TWI743501B - 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; a cyanate ester compound; and a maleimide compound. 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 a printed circuit, and a metal-clad laminate.

Metal-clad laminate is a kind of plate-shaped material made by impregnating electronic glass fiber cloth or other reinforcing materials with resin liquid, and covering one or both sides with metal foil and hot pressing. It is called metal-clad laminate, abbreviated as metal-clad laminate. It is a metal-clad laminate or a metal-clad laminate, such as a copper-clad laminate or a 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 (devices) such as integrated circuits, they must be used for electrical interconnection. Printing board. The metal-clad laminate is mainly responsible for the 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, microporosity 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 the characteristics 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 prepreg for printed circuits and a printed circuit board including the prepreg for printed circuits, 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: Silyl acetylene resin; Cyanate ester compounds; and Maleimide compounds, The weight ratio of the silyl acetylene resin, the cyanate ester compound, and the maleimide compound is (5-95): (5-70): (5-70).

其中 n為1至5之間的整數；並且 R₁ 和R₂ 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:

Where 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 silyl acetylene resin is 250 to 10,000.

According to another embodiment of the present invention, the cyanate ester compound is selected from 2,2-bis(4-cyanophenyl)propane, bis(3,5-dimethyl-4-cyanophenyl)methane , Any one or a combination of at least two of the prepolymers or monomers of 2,2-bis(4-cyanophenyl)ethane.

According to another embodiment of the present invention, the cyanate ester compound is selected from: 2,2-bis(4-cyanatephenyl)propane and bis(3,5-dimethyl-4-cyanatephenyl) A combination of methane, or a combination of bis(3,5-dimethyl-4-cyanophenyl)methane and 2,2-bis(4-cyanophenyl)ethane.

。According to another embodiment of the present invention, the maleimide compound contains at least one structure represented by the following formula in its molecular structure:

.

。According to another embodiment of the present invention, the maleimide compound contains at least two structures represented by the following formula in its molecular structure:

.

According to another embodiment of the present invention, the maleimide compound is selected from: 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide oligomer, m-phenylene Bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane Leximine, 4-methyl-1,3-phenylene bismaleimide and 1,6-bismaleimide-(2,2,4-trimethyl)hexane Any one or a combination of at least two.

According to another embodiment of the present invention, the resin composition further includes 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, triphenylphosphine , Boron trifluoride complex, metal salt of n-octanoic acid or isooctanoic acid, acetone, naphthenic acid, metal salt of stearic acid, and any one or a mixture of at least two of salicylic acid.

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 is the 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.

The technical solutions in the embodiments of the present invention will be clearly and completely described below 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, for example, within ±10%, or within ±5%, or within ±1% of the limited 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, if there is no specific indication, 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 comprising: Silyl acetylene resin; Cyanate ester compounds; and Maleimide compounds, The weight ratio of the silyl acetylene resin, the cyanate ester compound, and the maleimide compound is (5-95): (5-70): (5-70).

Silyl acetylene resin

The silyl alkyne 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 .

n為1至5之間的整數；並且 R₁ 和R₂ 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

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 the C _1-6 alkyl group 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, which can reduce the risk of resin precipitation and phase separation, and help to better form an 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 retardant properties of the resin composition. When the weight ratio of the silyl acetylene resin to the sum of the silyl acetylene resin, cyanate ester compound and maleimide compound is greater than 70%, the system can achieve V-0 resistance without the use of flame retardants. Burn.

Cyanate ester compound

The present invention has no limitation on the cyanate ester compound used.

Examples of cyanate ester compounds can be selected from 2,2-bis(4-cyanophenyl)propane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2,2-bis(4 -Cyanate phenyl) ethane and other cyanate ester prepolymers or monomers of any one or a combination of at least two.

The number average molecular weight of the cyanate ester prepolymer may be 200 to 10,000. When the molecular weight is too low, the viscosity of the resin is too low, and a longer curing time is required, which is not conducive to hot pressing. When the molecular weight is too large, the viscosity of the resin is too large, which is not conducive to the infiltration of the reinforcing material, and has poor fluidity during hot pressing, and it is easy to produce holes. In order to better adapt to the process requirements of the production of metal clad laminates, such as copper clad laminates, 400 to 6000 are preferred.

