WO2019214001A1

WO2019214001A1 - Resin composition, prepreg sheet for printed circuit, and metal-clad laminate

Info

Publication number: WO2019214001A1
Application number: PCT/CN2018/089250
Authority: WO
Inventors: 孟运东; 方克洪; 潘子洲
Original assignee: 广东生益科技股份有限公司
Priority date: 2018-05-07
Filing date: 2018-05-31
Publication date: 2019-11-14
Also published as: TW201946977A; TWI696666B; CN110452545B; CN110452545A

Abstract

Provided are a resin composition, a prepreg sheet for a printed circuit, and a metal-clad laminate. The resin composition comprises: a silicon arylacetylene resin; and a hydroxyl-terminated polyphenylether resin. The metal-clad laminate prepared by using the resin composition can at least have one of the following properties: a low dielectric loss factor, a high heat resistance, a low thermal expansion coefficient, halogen-free and phosphorus-free flame retardance, etc.

Description

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

Technical field

The present disclosure relates to the field of printed circuit board technology. Specifically, the present disclosure relates to a resin composition, a prepreg for a printed circuit, and a metal-clad laminate.

Background technique

A metal-clad laminate is a sheet-like material obtained by immersing an electronic glass fiber cloth or other reinforcing material in a resin liquid, and coating the metal foil on one or both sides and hot pressing, and is called a metal foil-clad laminate. Referred to as metal-clad laminate or metal-clad laminate, such as copper clad laminate or copper clad laminate (CCL). Metal-clad laminates, such as copper-clad laminates, are base laminates for the manufacture of Printed Circuit Boards (PCBs), one of the key components of the electronics industry. Almost every electronic device, from electronic watches and calculators to computers, communication electronics, military weapon systems, as long as there are electronic components such as integrated circuits, in order to electrically interconnect them, use printed boards. . Metal-clad laminates are responsible for three aspects of electrical conduction, insulation and support throughout the printed circuit board.

With the rapid development of electronic devices in terms of miniaturization, multi-function, high performance, and high reliability, the development of printed circuit boards in the direction of high precision, high density, high performance, microporation, and thinning is required. The sooner you come. The CCL largely determines the performance of the PCB.

The development trend of high precision, high density, high performance, microporation, thinning and multilayering of printed circuit boards requires higher thermal and mechanical properties of copper clad laminates. For example, more and more applications in electronic products are applied to multi-layer boards. In order to ensure the stability and reliability of multi-layer circuit boards, it is required to have a low dielectric loss factor, high heat resistance, low thermal expansion coefficient, halogen-free and phosphorus-free. Flame retardant and other characteristics.

Summary of the invention

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

Another object of the present disclosure is to provide an insulating sheet comprising the prepreg for a printed circuit, and a printed circuit board including the prepreg for the printed circuit, the insulating sheet or the metal-clad laminate. The insulating plate or the metal-clad laminate has one of low dielectric loss factor, high heat resistance, low coefficient of thermal expansion, and halogen-free and phosphorus-free flame retardant.

Accordingly, in one aspect, the present disclosure provides a resin composition comprising:

Silicon arylene resin; and

Hydroxy-terminated polyphenylene ether resin,

Wherein the weight ratio of the silicon arylene resin to the hydroxyl group polyphenylene ether resin is (30-95): (5-70);

The terminal hydroxyl polyphenylene ether resin has a number average molecular weight of 15,000 to 60,000.

According to an embodiment of the present disclosure, the silicon arylene resin is represented by the following formula:

among them

n is an integer between 1 and 5;

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 disclosure, the hydroxyl terminated polyphenylene ether resin is represented by the following formula:

Wherein m is an integer such that the number average molecular weight of the terminal hydroxyl polyphenylene ether resin is from 15,000 to 60,000.

According to another embodiment of the present disclosure, the resin composition further contains an accelerator, wherein a weight ratio of the accelerator to the silicon arylene resin is (0.01-5):100.

