, in one aspect, the present invention provides a resin composition comprising: Silane acetylene resin; Polyphenylene ether resin containing unsaturated bonds; and Butadiene polymer, The weight ratio of the silyl acetylene resin, the unsaturated bond-containing polyphenylene ether resin and the butadiene polymer is (1-95):(5-70):(5-70).

其中 n為1至5之間的整數；並且 R ₁和R ₂各自獨立地是選自由以下各項組成的組中的基團：氫、C _1-6烷基或C _3-6環烷基。 According to an embodiment of the present invention, the silyl acetylene resin is represented by the following formula:

Wherein n is an integer between 1 and 5; and R ₁ and R ₂ are each independently a group selected from the group consisting of hydrogen, C _1-6 alkyl, or C _3-6 cycloalkyl .

According to another embodiment of the present invention, the number average molecular weight of the silaryne is 250 to 10,000.

其中n是整數，使得所述含不飽和鍵的聚苯醚樹脂的數均分子量為1000至7000。 According to another embodiment of the present invention, the unsaturated bond-containing polyphenylene ether resin is a polyphenylene ether resin containing unsaturated double bonds at the end groups or side chains, and has a molecular backbone structure as shown below:

Wherein n is an integer, so that the number average molecular weight of the unsaturated bond-containing polyphenylene ether resin is 1,000 to 7,000.

According to another embodiment of the present invention, the butadiene polymer is selected from the group consisting of a butadiene homopolymer, a butadiene copolymer or a combination thereof.

According to another embodiment of the present invention, the butadiene copolymer is selected from the group consisting of polybutadiene homopolymer, styrene-butadiene copolymer, hydrogenated diene-butadiene-styrene copolymer, horse To anhydride diene-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinyl Any one or a mixture of at least two of the benzene copolymer and the maleic anhydride styrene-butadiene copolymer.

According to another embodiment of the present invention, the content of 1,2-vinyl groups on the side chain of the butadiene copolymer is 18% by weight or more.

According to another embodiment of the present invention, the number average molecular weight of the butadiene polymer is in the range of 1,000 to 10,000.

According to another embodiment of the present invention, the resin composition further comprises an accelerator, wherein the content of the accelerator in the resin composition is 0.01 to 5% by weight.

According to another embodiment of the present invention, the accelerator is selected from the group consisting of peroxides, metal salts of acetone, metal salts of naphthenic acid, vanadium pentoxide, amines, quaternary ammonium salts, imidazoles and triphenylphosphine Any one or a mixture of at least two of them.

According to another embodiment of the present invention, the resin composition further includes a filler.

According to another embodiment of the present invention, the filler is selected from: aluminum oxide, titanium oxide, mica, silicon dioxide, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, hydrogen Any one or at least two of magnesium oxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay and other clays, talc, aluminum borate, and silicon carbide mixture.

According to another embodiment of the present invention, the resin composition further includes a flame retardant.

According to another embodiment of the present invention, the resin composition further includes a solvent.

In another aspect, the present invention provides a prepreg for a printed circuit, the prepreg for a printed circuit comprising a reinforcing material and the resin composition as described in any one of the above attached to it after being dried by infiltration.

In yet another aspect, the present invention provides an insulating board containing at least one prepreg for printed circuit as described above.

In yet another aspect, the present invention provides a metal-clad laminate, the metal-clad laminate includes at least one prepreg for a printed circuit as described above and a metal foil.

In yet another aspect, the present invention provides a printed circuit board, the printed circuit board comprising: at least one prepreg for printed circuit as described above, or at least one insulating board as described above, or at least one Zhang as described above metal-clad laminate.

According to the present invention, it is possible to provide a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a reinforcing material, and a metal-clad laminate or insulating board containing the prepreg for a printed circuit, and The prepreg for printed circuit, the insulating board, or the printed circuit board of the metal-clad laminate, so that the metal-clad laminate can have at least one of the characteristics of low dielectric loss factor, high heat resistance, and low thermal expansion coefficient. One.

The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments and/or examples are only a part of the embodiments and/or examples of the present invention. Not all embodiments and/or examples. Based on the embodiments and/or examples of the present invention, all other embodiments and/or all other examples obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

In the following description, layers and films can be used interchangeably. The resin composition is sometimes also referred to as an adhesive hereinafter.

