A polyphenylene sulfide-based copper-clad plate and a method for manufacturing the same

Abstract

The present application relates to the technical field of the preparation of copper-clad plates for printed circuit boards, and specifically relates to a polyphenylene sulfide-based copper-clad plate, comprising a resin layer and a copper foil layer covering one side or both sides of the resin layer, wherein the resin layer comprises the following raw materials in parts by weight: polyphenylene sulfide resin 50-70 parts, phenolphthalein polyarylether ketone 10-20 parts, polyether sulfone 2-4 parts, modified glass fiber 10-40 parts, inorganic filler 10-30 parts, toughening agent 1-3 parts, and flame retardant 3-10 parts. The polyphenylene sulfide-based copper-clad plate produced by the present application has the advantages of simple preparation process, difficulty in crystallization, good dielectric properties, high heat resistance, excellent flame retardance, low water absorption, and low thermal expansion coefficient, and is suitable for application in the high-frequency high-speed copper-clad plate industry.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of preparation of copper-clad plate for printed circuit board, and particularly relates to a polyphenylene sulfide-based copper-clad plate and a preparation method thereof. BACKGROUND

[0002] With the advent of the 5G era, many high-throughput communication scenarios have entered the civilian market, such as ultra-low latency communication, wireless AR / VR, V2X, etc. Such communication scenarios that need to meet high throughput and low latency at the same time pose higher challenges to the materials of printed circuit boards inside the device, and in turn promote the further development of the high-frequency high-speed copper-clad plate (printed circuit board base material) industry.

[0003] Traditional epoxy copper-clad plate (FR4) materials are cheap and versatile, and the subsequent process is mature and perfect. However, its relatively high dielectric constant (Dk is about 4.4) and large dielectric loss (Df is about 0.02) result in slow transmission speed and large signal loss, greatly restricting its application in the high-frequency high-speed field.

[0004] There are generally three materials for high-frequency high-speed copper-clad plates, namely polytetrafluoroethylene (PTFE) material and thermosetting hydrocarbon material and polyphenylene ether (PPE) material. PTFE, as the oldest high-frequency high-speed copper-clad plate base material, has good dielectric properties (Dk is about 2.1, Df is about 0.0004), but its high lamination temperature (about 370 degrees) and large linear expansion coefficient (CTE is about 110 ppm) result in poor processability, which cannot be matched with the traditional FR4 material processing process. In recent years, the emerging thermosetting hydrocarbon material and PPE material have improved the processing performance (reduced the lamination temperature to adapt to the traditional FR4 processing) at the expense of part of the dielectric properties (usually the Dk of the two series is not less than 3, and the Df is 0.003 or more). However, a large amount of organic solvents such as toluene and methyl ethyl ketone are used in the production process, which puts great pressure on environmental protection and restricts its large-scale production and use.

[0005] In addition, a thermoplastic composite material type of copper-clad plate has appeared in recent years, such as the thermoplastic polyolefin copper-clad plate reported in patent CN108437593A, which has excellent dielectric properties (Dk is about 2.7, Df <0.002). However, the melting point of polyolefin is only 190 degrees, which cannot meet the lead-free reflow soldering (260 degrees) process. At the same time, the linear thermal expansion coefficient of polyolefin material is large (CTE is about 80 ppm / ℃), and the difference with copper foil (CTE is about 19 ppm / ℃) is obvious, which cannot meet the high-density interconnection (HDI) process.

[0006] The polyphenylene sulfide material gradually attracts the attention of people in the field of copper-clad plate due to its excellent mechanical properties, dielectric properties, good water resistance and low thermal expansion coefficient. The patent CN114106558B provides an extrusion calendering polyphenylene sulfide copper-clad plate material and a preparation method thereof. The polyphenylene sulfide resin is modified by blending polyarylate, polyphenyl ether resin and industrial liquid crystal polymer, which improves the problem that the polyphenylene sulfide material cannot be directly copper-clad on the surface due to brittleness caused by rapid crystallization. However, the polyphenyl ether resin itself has the defect of poor processing fluidity, which may affect the processing performance of the polyphenylene sulfide copper-clad plate material.

[0007] Therefore, there is an urgent need in the market for a copper-clad plate which has a simple preparation process, is not easy to crystallize, has good dielectric properties, high heat resistance, excellent flame retardation, low water absorption and low thermal expansion coefficient. SUMMARY

[0008] In view of the problems in the prior art, the purpose of the present application is to obtain a copper-clad plate which has a simple preparation process and good dielectric properties, high heat resistance, excellent flame retardation, low water absorption and low thermal expansion coefficient.