An example of a typical but non-limiting combination can be: a combination of 2,2-bis(4-cyanophenyl)propane and bis(3,5-dimethyl-4-cyanophenyl)methane, or A combination of (3,5-dimethyl-4-cyanophenyl)methane and 2,2-bis(4-cyanophenyl)ethane.

Among the three resin components, the cyanate ester compound has relatively weak heat resistance and better dielectric properties than the maleimide compound, but inferior to the silyl acetylene resin. The cyanate ester compound has the best manufacturability in the processing of metal clad laminates such as copper clad laminates. It helps to reduce the crystallinity of the silyl acetylene resin and the maleimide compound and improve the fluidity of the resin composition. However, excessive cyanide The acid ester compound has poor toughness and heat resistance.

Maleimide compound

The present invention has no limitation on the maleimide compound used.

。The maleimide compound contains at least one structure represented by the following formula in its molecular structure, and preferably contains at least two structures represented by the following formula in its molecular structure:

.

Examples of maleimide compounds can be selected from 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide oligomer, m-phenylene bismaleimide, bisphenol A Diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl Any one or a combination of at least two of -1,3-phenylene bismaleimide and 1,6-bismaleimide-(2,2,4-trimethyl)hexane.

The phenylmethane maleimide oligomer is a resin material with the following molecular structure, wherein n is 0, 1, 2, 3, 4, or 5, preferably a mixture of materials with different polymerization degrees.

The maleimide compound has good heat resistance, but poor solubility. Excessive use will cause precipitation and agglomeration, which will reduce the adhesion and toughness of metal clad laminates such as copper clad laminates.

Accelerator

Optionally, the resin composition further includes an accelerator, which corresponds 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: peroxide, metal salt of acetone, metal salt of naphthenic acid, vanadium pentoxide, amine, quaternary ammonium salt, imidazole, triphenylphosphine, boron trifluoride complex, normal Any one or a mixture of at least two of the metal salt of caprylic acid or isooctanoic acid, acetone, naphthenic acid, metal salt of stearic acid, and salicylic acid.

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 hydrogen peroxide, benzyl peroxide or benzyl peroxide derivatives. Examples of amines may include aniline.

The metal in the metal salt of n-octanoic acid or isooctanoic acid, the metal salt of stearic acid, the metal salt of acetone, and the metal salt of naphthenic acid may independently be an alkali metal, an alkaline earth metal or a transition metal, for example, potassium, calcium, Sodium, magnesium, aluminum, zinc, iron, cobalt, etc. Examples of the metal salt of isooctanoic acid may include zinc isooctanoate.

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

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

In addition, if an aromatic hydrocarbon-based solvent is contained, other solvents can 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, ethylene 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, etc., these solvents may 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 make a mixed solvent is preferably 50% by weight or more of the total solvent of the aromatic hydrocarbon-based 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 fillers may be added to the resin composition.

The filler 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, hydrogen can be used. Alumina, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay and other clays, talc, aluminum borate, silicon carbide, etc. These fillers may be used alone or in combination of two or more kinds. There is no particular limitation on the shape of the filler, but a spherical shape is preferred. There are certain restrictions on the particle size of the filler, and a filler with a particle size of preferably 0.01 to 30 μm, more preferably 0.1 to 15 μm is used.

When the particle size of the filler is 0.01 μm or less, the fluidity of the resin composition decreases. Therefore, the moldability during the production of prepregs and metal-clad laminates deteriorates, voids are likely to occur, or the surface area of the filler increases. The reduction of the bonding area between the metal and the resin causes a decrease in the peel strength of the printed wiring board, which is not preferable. On the other hand, if 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 bromine-based 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 retardants; tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate And brominated styrene and other brominated reactive flame retardants containing unsaturated double bond groups.

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 phosphate esters 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 diphenyl phenyl phosphate, diphenyl methyl 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 above-mentioned flame retardants may be used alone or in combination of two or more kinds.

In the case of containing a flame retardant, the content of the flame retardant in the resin composition may be about 1 to 40% by weight, preferably about 2 to 30% 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 any two or more of them can be used in combination.

The resin composition of the present invention can be used by known methods such as compounding, stirring, mixing silyl acetylene resin, cyanate ester compound and maleimide compound, and optional accelerators, solvents, fillers, flame retardants, dispersion Preparation of any one or a mixture of at least two of agents, defoamers, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants.