In the present invention, all numerical features refer to within the error range of the measurement, such as within ±10%, or within ±5%, or within ±1% of the defined value.

The "comprising", "including" or "containing" in the present invention means that in addition to the aforementioned components, it may also have other components, which impart different characteristics to the prepreg. In addition, the "comprising", "including" or "containing" in the present invention can also include "essentially consisting of", and can be replaced with "for" or "consisting of".

In the present invention, unless otherwise specified, the amount, ratio, etc. are by weight.

In the present invention, the resin composition containing a solvent may also be referred to as a resin glue.

As described above, the present invention can provide a resin composition, the resin composition comprising: Silane acetylene resin; Polyphenylene ether resin containing unsaturated bonds; and Butadiene polymer, The weight ratio of the silyl acetylene resin, the unsaturated bond-containing polyphenylene ether resin and the butadiene polymer is (1-95):(5-70):(5-70).

Silyl acetylene resin

The silyl acetylene resin can be a resin whose molecular backbone contains silicon, a benzene ring and an alkyne structure.

其中 n為1至5之間的整數； R’和R’’各自獨立地是選自由以下各項組成的組中的基團：氫、C _1-6烷基或C _3-6環烷基。 Silane acetylene resin can be represented by the following formula:

Wherein n is an integer between 1 and 5; R'and R" are each independently a group selected from the group consisting of hydrogen, C _1-6 alkyl or C _3-6 cycloalkyl .

其中 n為1至5之間的整數；並且 R ₁和R ₂各自獨立地是選自由以下各項組成的組中的基團：氫、C _1-6烷基或C _3-6環烷基。 Preferably, the silyl acetylene resin can be represented by the following formula

Wherein n is an integer between 1 and 5; and R ₁ and R ₂ are each independently a group selected from the group consisting of hydrogen, C _1-6 alkyl, or C _3-6 cycloalkyl .

In the above formula, the two alkynyl groups on the benzene ring may be in the ortho, meta or para positions. Silylyne resin can be obtained by polymerizing diethynylbenzene and dichlorosilane. For example, it can be obtained by the Grignard reaction polymerization of diethynylbenzene and dichlorosilane.

Examples of diethynylbenzene may include 1,2-diethynylbenzene, 1,3-diethynylbenzene, and 1,4-diethynylbenzene.

Examples of dichlorosilane may include R'R"SiCl ₂ , or R ₁ R ₂ SiCl ₂ , wherein R', R", R ₁ and R ₂ are each independently a group selected from the group consisting of : Hydrogen, C _1-6 alkyl or C _3-6 cycloalkyl.

Specific examples of dichlorosilane may include methyldichlorosilane and dichlorodimethylsilane.

Examples of C _1-6 alkyl groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, various pentyl groups, and various hexyl groups. Examples of C _3-6 cycloalkyl groups may include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

The number average molecular weight of the silyl acetylene resin may be about 250 to 10,000, preferably about 500 to 2,000. Low-molecular-weight silyl acetylene resins are more soluble in solvents, and have better compatibility with polyphenylene ether resins containing unsaturated bonds, which can reduce the risk of resin precipitation and phase separation, which is conducive to better formation of interpenetrating network structure . However, the reaction time of too low molecular weight silyl acetylene resin is too long, which is not conducive to the curing process of the resin system.

The weight ratio of the silyl acetylene resin in the resin composition has a significant effect on the flame retardancy of the resin composition. When the weight ratio of the silyl acetylene resin to the sum of the silyl acetylene resin, unsaturated bond-containing polyphenylene ether resin and butadiene polymer is greater than 75%, the system can be achieved without the use of flame retardants. V-0 flame retardant.

Polyphenylene ether resin with unsaturated bond

其中n是整數，使得所述含不飽和鍵的聚苯醚樹脂的數均分子量為1000至7000。 The polyphenylene ether resin containing unsaturated bonds can be a polyphenylene ether resin containing unsaturated double bonds in the end groups or side chains, and has a molecular main chain structure as shown below:

Wherein n is an integer, so that the number average molecular weight of the unsaturated bond-containing polyphenylene ether resin is 1,000 to 7,000.