[0009] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0010] In one aspect, the present application provides a polyphenylene sulfide-based copper-clad plate, which comprises a resin layer and a copper foil layer covering one side or both sides of the resin layer. The resin layer comprises, by weight, polyphenylene sulfide resin 50-70 parts, phenolphthalein polyaryletherketone 10-20 parts, polyether sulfone 2-4 parts, modified glass fiber 10-40 parts, inorganic filler 10-30 parts, toughening agent 1-3 parts and flame retardant 3-10 parts.

[0011] The applicant found that the polyphenylene sulfide substrate prepared by blending phenolphthalein polyaryletherketone and polyether sulfone with polyphenylene sulfide has good toughness, which solves the problem that the polyphenylene sulfide material cannot be directly copper-clad on the surface due to rapid crystallization. In addition, the polyphenylene sulfide substrate has good dielectric properties and heat resistance. This may be because the structure of phenolphthalein polyaryletherketone and polyether sulfone is similar to that of polyphenylene sulfide, and there are no too many active groups, so the blending of the two resins with polyphenylene sulfide will not affect the dielectric properties and heat resistance of polyphenylene sulfide. The applicant found in the research that the toughening effect is best when the two resins are used together, which may be due to the synergistic toughening effect of the two resins. The crystallinity of the two resins and polyphenylene sulfide is quite different, and thermoplastic microspheres can be formed after the substrate solidifies, which can be dispersed between polyphenylene sulfide to play the role of crack-rivet, absorb external stress and reduce the damage of external stress to polyphenylene sulfide.

[0012] On the other hand, the applicant found that the crystallinity of the polyphenyl sulfide material blended with the phenolphthalein type polyaryletherketone was reduced, which may be due to the thermal oxidative decomposition of the phenolphthalein type polyaryletherketone when heated, which can dissociate oxygen and carbonyl groups during the decomposition process, and can promote the thermal oxidative crosslinking of polyphenyl sulfide, thereby reducing the crystallinity and increasing the molecular weight of polyphenyl sulfide. And the phenolphthalein type polyaryletherketone itself will also undergo thermal oxidative crosslinking, and the molecular chains of the two substances form a crosslinked interpenetrating network, making the performance of the polyphenyl sulfide resin more excellent.

[0013] Persons skilled in the relevant field usually add glass fibers to reinforce the polyphenyl sulfide material and improve its impact resistance, but when the glass fiber reinforces the resin matrix, the stress is mainly concentrated between the layers, which can easily cause the material to be damaged and delaminated. The applicant added phenolphthalein type polyaryletherketone and polyether sulfone to make the stress distribution in the substrate more uniform, thereby improving the problem of interlaminar damage of glass fiber reinforced polyphenyl sulfide material.

[0014] In some embodiments, the polyphenyl sulfide resin is one or more of a polyphenyl sulfide resin with a molecular weight Mw≥55000 and a chlorine element content ≤1200ppm.

[0015] The size of the molecular weight affects the melting point and processing performance of the polyphenyl sulfide resin. The polyphenyl sulfide resin with Mw≥55000 is suitable for processing and molding in the field of copper-clad plate with high performance requirements. The chlorine content affects the mechanical properties and thermal stability of the polyphenyl sulfide, thereby affecting its application, and even possibly leading to degradation of the polymer. The polyphenyl sulfide prepared using chlorine element content ≤1200ppm has good mechanical properties and thermal stability.

[0016] In some embodiments, the copper foil used in the copper foil layer is a low roughness copper foil, and the thickness of the low roughness copper foil is 12μm-36μm, and the surface roughness Rz is between 0.5μm-12μm.

[0017] Preferably, the low roughness copper foil is a reverse copper foil.

[0018] In some embodiments, the method for preparing the modified glass fiber comprises the following steps:

[0019] (1) Add silane coupling agent and 40-60% mass fraction of ethanol aqueous solution into the reaction kettle, then add the cleaned glass fiber, and then heat to 50-80℃ and stir for 1-2h, and then dry after suction filtration to obtain pretreated glass fiber;

[0020] (2) mixing the pretreated glass fiber obtained in step (1) with trifluorovinyl ether, glycidyl methacrylate, ethylene, octene, four kinds of monomers and toluene, adding benzoyl peroxide, and reacting at 90-110°C for 4-5h to obtain modified glass fiber.