According to another embodiment of the present disclosure, the promoter is selected from the group consisting of: a peroxide, a metal salt of acetylacetone, a metal salt of a naphthenic acid, a vanadium pentoxide, an amine, a quaternary ammonium salt, an imidazole, a triphenylphosphine or A mixture of any two or more thereof.

According to another embodiment of the present disclosure, the resin composition further comprises a filler.

According to another embodiment of the present disclosure, the filler is selected from the group consisting of spherical silica micropowder, fused silica micropowder, aluminum hydroxide, boehmite, talc, hollow glass beads, barium titanate, alumina, boron nitride or Any mixture of two or more.

According to another embodiment of the present disclosure, the resin composition further contains a dispersant, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, or any two thereof a mixture of one or more.

According to another embodiment of the present disclosure, the resin composition further contains a solvent. Preferably, the solvent is selected from the group consisting of toluene, xylene, cyclohexane, tetrahydrofuran, methyl ethyl ketone or a mixture of any two or more thereof.

In another aspect, the present disclosure provides a prepreg for a printed circuit, the prepreg for a printed circuit comprising a reinforcing material, and a resin composition according to any one of the above, which is adhered thereto by dipping and drying .

In still another aspect, the present disclosure provides an insulating sheet comprising at least one prepreg for a printed circuit as described above.

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

In still another aspect, the present disclosure provides a printed circuit board comprising: at least one prepreg for a printed circuit as described above, or at least one insulating plate as described above, Or at least one metal clad laminate as described above.

According to the present disclosure, 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 an insulating sheet comprising the prepreg for the printed circuit, and a printed circuit board comprising the prepreg for a printed circuit, the insulating plate or the metal-clad laminate, so that the metal-clad laminate can have at least a low dielectric loss factor, high heat resistance, low coefficient of thermal expansion, One of the characteristics of halogen-free and phosphorus-free flame retardant.

detailed description

The technical solutions in the embodiments of the present disclosure will be clearly and completely described in the following, and the embodiments and/or embodiments described are only a part of the embodiments and/or embodiments of the present disclosure. Rather than all embodiments and/or embodiments. All other embodiments and/or all other embodiments obtained by a person of ordinary skill in the art based on the embodiments and/or embodiments of the present disclosure without departing from the inventive scope are the scope of the disclosure.

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

In the present disclosure, all numerical features are within the measurement error range, for example within ±10% of the defined value, or within ±5%, or within ±1%.

"Inclusion," "including," or "containing," as used in the present disclosure, means that in addition to the components, there may be other components which impart different characteristics to the prepreg. In addition, "including", "including" or "containing" as used in the present disclosure may also include "consisting essentially of" and may be replaced by "for" or "by: ....composition".

In the present disclosure, the amounts, ratios, and the like are by weight unless otherwise specified.

For the purposes of the present disclosure, the term "halogen-free and phosphorus-free flame retardant" means that the compositions of the present disclosure do not contain intentionally added halogen-containing flame retardants or phosphorus-containing flame retardants.

In the composition of the present disclosure, the content of the halogen element is preferably not more than 1% by weight, more preferably not more than 0.1% by weight, still more preferably not more than 0.01% by weight, and further preferably not more than 0.001% by weight, or 0.

In the composition of the present disclosure, the content of the phosphorus element is preferably not more than 1% by weight, more preferably not more than 0.1% by weight, still more preferably not more than 0.01% by weight, and further preferably not more than 0.001% by weight, or 0.

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

As described above, the present disclosure can provide a resin composition comprising:

Silicon arylene resin; and

Hydroxy-terminated polyphenylene ether resin,

Silicon arylene resin

The silicon arylene resin may be a resin having a molecular structure containing a silicon element, a benzene ring, and an alkyne structure.

The silicon arylene resin can be represented by the following formula:

among them

n is an integer between 1 and 5;

R' and R" are each independently a group selected from the group consisting of hydrogen, _C1-6 alkyl or _C3-6 cycloalkyl.