The unsaturated double bond contained in the terminal group or side chain in the polyphenylene ether resin containing unsaturated bonds can be cured and crosslinked, so that a crosslinked cured product can be formed.

Polyphenylene ether resins containing unsaturated bonds are generally prepared by replacing the hydrogen atoms on the end groups or side chains of polyphenylene ether resins such as low molecular weight polyphenylene ether resins with compounds containing unsaturated double bonds. The polyphenylene ether resin containing unsaturated bonds may be liquid or solid at room temperature. The molecular weight of the polyphenylene ether resin containing unsaturated bonds affects its processing technology and the performance of the final cross-linked cured product. The larger the molecular weight, the viscosity of the polyphenylene ether resin liquid containing unsaturated bonds or the polyphenylene ether resin containing unsaturated bonds. The greater the viscosity of the solution of the phenylene ether resin liquid or solid in the solvent, the fewer the reactive groups and the worse the compatibility with other components; the smaller the molecular weight, the viscosity of the polyphenylene ether resin liquid containing unsaturated bonds Or the polyphenylene ether resin liquid or solid containing unsaturated bonds has a lower viscosity in a solvent solution, the more reactive groups and the better the compatibility with other components, but the molecular weight is too small and crosslinking The dielectric properties and toughness of the cured product are lost. Therefore, the number average molecular weight of the polyphenylene ether resin containing unsaturated double bonds is about 1,000 to 7,000, and preferably the number average molecular weight of the polyphenylene ether resin containing unsaturated double bonds is about 1,000 to 4,000.

The polyphenylene ether resin containing unsaturated bonds mainly functions in the resin composition to improve the adhesion and toughness of the resin composition. Too little amount is not enough to improve the peel strength and interlayer adhesion of metal clad laminates such as copper clad laminates, but too much polyphenylene ether resin containing unsaturated bonds will lower the glass transition temperature. Moreover, the dielectric properties of the polyphenylene ether resin containing unsaturated bonds are inferior to that of the silyl alkyne resin and the butadiene polymer. Therefore, the dielectric constant and the dielectric loss of the metal clad laminate such as the copper clad laminate will be increased when the amount is too large.

Butadiene polymer

The butadiene polymer may be selected from: butadiene homopolymer, butadiene copolymer, or a combination thereof.

Examples of butadiene copolymers may include styrene-butadiene copolymers, hydrogenated diene-butadiene-styrene copolymers, maleic anhydride diene-butadiene-styrene copolymers, styrene -Butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer and maleic anhydride styrene-butadiene copolymer Any one or a mixture of at least two of them.

In order to ensure the curing performance of the resin composition, the content of the 1,2-vinyl group on the side chain of the polymer is preferably about 18% by weight or more, more preferably 30% by weight or more.

In order to ensure the curability of the resin composition and the dielectric properties of the cured product, as well as the fluidity of the prepreg or prepreg, the number average molecular weight of the butadiene polymer may be in the range of about 1,000 to 10,000.

The butadiene polymer has better dielectric properties, but poor adhesion and flame retardancy. Its role in the resin composition is to increase the fluidity of the silyl acetylene resin and reduce the crystallinity of the silyl acetylene resin . When the amount is too small, it is not enough to show its effect, but when the amount is too large, the peeling strength of the metal clad laminate such as copper clad laminate will be reduced, and the flame retardancy will be worse.

Accelerator

Optionally, the resin composition further includes an accelerator, corresponding to the requirements of different curing conditions.

In the case of containing an accelerator, the content of the accelerator in the above resin composition may be about 0.01 to 5% by weight.

The accelerator can be selected from any one or a mixture of at least two of peroxide, metal salt of acetone, metal salt of naphthenic acid, vanadium pentoxide, amine, quaternary ammonium salt, imidazole and triphenylphosphine .

Examples of peroxides may include: dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide isopropyl carbonate, 2,5-dimethyl-2,5 -Di-tert-butylcumylperoxyhexyne-3, 2,5-dimethyl 2,5-di-tert-butylperoxyhexane, p-menthane peroxide, 1,1-bis(tert-pentyl Peroxy)cyclohexane, diisopropylbenzene hydroperoxide, benzyl peroxide or benzyl peroxide derivatives. Examples of amines may include aniline.