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 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 50-90°C, more preferably about 55-85°C.

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

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

In another aspect, the present invention can 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 solution of the present invention will be further explained by specific embodiments below. However, these examples are for exemplifying 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 at room temperature and add 13.5 parts of bromoethane (chemically pure). , 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 cooling 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 washed thoroughly with water to neutrality, then dried, filtered, and distilled to remove toluene 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 1-7 and Comparative Examples 1-3

According to the amount (parts by weight) shown in Table 1 or Table 2, dissolve the silyl acetylene resin, the cyanate ester compound, the maleimide compound, and the accelerator in the solvent, and mix them evenly, and then add the filler And/or flame retardant, mix evenly to obtain glue solution. Take the 1080 E-type glass fiber cloth (manufactured by Nittobo) to evenly immerse 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 prepregs, and cover the top and bottom with 18 mm 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 Samples of laminates (hereinafter, sometimes referred to as copper clad laminates or copper clad laminates).

The amounts of components in the resin composition and the test results of the resin composition are shown in Tables 1 and 2 below.

Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Silyl acetylene resin PSA1200 50 50 10 120 50 50 Cyanate ester compound CE01PS 90 50 100 20 30 30 CE01MO 40 20 20 Maleimide compound BMI-E 10 50 50 BMI-1000 10 30 BMI-50P 40 Accelerator Zinc Isooctanoate 0.5 0.2 0.2 filler DQ1028L 230 SC2050 200 200 0 190 200 Flame retardant BT-93w 40 0 XP7866 45 Aluminum hydroxide Solvent DMF 50 50 50 50 50 50 Toluene 100 100 100 100 100 100 Glass transition temperature (Tg)℃ 260 240 220 260 260 260 Thermal decomposition temperature (Td) 440 430 400 ＞500 360 420 Peel strength (PS) N/mm 0.9 0.9 0.9 1.1 0.9 0.9 10GHz dielectric constant (Dk) 3.8 3.8 3.6 3.8 3.8 3.8 10GHz dielectric loss factor (Df) 0.0055 0.0055 0.0068 0.0045 0.0055 0.0055 Flame retardant V-1 V-1 V-1 V-0 V-0 V-0 Z-axis thermal expansion coefficient (ppm/℃) 20 twenty one 30 25 20 20 XY axis thermal expansion coefficient (ppm/℃) 12, 14 13, 14 13, 14 13, 14 12, 13 12, 13 50-260℃ thermal expansion ratio (%) 0.55 0.68 1.2 0.5 0.55 0.7 Thermal stress (min) ＞10 ＞10 ＞10 ＞10 ＞10 ＞10

Table 2 Example 7 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Silyl acetylene resin PSA1200 50 50 50 150 Cyanate ester compound CE01PS 30 100 100 CE01MO 20 Maleimide compound BMI-E 50 100 50 BMI-1000 BMI-50P Accelerator Zinc Isooctanoate 0.2 0.5 filler DQ1028L 200 SC2050 200 200 200 200 Flame retardant BT-93w 0 40 40 40 40 XP7866 30 Aluminum hydroxide 20 Solvent DMF 50 100 50 Toluene 150 180 80 130 180 Glass transition temperature (Tg)℃ 260 190 230 220 260 Thermal decomposition temperature (Td) 400 350 345 340 ＞500 Peel strength (PS) N/mm 0.9 0.3 0.1 0.4 0.2 10GHz dielectric constant (Dk) 4 4 4.3 4.1 4.5 10GHz dielectric loss factor (Df) 0.0075 0.008 0.008 0.0085 0.0045 Flame retardant V-0 V-0 V-0 V-0 V-0 Z-axis thermal expansion coefficient (ppm/℃) 20 50 50 65 32 XY axis thermal expansion coefficient (ppm/℃) 12, 13 16, 17 14, 15 15, 16 12, 13 50-260℃ thermal expansion ratio (%) 0.6 2.9 2.4 2.4 1.1 Thermal stress (min) ＞10 ＞10 ＞10 ＞10 ＞10

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

CE01PS: Bisphenol A cyanate ester prepolymer (number average molecular weight: 3000), produced by Tianqi Chemical;

CE01MO: Bisphenol A cyanate ester monomer, produced by Tianqi Chemical;

BMI-E: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, produced by Jiangsu Feixiang Chemical Industry;

BMI-1000: 4,4’-diphenylmethane bismaleimide, produced by Yamato, Japan;

BMI-50P: Phenylmethane maleimide oligomer, produced by KI in Japan;

Zinc isooctanoate: reagent, commercially available;

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

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

BT-93w: Additive brominated flame retardant, produced by Albemarle, USA;

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

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

DMF: N,N-dimethylformamide, industrial product, commercially available;

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-6502.4.24.