Preferably, the silicon arylene resin can be represented by the following formula

among them

n is an integer between 1 and 5;

In the above formula, the two alkynyl groups on the phenyl ring may be in the ortho, meta or para position. The silicon arylene resin can be obtained by polymerizing diacetylenylbenzene with dichlorosilane. For example, it can be obtained by a Grignard reaction polymerization of diacetylenylbenzene and dichlorosilane.

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

Examples of the 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 the following: : hydrogen, C _1-6 alkyl or C _3-6 cycloalkyl.

Specific examples of the dichlorosilane may include methyldichlorosilane and dichlorodimethylsilane.

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

The silicon aralyne resin may have a number average molecular weight of from about 250 to 10,000, preferably from 500 to 2,000. The low molecular weight silicon arylene resin is more soluble in the solvent and has better compatibility with the polyphenylene ether resin, which can reduce the risk of resin precipitation and phase separation, and is advantageous for forming an interpenetrating network structure. However, the reaction time of the low molecular weight silicon arylene resin is too long, which is disadvantageous for the curing process of the resin system.

Hydroxy-terminated polyphenylene ether resin

The hydroxyl terminated polyphenylene ether resin is represented by the following formula:

Wherein m is an integer such that the number average molecular weight of the terminal hydroxy polyphenylene ether resin is from 15,000 to 60,000, preferably from 15,000 to 40,000.

In the present disclosure, a hydroxyl terminated polyphenylene ether resin is sometimes also referred to as a polyphenylene ether resin, and a terminal hydroxyl polyphenylene ether is sometimes referred to as a polyphenylene ether. In the present disclosure, a terminal hydroxyl group polyphenylene ether resin having a number average molecular weight of 15,000 to 60,000 is sometimes referred to as a high molecular weight polyphenylene ether resin.

The hydroxyl-terminated polyphenylene ether resin is used as a thermoplastic polymer material, and the high molecular weight can ensure the heat resistance of the material itself, reduce the content of the terminal functional group, and reduce the negative influence of the functional group. However, too high a molecular weight will also increase the melting temperature of the material and increase the difficulty of dissolution, that is, increase the processing difficulty of the material itself.

A polyphenylene ether resin having a number average molecular weight of 15,000 or more has a stable glass transition temperature (Tg>220° C.), and has a relatively low terminal hydroxyl group content, and exhibits a lower dielectric loss in a high-speed high-frequency application. Conducive to the transmission of signals. In addition, the high molecular weight polyphenylene ether resin has better flame retardancy, and thus has certain advantages for the flame retardancy of the board.

When the number average molecular weight exceeds 60000, the solubility of the polyphenylene ether resin is too large, which is not conducive to the mixing of the resin glue. The viscosity of the obtained resin glue is high, which is not conducive to reinforcing materials such as fiberglass cloth (referred to as fiberglass cloth). Infiltration in the resin composition. That is, the excessively high molecular weight polyphenylene ether will bring extremely high difficulty to the production and processing of the copper clad laminate.

According to the processing capability of the current copper clad laminate manufacturer, it is preferred that the polyphenylene ether has a number average molecular weight of 15,000 to 40,000.

The composition containing a high molecular weight polyphenylene ether resin and containing a silicon arylene resin is a composite material processing requirement such as a copper clad laminate, and has a low dielectric loss factor, high heat resistance, low thermal expansion coefficient, flame retardancy, etc. A characteristic resin composition. Both high molecular weight polyphenylene ether resin and silicon aromatic arsenic resin have low dielectric loss factor, high heat resistance and low coefficient of thermal expansion, but high molecular weight polyphenylene ether has high melt viscosity, which is not conducive to reinforcing materials such as A glass fiber cloth (abbreviated as a fiberglass cloth) is infiltrated in the resin composition or the like. In the present disclosure, by using a silicon arylene resin and a composition thereof, the silicon arylene resin has a low melt viscosity characteristic, and can be cross-linked and cured at a high temperature to form a cured product having an ultrahigh glass transition temperature (Tg). Has excellent heat resistance. Through the present disclosure, it is ensured that the silicon arylene resin and the high molecular weight polyphenylene ether resin can be better fused, and the silicon aryl acetylene resin acts as a plasticizer for the polyphenylene ether in the process to improve the processing of the high molecular weight polyphenylene ether. And forming an interpenetrating network structure under hot pressing conditions, thereby obtaining a stable resin cured product having excellent comprehensive properties.