The metal in the metal salt of acetone and the metal salt of naphthenic acid may independently be an alkali metal, alkaline earth metal or transition metal, for example, potassium, calcium, sodium, magnesium, aluminum, zinc, iron, cobalt, and the like.

In order to better adapt to processing techniques such as impregnation, a solvent can be added to the resin composition to reduce the resin viscosity during the impregnation process.

The solvent is not particularly limited, but it is preferably one or more types containing aromatic hydrocarbon solvents. As specific examples of the aromatic hydrocarbon solvent, toluene, xylene, mesitylene, etc. are preferably used. These aromatic hydrocarbon solvents may be used alone or in combination of two or more.

In addition, if an aromatic hydrocarbon-based solvent is contained, other solvents may be used in combination. The combined solvent is not particularly limited. Specific examples include alcohols such as methanol, ethanol and butanol; ethyl cellosolve and butyl solvent. Cellulose, glycol monomethyl ether, carbitol, butyl carbitol and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; methoxy ethyl acetic acid Ester, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate and other esters; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl Nitrogen-containing solvents such as oxy-2-pyrrolidone can be used alone or in combination of two or more. In addition, the mixing ratio when the aromatic hydrocarbon-based solvent is combined with other solvents to form a mixed solvent is preferably 50% by weight or more of the total solvent.

In the case of containing a solvent, the content of the solvent in the resin composition may be 10-99.5 wt%, preferably about 20-99 wt%.

In order for the metal-clad laminate prepared from the resin composition to have better modulus and heat resistance, fillers such as inorganic fillers may be added to the resin composition.

It is not particularly limited. Specifically, aluminum oxide, titanium oxide, mica, silicon dioxide, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, and hydroxide can be used. Aluminum, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay and other clays, talc, aluminum borate, silicon carbide, etc. These may be used alone or in combination of two or more kinds. The shape of the filler is not particularly limited, but a spherical shape is preferred. There are certain restrictions on the particle size of the filler. The particle size is preferably 0.01 to 30 μm, more preferably 0.1 to 15 μm.

When the particle size of the filler is 0.01 μm or less, the fluidity of the resin composition decreases. Therefore, the moldability of the prepreg and the metal-clad laminate is poor, voids, etc., or the surface area is increased. Therefore, the metal and The reduction in the bonding area of the resin causes a decrease in the peel strength of the printed wiring board, which is not preferable. On the other hand, when the particle size exceeds 30 μm, the insulation reliability of the wiring compartment or the insulating layer of the printed wiring board will decrease, which is not preferable.

In the case of containing a filler, the content of the filler in the resin composition may be about 1 to 90% by weight, preferably about 5 to 80% by weight.

In order to better meet the requirements of flame retardancy, etc., a flame retardant can also be added to the resin composition.

As the flame retardant, flame retardants such as bromine-based, phosphorus-based, and metal hydroxides are preferably used.

Examples of brominated flame retardants are: brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis (pentabromo Phenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclo Dodecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine Equal brominated additive flame retardant; tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate And brominated styrene and other containing unsaturated double bond group brominated reactive flame retardant, etc.

Examples of phosphorus-based flame retardants are: triphenyl phosphate, tricresyl phosphate, tris(xylene) phosphate, cresol diphenyl phosphate, cresol bis-2,6-xylenyl phosphate, and isophthalic acid Aromatic phosphates such as phenol bis (diphenyl phosphate); phosphonates such as divinyl phenyl phosphonate, diallyl phenyl phosphonate and bis (1-butenyl) phenyl phosphonate ; Phosphate esters such as phenyl diphenyl phosphate, methyl diphenyl phosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives; bis(2-allyl Phenoxy) phosphazene, xylenol phosphazene and other phosphazene compounds; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinyl benzyl compounds, red phosphorus and other phosphorus Class flame retardant.

Examples of metal hydroxide flame retardants are magnesium hydroxide or aluminum hydroxide.

In addition, the aforementioned flame retardants may be used alone or in combination of two or more.

In the case of containing a flame retardant, the content of the flame retardant in the resin composition may be about 1 to 60% by weight, preferably about 2 to 40% by weight.