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: Tested in accordance with the UL94 "50W (20mm) vertical burning test: V-0, V-1 and V-2" test method.

6) Coefficient of Thermal Expansion (CTE) and 50-260℃ Thermal Expansion Ratio: The test uses a static thermal analyzer (TMA) test, the test is in accordance with the standard IPC-TM-650 2.4.24, where the Z axis represents the thickness direction of the laminate sample, X The axis represents the length direction of the laminate sample, and the Y axis represents the width direction of the laminate sample. The 50-260°C thermal expansion ratio is measured in the Z-axis 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 particles is taken as 100% and the cumulative power distribution curve based on particle size is calculated, the particle size at the point corresponding to 50% of the volume is used. Laser diffraction is used. Measurement of fineness distribution by scattering method.

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 printed circuit boards commonly used 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°C thermal expansion ratio and thermal stress performance in all directions are excellent.

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, and low thermal expansion coefficient 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 equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims (16)

A resin composition comprising: a silyl acetylene resin; a cyanate ester compound; and a maleimide compound, wherein the silyl acetylene resin, the cyanate ester compound and the maleimide compound The weight ratio of the imine compound is (5-95): (5-70): (5-70); the silyl acetylene resin is represented by the following formula:

Where 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 And the number average molecular weight of the silyl acetylene resin is 250 to 10,000. The resin composition according to claim 1, wherein the cyanate ester compound is selected from 2,2-bis(4-cyanophenyl)propane, bis(3,5-dimethyl-4-cyanobenzene) Any one or a combination of at least two of the prepolymers or monomers of methyl)methane or 2,2-bis(4-cyanophenyl)ethane. The resin composition according to claim 1, wherein the cyanate ester compound is selected from: 2,2-bis(4-cyanophenyl)propane and bis(3,5-dimethyl-4-cyanic acid) A combination of phenyl)methane, or a combination of bis(3,5-dimethyl-4-cyanophenyl)methane and 2,2-bis(4-cyanophenyl)ethane. The resin composition according to claim 1, wherein the maleimide compound contains at least one structure represented by the following formula in its molecular structure:

The resin composition according to claim 1, wherein the maleimide compound contains at least two structures represented by the following formula in its molecular structure:

The resin composition according to claim 1, wherein the maleimide compound is selected from the group consisting of 4,4'-diphenylmethane bismaleimide, phenylmethane maleimide oligomer, and Phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenyl Methane bismaleimide, 4-methyl-1,3-phenylene bismaleimide and 1,6-bismaleimide-(2,2,4-trimethyl)hexane Any one or a combination of at least two of the alkanes. 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 7, 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, tri Any one or a mixture of at least two of phenylphosphine, boron trifluoride complex, metal salt of n-octanoic acid or isooctanoic acid, acetone, naphthenic acid, metal salt of stearic acid, and salicylic acid. The resin composition according to claim 1, wherein the resin composition further includes a filler. The resin composition according to claim 9, wherein the filler is selected from: alumina, Titanium oxide, mica, silicon dioxide, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, Any one or a mixture of at least two of clays such as magnesium silicate, silicon nitride, boron nitride, and calcined clay, talc, aluminum borate, and silicon carbide. 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 a printed circuit, the prepreg sheet for a printed circuit comprising a reinforcing material and the resin composition according to any one of claims 1 to 11 attached to it after being dried by infiltration. An insulating board containing at least one prepreg sheet for printed circuits as described in claim 13. A metal-clad laminate, the metal-clad laminate includes at least one prepreg for a printed circuit according to claim 13 and a metal foil. A printed circuit board, the printed circuit board comprising: at least one printed circuit prepreg as described in claim 13, or at least one insulating board as described in claim 14, or at least one as claimed in claim 15. The metal-clad laminate.