In addition, polyphenylene ether resin may be difficult to ensure the flame retardant requirements of the copper clad laminate, and the introduction of the silicon aromatic arsenic resin can improve the flame retardancy of the resin system and ensure the overall flame retardancy.

According to the above reasons, the ratio of polyphenylene ether to silicon arylene resin has an important influence on the actual application process. If the proportion of polyphenylene ether is too high, the viscosity will be too high, and it is difficult to infiltrate the reinforcing material. The hot press flow gel is too small, and the sheet cannot meet the flame retardant requirement; when the ratio of silicon arylene is too high, the hot press flow is too large, and the sheet is processed. The accuracy is difficult to control. Therefore, the weight ratio of the silicon arylene resin to the hydroxyl group polyphenylene ether resin may be about (30-95): (5-70), preferably about (30-90): (10-70), and further preferably about 30. -85): (15-70).

Accelerator

Optionally, the resin composition further comprises an accelerator. The accelerator is used to promote the curing reaction of the silicon arylene resin.

The promoter may be selected from the group consisting of peroxides, metal salts of acetylacetone, metal salts of naphthenic acids, vanadium pentoxide, amines, quaternary ammonium salts, imidazoles, triphenylphosphine or mixtures of any two or more thereof. .

Preferably, in the case where it is desired to control the phosphorus content of the composition, the promoter may be selected from the group consisting of: a peroxide, a metal salt of acetylacetone, a metal salt of a naphthenic acid, a vanadium pentoxide, an amine, a quaternary ammonium salt, an imidazole or Any mixture of two or more thereof to obtain a phosphorus-free resin composition.

Examples of the peroxide may include: dicumyl peroxide, t-butyl peroxy cumyl, di-tert-butyl peroxide, t-butyl peroxy isopropyl carbonate, 2,5-dimethyl-2,5 -di-tert-butyl-cumylperoxyhexyne-3,2,5-dimethyl 2,5-di-tert-butylperoxyhexane, peroxy-paraben, 1,1-bis(tert-amyl) Peroxy) cyclohexane, diisopropylbenzene hydrogen peroxide, benzoyl peroxide or benzoyl peroxide derivatives. Examples of the amine may include aniline.

The metal in the metal salt of acetylacetone 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, and the like.

The weight ratio of the promoter to the silicone arylene resin may be from about (0.01 to 5):100, preferably from about (0.05 to 2.5):100. The accelerator is used in an amount of about 0.01 to 5 parts by mass, such as 0.05 parts by mass, 0.08 parts by mass, 0.15 parts by mass, 0.25 parts by mass, 0.35 parts by mass, 0.45 parts by mass, 0.55 by mass, based on 100 parts by mass of the silicon arylene resin. Parts, 0.65 parts by mass, 0.75 parts by mass, 0.85 parts by mass, 0.95 parts by mass, 1.0 parts by mass, 1.2 parts by mass, 1.5 parts by mass, 2.0 parts by mass, 2.5 parts by mass, 3.0 parts by mass, 3.5 parts by mass, 4.0 parts by mass, Or 4.5 parts by mass, or a range or value between any two of them, preferably about 0.05 to 2.5 parts by mass.

filler

A filler component can also be added to the resin composition of the present disclosure to adjust the properties of the composition.

The filler may include an inorganic filler and an organic filler.

The inorganic filler may be selected from the group consisting of silica, boehmite, alumina, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc molybdate, zinc oxide, titanium oxide, and nitriding. Any one or at least two of boron, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, E glass powder, S glass powder, D glass powder, NE glass powder, hollow fine powder or boehmite mixture.