In addition, the resin composition may further contain various auxiliary agents. Specific examples of auxiliary agents include filler dispersants, defoamers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and the like. These auxiliaries can be used alone or in combination of any two or more.

The resin composition of the present invention can be mixed by known methods such as compounding, stirring, mixing silyl acetylene resin, unsaturated bond-containing polyphenylene ether resin and butadiene polymer, and optional accelerators, solvents, fillers, and barriers. Any one or a mixture of at least two of the burning agent, dispersant, defoaming agent, antioxidant, heat stabilizer, antistatic agent, ultraviolet absorber, pigment, colorant and lubricant is prepared.

Through mechanical stirring, emulsification or ball milling dispersion, the resin composition is formulated into a resin glue solution, and then the resin glue solution is used to infiltrate the reinforcing material and dried to obtain a prepreg sheet. The prepreg sheet and metal foil such as copper foil or aluminum foil are hot pressed in a vacuum press to prepare a metal-clad laminate.

Examples of reinforcing materials may include glass fiber cloth, glass fiber non-woven fabric, organic non-woven fabric, and the like.

In order to reduce the viscosity of the resin glue, it can be infiltrated under heating. Heating is performed so that the temperature of the resin glue solution is lower than the boiling point of the solvent used. Preferably, the temperature of the resin glue solution during infiltration is about 20-90°C, more preferably about 25-55°C.

In another aspect, the present invention can also provide a prepreg for a printed circuit, the prepreg for a printed circuit comprising a reinforcing material and the resin composition of any one of the above attached to it after being dried by infiltration .

In another aspect, the present invention can also provide an insulating board or metal-clad laminate, which contains at least one prepreg for printed circuit as described above.

In another aspect, the present invention may also provide a printed circuit board, the printed circuit board comprising: at least one prepreg for printed circuit as described above, or at least one insulating board as described above, or At least one metal-clad laminate as described above.

According to the present invention, it is possible to provide a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a reinforcing material, and a metal-clad laminate or insulating board containing the prepreg for a printed circuit, and The prepreg for printed circuit, the insulating board, or the printed circuit board of the metal-clad laminate, so that the metal-clad laminate can have at least one of the characteristics of low dielectric loss factor, high heat resistance, and low thermal expansion coefficient. One.

Example

The technical solutions of the present invention will be further explained through specific implementations below. However, these examples are to illustrate the present invention, and should not be construed as limiting the present invention.

Preparation example

The silyl acetylene resins used in the examples and comparative examples were prepared as follows.

Add 3.5 parts of magnesium powder (chemically pure, Shanghai Sinopharm Chemical Reagent Co., Ltd.) and 40 parts of tetrahydrofuran (THF) solvent into a reactor filled with nitrogen. Stir and drop 13.5 parts of bromoethane (chemically pure) at room temperature. , Shanghai Sinopharm Chemical Reagent Co., Ltd.) and 40 parts of THF mixed solution, after the completion of dripping, keep it at 50℃ for 1h. Then, under the condition of an ice-water cooling bath, a mixture of 7.5 parts of 1,3-diethynylbenzene (Shandong Jiaozhou Fine Chemical Co., Ltd.) and 40 parts of THF solvent was added dropwise. After the addition, the mixture was kept at 65°C for 1 hour. Then cool again, and add 5.5 parts of dichlorodimethylsilane (chemically pure, Zhejiang Xin'an Chemical Group Co., Ltd., used after distillation) and 40ml of THF under the ice-water cooling bath. Incubate at 70°C for 1 hour. After the reaction is completed, the THF in the reactant is distilled off, and a mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene solvent is added dropwise under the condition of ice-water cold bath, and then 140 parts of 2.0% dilute hydrochloric acid aqueous solution are added dropwise after thorough stirring. The upper organic phase was separated. The organic phase was thoroughly washed with water to neutrality, then dried, filtered, and toluene was distilled off to obtain the silyl acetylene resin (that is, the silyl acetylene resin used in the examples and comparative examples (number average molecular weight 1200, GPC test mobile phase) THF), hereinafter referred to as PSA1200).