[0021] Preferably, the method for preparing the modified glass fiber comprises the following steps:

[0022] (1) adding silane coupling agent and 40-60% mass fraction of ethanol aqueous solution into a reaction kettle, then adding cleaned glass fiber, the weight ratio of glass fiber, silane coupling agent and ethanol aqueous solution being 9-11:0.5-2:30-50, and then heating to 50-80°C and stirring for 1-2h to obtain pretreated glass fiber;

[0023] (2) mixing the pretreated glass fiber obtained in step (1) with trifluorovinyl ether, glycidyl methacrylate, ethylene, octene, four kinds of monomers and toluene, adding benzoyl peroxide, and reacting at 90-110°C for 4-5h to obtain modified glass fiber.

[0024] In some embodiments, the weight ratio of the glass fiber grafted with silane coupling agent, trifluorovinyl ether, glycidyl methacrylate, ethylene and octene is 9-11:0.05-0.1:0.05-0.1:0.1-0.2:0.1-0.2.

[0025] In some embodiments, the glass fiber is E glass fiber or LD glass fiber, and the Dk thereof is 4.0-6.6, and the single fiber diameter is ≥10μm.

[0026] Preferably, the glass fiber is LD glass fiber.

[0027] In some embodiments, the silane coupling agent is vinyltriethoxysilane or vinyltrimethoxysilane.

[0028] The silane coupling agent is commonly used by those skilled in the art to modify glass fiber to increase the compatibility of glass fiber with polymer, but there is no active group on the polyphenylene sulfide segment that can react with the amino group, double bond, hydroxyl group and the like carried on the conventional silane coupling agent, and the modification of glass fiber by only using silane coupling agent cannot play a great role in the polyphenylene sulfide system. The applicant grafts the silane coupling agent containing double bond on the glass fiber, and then copolymerizes glycidyl methacrylate, ethylene and octene to load the segment of the compatibilizer on the glass fiber, so that the glass fiber can be well dispersed in the polyphenylene sulfide system.

[0029] However, glycidyl methacrylate carries a large number of active groups, which can easily affect the excellent dielectric properties of glass fibers. The applicant found that adding a trifluorovinyl ether to introduce a trifluoromethyl group on the organic chain can eliminate the influence of active groups on the dielectric properties of glass fibers, and the dielectric properties of the copper-clad plate are also improved.

[0030] In some embodiments, the inorganic filler is one or more of magnesium oxide, zinc oxide, titanium dioxide, barium titanate, strontium titanate, barium strontium titanate, aluminum oxide, kaolin, talc, silicon dioxide, solid silica microspheres, hollow glass microspheres, and boehmite.

[0031] Preferably, the inorganic filler is silicon dioxide.

[0032] In some embodiments, the toughening agent is one or more of a terpolymer of ethylene, maleic anhydride, and glycidyl methacrylate (E-GMA), a block copolymer of hydrogenated styrene, butadiene, and styrene (SEBS), and a terpolymer of ethylene, methyl acrylate, and glycidyl methacrylate (EMA).

[0033] Preferably, the toughening agent is EMA.

[0034] In some embodiments, the flame retardant is one or more of a phosphorus-based flame retardant, a nitrogen-based flame retardant, and an aluminum-magnesium-based flame retardant.

[0035] Preferably, the flame retardant is a phosphorus-based flame retardant.

[0036] Further preferably, the flame retardant is triphenyl phosphate (TPP).

[0037] In some embodiments, the lubricant is one or more of silicone, polyolefin wax, stearate, and pentaerythritol stearate.

[0038] Preferably, the lubricant is pentaerythritol stearate.