The organic filler may be selected from any one or a combination of at least two of polytetrafluoroethylene powder, polyimide powder, polyethersulfone powder or rubber microparticles.

The average particle diameter of the filler is in the range of 0.005 μm to 20 μm. Preferably, the average particle diameter of the filler is in the range of 0.01 μm to 10 μm.

The filler may be appropriately adjusted according to the purpose of use, and the filler is used in an amount of about 0 to 70 parts by mass, for example, 0.004 parts by mass, 0.02 parts by mass, 1 part by mass, and 2 parts by mass, based on 100 parts by mass of the total weight of the resin composition. 8 parts by mass, 12 parts by mass, 17 parts by mass, 20 parts by mass, 24 parts by mass, 26 parts by mass, 32 parts by mass, 36 parts by mass, 40 parts by mass, 45 parts by mass, 50 parts by mass, 55 parts by mass, 60 parts by weight The parts by mass, 62 parts by mass, 66 parts by mass, 68 parts by mass or 69 parts by mass or a range or value between any two of them are preferably about 5 to 40 parts by mass.

In order to better disperse the filler in the resin composition, a coupling agent may also be added to the resin composition of the present disclosure. The coupling agent can prevent the agglomeration of the filler, improve the bonding force between the resin and the filler, reduce the defects caused by the addition of the filler, reduce the water absorption rate, and the coupling agent can also improve the surface tension of the resin composition and further improve the resin composition. The fluidity of the object enhances the infiltration effect. The coupling agent may be a silane coupling agent, preferably an epoxy silane coupling agent, an amino silane coupling agent, an anilino silane coupling agent, a vinyl silane coupling agent, an isocyanate silane coupling agent, or a propylene group. Any one or a mixture of at least two of a silane coupling agent, an isobutylene silane coupling agent, a styrene silane coupling agent, an anionic silane coupling agent, or a ureido silane coupling agent. Specific examples thereof include an aminosilane coupling agent such as γ-aminopropyltriethoxysilane or N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-glycidyl ether. Ethoxysilane coupling agent such as oxypropyltrimethoxysilane, vinyl silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, or N-β-(N-vinylbenzene-acryloylamide An anionic silane coupling agent such as ethyl)-γ-aminopropyltrimethoxysilane hydrochloride.

The amount of the coupling agent to be used is not particularly limited, and preferably, the coupling agent is used in an amount of from about 0 to 5 parts by mass, more preferably from about 0.005 to 4 parts by mass, based on 100 parts by mass based on the total mass of the resin composition. About 0.05-3 parts by mass. The amount of the coupling agent used is, for example, 0.5 parts by mass, 1 part by mass, 1.5 parts by mass, 2 parts by mass, 2.5 parts by mass, 3 parts by mass, 3.5 parts by mass, 4 parts by mass or 4.5 parts by mass, or any two of them. Range or value between.

Further, the resin composition may further contain various auxiliary agents. Specific examples of the auxiliary agent include a filler dispersant, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These additives may be used singly or in combination of any two or more.

The resin composition of the present disclosure may be subjected to a known method such as compounding, stirring, mixing a silicon alkyne resin, a hydroxyl terminated polyphenylene ether resin, and optionally a promoter, a dispersing agent, an antifoaming agent, an antioxidant, and a heat stabilizer. Prepared with an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, or a mixture of any two or more thereof.

The resin composition according to the present disclosure may further contain a solvent.

The solvent in the present disclosure is not particularly limited, and specific examples thereof include toluene, xylene, cyclohexane, tetrahydrofuran, methyl ethyl ketone or a mixture of any two or more thereof. These solvents may be used alone or in combination of two or more. The amount of the solvent to be used can be selected by those skilled in the art according to their own experience, so that the obtained resin glue can reach a viscosity suitable for use.

The resin composition according to the present disclosure may be a halogen-free and phosphorus-free resin composition.

The reinforcing material according to the present disclosure may include: a glass fiber cloth, a glass fiber nonwoven fabric, an organic nonwoven fabric, and the like.