Examples 1-8 and Comparative Examples 1-4

According to the amount (parts by weight) shown in Table 1 or Table 2, dissolve the silyl acetylene resin, unsaturated bond-containing polyphenylene ether resin and butadiene polymer, as well as the accelerator in the solvent, and mix well , Then add inorganic filler and/or flame retardant, mix evenly to obtain glue liquid. Take a 1080 E-type glass fiber cloth (manufactured by Nittobo) and evenly impregnate the above glue solution, and bake it in a blast oven at 155°C for 3 minutes to prepare a prepreg. Respectively overlap 4 or 8 of the above prepreg sheets, cover with 18μm inverted copper foil (produced by Suzhou Futian Metal Co., Ltd.), and press in a vacuum hot press at 3MPa pressure and 210°C for 90 minutes to obtain two thicknesses Laminate samples (hereinafter, sometimes referred to as copper clad laminates or copper clad laminates) (ie, 8*1080 HH laminate samples and 4*1080 HH laminate samples).

The amount of components in the resin composition and the test results of the resin composition are shown in Tables 1 and 2 below. The thermal expansion coefficient, thermal expansion ratio and thermal stress are tested using 8*1080 HH laminate samples, and the others are 4*1080 HH Laminate sample test.

Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Silyl acetylene resin PSA1200 50 50 120 20 50 50 Polyphenylene ether with unsaturated double bond SA9000 50 50 10 40 30 30 OPE-2St Butadiene polymer Ricon100 50 50 50 Ricon181 50 Ricon257 20 B1000 20 20 B3000 90 Accelerator DCP 0.2 0.2 0.2 0.2 1 part acetone cobalt and 1.5 parts triphenylphosphine in ethanol 0.5 filler DQ1028L 230 SC2050 200 200 200 190 200 Flame retardant BT-93w 40 0 XP7866 45 Aluminum hydroxide Solvent Toluene 150 150 150 150 180 180 Glass transition temperature (Tg)℃ ＞230 ＞230 ＞230 ＞230 ＞230 ＞230 Thermal decomposition temperature (Td) 440 450 ＞500 410 390 420 Peel strength (PS) N/mm 0.6 0.6 0.6 0.6 0.8 0.8 10GHz dielectric constant (Dk) 3.7 3.7 3.9 3.6 3.7 3.7 10GHz dielectric loss factor (Df) 0.0035 0.0032 0.0039 0.0032 0.0032 0.0032 Flame retardant V-1 V-1 V-0 V-1 V-0 V-0 Coefficient of thermal expansion (ppm/℃) 40 40 35 40 40 40 50-260℃ thermal expansion ratio (%) 1.5 1.5 1.2 1.5 1.5 1.5 Thermal stress (min) ＞10 ＞10 ＞10 ＞10 ＞10 ＞10

Table 2 Example 7 Example 8 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Silyl acetylene resin PSA1200 50 50 50 50 150 Polyphenylene ether with unsaturated double bond SA9000 30 100 100 OPE-2St 30 Butadiene copolymer Ricon100 50 50 100 50 Ricon181 Ricon257 B1000 20 20 B3000 Accelerator DCP 0.2 0.2 0.2 0.2 0.2 1 part acetone cobalt and 1.5 parts triphenylphosphine in ethanol 0.5 filler DQ1028L 200 200 SC2050 200 200 200 200 Flame retardant BT-93w 0 0 40 40 40 40 XP7866 30 30 Aluminum hydroxide 20 20 Solvent Toluene 180 180 180 180 180 180 Glass transition temperature (Tg)℃ ＞230 ＞230 170 ＞230 200 ＞230 Thermal decomposition temperature (Td) 420 420 400 410 390 ＞500 Peel strength (PS) N/mm 0.8 0.8 0.3 0.1 0.2 0.2 10GHz dielectric constant (Dk) 3.7 3.7 4.2 4 3.9 4.5 10GHz dielectric loss factor (Df) 0.0032 0.0032 0.0045 0.004 0.0045 0.0045 Flame retardant V-0 V-0 V-0 V-0 V-0 V-0 Coefficient of thermal expansion (ppm/℃) 40 40 60 50 50 32 50-260℃ thermal expansion ratio (%) 1.5 1.5 2.9 2.4 2.4 1.1 Thermal stress (min) ＞10 ＞10 ＞10 ＞10 ＞10 ＞10