[0039] Another aspect of the present application provides a preparation method of a polyphenylene sulfide-based copper-clad plate, comprising the following steps:

[0040] (1) Put polyphenylene sulfide resin, phenolphthalein-type polyaryletherketone, polyether sulfone, inorganic filler, toughening agent, and flame retardant into a high-speed mixer, set the paddle speed to 200-500 RPM / min, and mix for 5-8 min to obtain a premix;

[0041] (2) Put the premix prepared in step (1) in the main feeder, and put the modified glass fiber in the side feeder; set the temperature of the feeding zone of the twin-screw extruder to 50-80 DEG C, the temperature of the melting zone to 300-320 DEG C, the temperature of the mixing zone to 320-330 DEG C, and the temperature of the dispersion zone to 300-320 DEG C; set the rotation speed of the twin-screw extruder to 300-350 RPM, and the total extrusion speed to 15-30 kg / h to perform modification and granulation, and obtain polyphenylene sulfide composition granules;

[0042] (3) Put the polyphenylene sulfide composition granules obtained in step (2) into an extrusion caster, set the cylinder temperature to 300-330 DEG C, the roller temperature to 150-220 DEG C, and the linear speed to 0.3-4.5 m / min to obtain a resin layer with a thickness of 0.2 mm-1.6 mm;

[0043] (4) Stack the resin layer obtained in step (3) and the copper foil according to the copper foil layer-resin layer or copper foil layer-resin layer-copper foil layer, then cover both sides with steel plates and kraft paper, and put them into a vacuum press, set the vacuum degree to 0.1-0.2 Bar A, the hot table temperature to 280-300 DEG C, the temperature rising rate to 8-10 DEG C / min, the pressure to 5-15 Mpa, and the duration to 10-30 min, then slowly cool to below 120 DEG C, release the pressure, and take out to obtain a polyphenylene sulfide-based copper-clad plate.

[0044] Compared with the prior art, the present application has the following beneficial effects:

[0045] 1. The present application selects polyphenylene sulfide as the base sheet of the copper-clad plate, and adds phenolphthalein type polyaryletherketone and polyether sulfone to obtain a copper-clad plate with simple preparation process, low crystallization, good dielectric performance, high heat resistance, excellent flame retardation, low water absorption, and low thermal expansion coefficient.

[0046] 2. The present application uses the addition of phenolphthalein type polyaryletherketone and polyether sulfone to achieve the effect of synergistic toughening while ensuring the low dielectric performance and heat resistance of the composite material.

[0047] 3. The present application adds phenolphthalein type polyaryletherketone to promote the thermal oxidative crosslinking of polyphenylene sulfide by thermal decomposition of oxygen atoms and carbonyl groups to act as oxidizing agents, improve the performance of polyphenylene sulfide, and at the same time, the phenolphthalein type polyaryletherketone also undergoes thermal oxidative crosslinking to form an interpenetrating network in the polyphenylene sulfide, further improving the performance of the polyphenylene sulfide-based copper-clad plate.

[0048] 4. The present application improves the dispersion performance of glass fibers by using silane coupling agents containing double bonds to modify the glass fibers and grafting compatible agent segments, ensures the uniformity and stability of the dielectric properties of each part of the copper-clad plate, and introduces trifluorovinyl ether on the modified glass fibers to eliminate the negative effects of the compatible agent segments on the dielectric properties of the glass fibers, and at the same time, the dielectric properties of the copper-clad plate are also improved. DETAILED DESCRIPTION

[0049] The present application will be described below in conjunction with specific embodiments. It should be noted that the following examples are examples of the present application and are only used to illustrate the present application, but not to limit the present application. Other combinations and various modifications within the concept of the present application can be made without departing from the spirit or scope of the present application.

[0050] In the following examples and comparative examples, the related reagents used except for the modified glass fibers can be purchased from the market, wherein the reverse copper foil with a thickness of 35 μm is purchased from Yantai Chenyu Electronics Co., Ltd.; the polyphenylene sulfide with a type of 1350C, Mw≥55000, and a chlorine element content of ≤1200 ppm is purchased from Zhejiang Xinhengcheng Co., Ltd.; the phenolphthalein type polyaryletherketone is purchased from the Xu Zhou Engineering Plastics Company of the Changchun Institute of Applied Chemistry, Chinese Academy of Sciences; the polyether sulfone (Mw=55000) is purchased from the BASF-China Group Co., Ltd. in Germany; the LD glass fiber with a type of 309HL, a Dk between 4.0-6.6, and a single filament diameter of ≥10 μm is purchased from Chongqing International Composite Material Co., Ltd.; the silicon dioxide with a type of SJF-0020 is purchased from Anhui Yishitong Material Technology Co., Ltd.; the ethylene-methyl acrylate-glycidyl methacrylate (EMA) with a type of AX8900 is purchased from South Korea SK; the triphenyl phosphate (TPP) is purchased from Zhejiang Wansheng Co., Ltd.; and the pentaerythritol stearate is purchased from Lonza in Switzerland.