The resin composition is formulated into a resin glue by mechanical stirring, emulsification or ball mill dispersion, and then the resin glue is used to infiltrate a reinforcing material such as a glass fiber cloth, and dried to obtain a prepreg. A metal-clad laminate can be prepared by hot pressing the prepreg sheet and a metal foil such as a copper foil or an aluminum foil in a vacuum press.

In order to lower the viscosity of the resin glue, it is possible to infiltrate under heating. Heating is carried out so that the temperature of the resin glue is lower than the boiling point of the solvent used, and it is preferred that the temperature of the resin glue at the time of wetting is about 50 to 90 ° C, and more preferably about 55 to 85 ° C.

In another aspect, the present disclosure may also provide a prepreg for a printed circuit, the prepreg for a printed circuit comprising a reinforcing material and a resin combination according to any one of the above attached by dampening and drying thereon Things.

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

In still another aspect, the present disclosure may also provide a printed circuit board comprising: at least one prepreg for a printed circuit as described above, or at least one insulation as described above A board, or at least one metal clad laminate as described above.

Example

The technical solutions of the present disclosure will be further described below by way of specific embodiments. However, the examples are intended to illustrate the disclosure and are not to be construed as limiting the disclosure.

The materials used in the examples are as follows:

Silicon Aromatic Resin Resin: The preparation process is as follows.

Add 3.5 parts of magnesium powder (chemically pure, Shanghai Sinopharm Chemical Co., Ltd.), and 40 parts of tetrahydrofuran (THF) solvent to the reactor filled with nitrogen, and stir and add 13.5 parts of ethyl bromide at room temperature (chemically pure, Shanghai Sinopharm Chemical Reagent Co., Ltd.) and 40 parts of THF were mixed and kept at 50 ° C for 1 h after the completion of the dropwise addition. Then, a mixture of 7.5 parts of 1,3-diacetylenylbenzene (Shandong Jiaozhou Fine Chemical Co., Ltd.) and 40 parts of THF solvent was added dropwise under ice-cold bath conditions, and after the addition was completed, the mixture was incubated at 65 ° C for 1 h. Then, it was cooled again, and 5.5 parts of dichlorodimethylsilane (chemically pure, Zhejiang Xinan Chemical Group Co., Ltd., used after distillation) and 40 ml of THF were added dropwise under ice-cold bath, and the mixture was added at 40 ° C and 70 respectively. Incubate at °C for 1 h. After the reaction was completed, the THF in the reaction mixture was distilled off, and a mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene solvent was added dropwise thereto under ice-cold bath, and after stirring well, 140 parts of a 2.0% diluted hydrochloric acid aqueous solution was added dropwise, and the mixture was thoroughly stirred. The upper organic phase is separated. The organic phase was sufficiently washed with water to neutrality, then dried, filtered, and toluene evaporated to give a silicon phenylene resin (i.e., a silicon arylene resin used in the examples and the comparative examples).

Fiberglass cloth: E-type fiberglass cloth of type 2116, Nittofang

Copper foil: 35μm (1Oz) RTF copper foil, Suzhou Futian Metal Co., Ltd.

D50: the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when the cumulative volume distribution curve based on the particle diameter is obtained by taking the total volume of the particles as 100%, and the laser diffraction scattering method is used. Particle size distribution determination.

Example 1

100 parts of silicon arylene resin (number average molecular weight 1200) and 200 parts of polyphenylene ether resin (PPO-640, Mn about 20,000, SABIC Innovative Plastics) are fully dissolved in 300 parts of xylene at 100 ° C to obtain resin glue. liquid. Take the flat and smooth, type 2116 E-glass fiber cloth to uniformly infiltrate the above resin glue at 80 ° C, and bake at 170 ° C for 5 min in a forced air oven to obtain a prepreg for printed circuit, and use 6 sheets of the above printed circuit. The prepreg sheets were overlapped, and 35 μm copper foil was overlaid on the upper and lower sides, and pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220 ° C for 90 minutes to obtain a copper clad laminate.