PSA1200: the silyl acetylene resin obtained in the preparation example;

SA9000: Allyl modified polyphenylene ether resin, produced by SABIC;

Ricon100: Butadiene-styrene copolymer, number average molecular weight 4500, side chain vinyl content 70% by weight, produced by CRAYVALLEY;

Ricon181: Butadiene-styrene copolymer, number average molecular weight 3200, side chain vinyl content 20-40% by weight, produced by CRAYVALLEY;

Ricon257: Butadiene-styrene-divinylbenzene branched terpolymer, number average molecular weight 5300, pendant vinyl content 30-50% by weight, produced by CRAYVALLEY;

B1000: Butadiene homopolymer, with a number average molecular weight of about 1200 and a side chain vinyl content of 85% by weight, produced by NISSO in Japan;

B3000: Butadiene homopolymer with a number average molecular weight of about 3200 and a side chain vinyl content of 92% by weight, produced by NISSO in Japan;

DCP: Dicumyl peroxide, reagent;

A solution of 1 part of acetone cobalt and 1.5 parts of triphenylphosphine in 100 parts of ethanol: the amount in the table refers to the amount of acetone cobalt and triphenylphosphine, that is, 0.5 parts by weight is 0.2 parts by weight of acetone Cobalt acetone and 0.3 parts by weight of triphenylphosphine;

DQ1028L: Spherical silicon dioxide, D50 is about 3.0μm, produced by Jiangsu Lianrui;

SC2050: spherical silicon dioxide, D50 is about 0.5μm, provided by Toyota Tsusho;

BT-93w: additive bromine flame retardant, produced by Albemarle, USA;

XP7866: Additive phosphorus flame retardant, produced by Albemarle, USA;

Aluminum hydroxide: OL-104, produced by Albemarle, USA;

Toluene: industrial product, commercially available.

The method of testing the performance described in the table is as follows:

1) Glass transition temperature Tg: Use dynamic thermomechanical analysis (DMA) test, in accordance with the DMA test method specified in IPC-TM-650 2.4.24.

2) Thermal decomposition temperature (Td): Use thermal weight loss analysis (TGA) test, according to standard IPC-TM-650 2.4.24.6.

3) Peel strength (PS): refers to the tensile force required to peel off the copper clad laminate per millimeter of copper foil at room temperature.

4) Dielectric constant (Dk) and dielectric loss factor (Df): 10GHz is measured using the resonant cavity method (SPDR) method, according to the standard IPC-TM-650 2.5.5.5.

5) Flame retardancy: According to UL94 "50W (20mm) vertical burning test: V-0, V-1 and V-2" test method, V-0 is recognized as flame retardant.

6) Coefficient of thermal expansion (CTE) and ratio of thermal expansion at 50-260°C: The test uses a static thermal analyzer (TMA) test, and the test is in accordance with the standard IPC-TM-650 2.4.24. The coefficient of thermal expansion (CTE) and the ratio of thermal expansion at 50-260°C are measured in the length direction of the laminate sample.

7) Thermal stress: Float the copper clad laminate on the surface of molten tin at a temperature of 288°C, and use the time of delamination or bubbles as the test result.

8) D50: Mean particle size, which means that when the total volume of the particles is taken as 100% and the cumulative power distribution curve based on the particle size is calculated, the particle size is exactly equivalent to the point where the volume is 50%, which uses laser diffraction scattering Method of fineness distribution measurement.

It can be seen from the test results of the foregoing examples and comparative examples that the test results of Tg and Td of the samples of this example are higher than those of common printed circuit boards in the industry. The dielectric loss factor results of copper clad laminates show that it will have good application performance in high-frequency and high-speed laminates, and its CTE, 50-260 ℃ thermal expansion ratio and thermal stress performance are excellent.

Compared with the comparative example, there is no butadiene copolymer resin in comparative example 1, and its dielectric loss is relatively low, and the expansion coefficient is relatively large; in comparative example 2, there is no polyphenylene ether resin containing unsaturated double bonds, and its peel strength is obvious Too low, does not meet the requirements of the use of copper clad laminates; in Comparative Example 3, there is no silylyne resin, and its dielectric loss is relatively large, and the expansion coefficient is also large; in Comparative Example 4, it is a single silylyne resin system, which The expansion coefficient is small, but the dielectric constant is large.