Example 2

250 parts of silicon arylene resin (number average molecular weight 1200) and 50 parts of polyphenylene ether resin (PPO-640, Mn about 20,000, SABIC Innovative Plastics) are fully dissolved in 200 parts of xylene at 100 ° C, then added 1 A solution of cobalt acetylacetonate and 1.5 parts of triphenylphosphine in ethanol was uniformly mixed to obtain a resin glue. Take the flat and smooth, type 2116 E-glass fiber cloth to uniformly infiltrate the above resin glue at 60 ° C, and bake at 170 ° C for 5 min in a forced air oven to obtain a prepreg for printed circuit, and use 6 sheets of the above printed circuit. The prepreg sheets were overlapped, and 35 μm copper foil was overlaid on the upper and lower sides, and pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 200 ° C for 90 minutes to obtain a copper clad laminate.

Example 3

100 parts of silicon arylene resin (number average molecular weight 1200) and 200 parts of polyphenylene ether resin (PPO-640, Mn about 20,000, SABIC Innovative Plastics) are fully dissolved in 500 parts of xylene at 100 ° C, then added 300 The fused silica (D50 = 3.0 μm, Jiangsu Lianrui New Material Co., Ltd.) was uniformly mixed to obtain a resin glue. Take the flat and smooth, type 2116 E-glass fiber cloth to uniformly infiltrate the above resin glue at 80 ° C, and bake at 170 ° C for 5 min in a forced air oven to obtain a prepreg for printed circuit, and use 6 sheets of the above printed circuit. The prepreg sheets were overlapped, and 35 μm copper foil was overlaid on the upper and lower sides, and pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220 ° C for 90 minutes to obtain a copper clad laminate.

Comparative example 1

100 parts of silicon arylene resin (number average molecular weight 1200) and 200 parts of polyphenylene ether resin (SA90, Mn about 1800, SABIC Innovative Plastics) are fully dissolved in 500 parts of xylene at 100 ° C, then 300 parts of molten Silica (D50=3.0 μm, Jiangsu Lianrui New Material Co., Ltd.) was uniformly mixed to obtain a resin glue. The E-type fiberglass cloth of type 2116 is evenly immersed in the above-mentioned resin glue at room temperature, and baked in a blower oven at 170 ° C for 5 minutes to prepare a prepreg for the printed circuit, and six of the above printed circuits are used. The immersion sheets were overlapped, and 35 μm copper foil was overlaid on the upper and lower sides, and pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220 ° C for 90 minutes to obtain a copper clad laminate.

Comparative example 2

300 parts of silicon arylene resin (number average molecular weight 1200) was fully dissolved in 500 parts of xylene at 100 ° C, and then 300 parts of fused silica (D50 = 3.0 μm, Jiangsu Lianrui New Material Co., Ltd.) was added and mixed. Evenly, a resin glue is obtained. The E-type fiberglass cloth of type 2116 is evenly immersed in the above-mentioned resin glue liquid, and baked in a blast oven at 170 ° C for 5 minutes to obtain a prepreg for the printed circuit, and six prepregs for the above printed circuit are used. Overlap, 35 μm copper foil was overlaid on top and bottom, and pressed in a vacuum hot press at a pressure of 3 MPa and a temperature of 220 ° C for 90 min to obtain a copper clad laminate.

The copper clad laminates obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated for performance. The evaluation results are summarized in the table below.

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

1) Glass transition temperature Tg: using dynamic mechanical analysis (DMA) test, according to the DMA test method specified in IPC-TM-650 2.4.24;

2) Thermal decomposition temperature (Td): using the thermogravimetric analysis (TGA) test according to the standard IPC-TM-650 2.4.24.6;

3) Peel strength (PS): refers to the tensile force required to peel off the copper clad plate per mm of copper foil at room temperature;

4) Dielectric constant (Dk) and dielectric loss factor (Df): 1 GHz is measured by the plate capacitance method according to the standard IPC-TM-650 2.4.24, and 10 GHz is measured by the resonant cavity method (SPDR) method according to the standard IPC. -TM-650 2.5.5.5.

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

6) Thermal expansion coefficient and 50-260 ° C thermal expansion ratio: The test was tested by static thermal analyzer (TMA) according to the standard IPC-TM-650 2.4.24.

7) Thermal stress: The copper-clad laminate was floated on the surface of the molten tin bath at a temperature of 288 ° C, and the time of delamination or bubble was used as a test result.

With the above examples and comparative test results, it can be seen that the samples of this example can achieve halogen-free and phosphorus-free flame retardant, and the test results of Tg and Td are higher than the Tg and Td of the conventional printed circuit board. The dielectric loss factor results for copper clad laminates indicate that they will have good application properties in high frequency high speed laminates and have excellent CTE and thermal stress performance.

When the molecular weight of the polyphenylene ether resin is low, the Tg and Td of Comparative Example 1 are low, and the flame retardancy is inferior.

In contrast to Example 3, the composition of Comparative Example 2 was free of polyphenylene ether resin, and the copper-clad laminate had a dielectric constant of 4.6 at 10 GHz, which was much higher than 3.9 of the copper-clad laminate of Example 3, indicating polyphenylene ether. The addition of this type of composition has a strong advantage in the application of high frequency and high speed.

As described above, a resin composition, a prepreg for a printed circuit obtained by impregnating the resin composition with a fiberglass cloth, and a metal-clad laminate or an insulating sheet comprising the prepreg for a printed circuit, and the like, The prepreg for the printed circuit, the insulating plate or the printed circuit board of the metal-clad laminate, so that the metal-clad laminate can have at least a low dielectric loss factor, high heat resistance, low thermal expansion coefficient, and no One of the characteristics of halogen-free phosphorus flame retardant.

It will be apparent to those skilled in the art that various modifications and changes can be made in the embodiments of the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present invention cover the modifications and the modifications

Claims

A resin composition comprising:

Silicon arylene resin; and

Hydroxy-terminated polyphenylene ether resin,

Wherein the weight ratio of the silicon arylene resin to the hydroxyl group polyphenylene ether resin is (30-95): (5-70);

The terminal hydroxyl polyphenylene ether resin has a number average molecular weight of 15,000 to 60,000.
The resin composition according to claim 1, wherein said silicon aralcene resin is represented by the following formula:

among them

n is an integer between 1 and 5;

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 said hydroxyl group polyphenylene ether resin is represented by the following formula:

Wherein m is an integer such that the number average molecular weight of the terminal hydroxyl polyphenylene ether resin is from 15,000 to 60,000.
The resin composition according to claim 1, further comprising an accelerator, wherein a weight ratio of the accelerator to the silicon arylene resin is from (0.01 to 5):100.
The resin composition according to claim 4, wherein the accelerator is selected from the group consisting of peroxides, metal salts of acetylacetone, metal salts of naphthenic acids, vanadium pentoxide, amines, quaternary ammonium salts, imidazoles, triphenyls. A phosphine or a mixture of any two or more thereof.
The resin composition according to claim 1, which further comprises a filler.
The resin composition according to claim 6, wherein the filler is selected from the group consisting of spherical silica micropowder, fused silica micropowder, aluminum hydroxide, boehmite, talc, hollow glass beads, barium titanate, alumina, and nitriding. Boron or a mixture of any two or more thereof.
The resin composition according to claim 1, further comprising a dispersant, an antifoaming agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant or the like Any mixture of two or more.
The resin composition according to claim 1, which further comprises a solvent.
A prepreg for a printed circuit comprising a reinforcing material and a resin composition according to any one of claims 1 to 8 adhered thereto by dampening and drying.
An insulating sheet comprising at least one prepreg for a printed circuit according to claim 10.
A metal-clad laminate comprising at least one prepreg for a printed circuit according to claim 11 and a metal foil.
A printed circuit board comprising: at least one prepreg for a printed circuit according to claim 10, or at least one insulating plate according to claim 11, or at least one A metal clad laminate according to claim 12.