As above, it is possible to provide a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a glass fiber cloth, and a metal-clad laminate or insulating board containing the prepreg for a printed circuit, and the The prepreg for printed circuit, the insulating board or the printed circuit board of the metal-clad laminate, so that the metal-clad laminate can have at least one of low dielectric loss factor, high heat resistance, low thermal expansion coefficient and other characteristics , It is preferable to have a low dielectric loss factor, high heat resistance, and low thermal expansion coefficient at the same time. At the same time, by adding flame retardants, V-0 flame retardant performance can be achieved, making it suitable for applications that require flame retardancy.

Obviously, those skilled in the art can make various changes and modifications to the embodiments of the present invention without departing from the spirit and scope of the present invention. In this way, if these modifications and variations of the present invention fall within the scope of the patent application of the present invention and the equivalent technology, the present invention also intends to include these modifications and variations.

Claims (18)

A resin composition, the resin composition comprising: Silane acetylene resin; Polyphenylene ether resin containing unsaturated bonds; and Butadiene polymer, The weight ratio of the silyl acetylene resin, the unsaturated bond-containing polyphenylene ether resin and the butadiene polymer is (1-95):(5-70):(5-70). The resin composition according to claim 1, wherein the silyl acetylene resin is represented by the following formula:

Wherein n is an integer between 1 and 5; and R ₁ and R ₂ are each independently a group selected from the group consisting of hydrogen, C _1-6 alkyl, or C _3-6 cycloalkyl . The resin composition according to claim 1, wherein the number average molecular weight of the silyl acetylene resin is 250 to 10,000. The resin composition according to claim 1, wherein the polyphenylene ether resin containing an unsaturated bond is a polyphenylene ether resin containing an unsaturated double bond in a terminal group or a side chain, and has a molecular main chain as shown below structure:

Wherein n is an integer, so that the number average molecular weight of the unsaturated bond-containing polyphenylene ether resin is 1,000 to 7,000. The resin composition according to claim 1, wherein the butadiene polymer is selected from a butadiene homopolymer, a butadiene copolymer or a combination thereof. The resin composition according to claim 5, wherein the butadiene copolymer is selected from the group consisting of polybutadiene homopolymer, styrene-butadiene copolymer, hydrogenated diene-butadiene-styrene copolymer Compound, maleic anhydride diene-butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene- Any one or a mixture of at least two of the divinylbenzene copolymer and the maleic anhydride styrene-butadiene copolymer. The resin composition according to claim 1, wherein the content of the 1,2-vinyl group in the side chain of the butadiene polymer is 18% by weight or more. The resin composition according to claim 1, wherein the number average molecular weight of the butadiene polymer is in the range of 1,000 to 10,000. The resin composition according to claim 1, further comprising an accelerator, wherein the content of the accelerator in the resin composition is 0.01 to 5% by weight. The resin composition according to claim 9, wherein the accelerator is selected from the group consisting of peroxide, metal salt of acetone, metal salt of naphthenic acid, vanadium pentoxide, amine, quaternary ammonium salt, imidazole and tri Any one or a mixture of at least two of phenylphosphines. The resin composition according to claim 1, wherein the resin composition further includes a filler. The resin composition according to claim 11, wherein the filler is selected from the group consisting of aluminum oxide, titanium oxide, mica, silicon dioxide, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, carbonic acid Any one of aluminum, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, talc, aluminum borate, and silicon carbide, or A mixture of at least two. The resin composition according to claim 1, wherein the resin composition further includes a flame retardant. The resin composition according to claim 1, wherein the resin composition further includes a solvent. A prepreg sheet for printed circuits, the prepreg sheet for printed circuits comprising a reinforcing material and the resin composition according to any one of claims 1 to 13 attached to it after being dried by infiltration. An insulating board containing at least one prepreg sheet for printed circuits according to claim 15. A metal-clad laminate comprising at least one prepreg for printed circuit and metal foil according to claim 15. A printed circuit board comprising: at least one printed circuit prepreg as described in claim 15, or at least one insulating board as described in claim 16, or at least one as claimed in claim 17. The metal-clad laminate.