[0051] Preparation Example 1

[0052] The preparation method of the modified glass fiber-1 comprises the following steps:

[0053] (1) 1 g of vinyl trimethoxysilane and 40 g of 50% mass fraction ethanol aqueous solution were added into a three-necked flask, then 10 g of washed LD glass fiber was added, and then the temperature was increased to 65°C for stirring for 1.5 h, and then the pretreated LD glass fiber was obtained after filtration and drying;

[0054] (2) 10 g of the pretreated LD glass fiber obtained in step (1) was uniformly mixed with 0.5 g of trifluorovinyl ether, 0.075 g of glycidyl methacrylate, 0.15 g of ethylene, 0.15 g of octene, and 20 g of toluene, 0.01 g of benzoyl peroxide was added, and then the reaction was carried out at 100°C for 4 h, and then the modified glass fiber-1 was obtained after filtration and drying.

[0055] Preparation Example 2

[0056] The preparation method of the modified glass fiber-2 comprises the following steps:

[0057] (1) 1 g of vinyl trimethoxysilane and 40 g of 50% ethanol aqueous solution were added into a three-necked flask, then 10 g of washed LD glass fiber was added, and the temperature was increased to 65°C for stirring for 1.5 h, and then the pretreated LD glass fiber was obtained by filtration and drying;

[0058] (2) 10 g of the pretreated LD glass fiber obtained in step (1) was uniformly mixed with 0.075 g of glycidyl methacrylate, 0.15 g of ethylene, 0.15 g of octene, and 20 g of toluene, 0.01 g of benzoyl peroxide was added, and the reaction was carried out at 100°C for 40 h, and then the modified glass fiber-2 was obtained by filtration and drying.

[0059] Preparation Example 3

[0060] The preparation method of the modified glass fiber-3 is as follows: 1 g of vinyl trimethoxysilane and 40 g of 50% ethanol aqueous solution were added into a three-necked flask, then 10 g of washed LD glass fiber was added, and the temperature was increased to 65°C for stirring for 1.5 h, and then the modified glass fiber-3 was obtained by filtration and drying;

[0061] Example 1

[0062] A polyphenylene sulfide-based copper-clad plate comprises a resin layer and a copper foil layer covering one side of the resin layer, wherein the resin layer comprises, by weight, 60 parts of polyphenylene sulfide resin, 15 parts of phenolphthalein polyaryletherketone, 3 parts of polyether sulfone, 25 parts of modified glass fiber-1, 15 parts of silicon dioxide, 2 parts of EMA, and 5 parts of triphenyl phosphate.

[0063] The preparation method of the polyphenylene sulfide-based copper-clad plate comprises the following steps:

[0064] (1) The polyphenylene sulfide resin, phenolphthalein polyaryletherketone, polyether sulfone, silicon dioxide, EMA, and TPP were put into a high-speed mixer, the paddle rotation speed was set to 350 RPM / min, and the pre-mixture was obtained by mixing for 6 min;

[0065] (2) The pre-mixture prepared in step (1) was placed in the main feeder, and the modified glass fiber-1 was placed in the side feeder; the feeding zone temperature of the twin-screw extruder was set to 60°C, the melting zone temperature was set to 310°C, the mixing zone temperature was set to 325°C, and the dispersion zone temperature was set to 310°C; the rotation speed of the twin-screw extruder was set to 325 RPM, and the total extrusion speed was set to 23 kg / h for modified granulation, and the polyphenylene sulfide composition granules were obtained.

[0066] (3) Put the polyphenylene sulfide composition pellets obtained in step (2) into an extrusion casting machine, set the cylinder temperature at 315°C, the roller temperature at 200°C, and the linear speed at 2.5 m / min, to prepare a resin layer with a thickness of 0.8 mm;

[0067] (4) Stack the resin layer obtained in step (3) and the copper foil according to the copper foil layer-resin layer, then cover both sides with steel plates and kraft paper, and put them into a vacuum press, set the vacuum degree at 0.15 Bar A, the hot table temperature at 290°C, the heating rate at 9°C / min, the pressure at 10 Mpa, and keep for 20 min, then slowly cool to 90°C, release the pressure, and take out, to obtain a polyphenylene sulfide-based copper-clad plate.

[0068] Example 2

[0069] A polyphenylene sulfide-based copper-clad plate, comprising a resin layer and a copper foil layer covering one side of the resin layer, wherein the resin layer comprises, by weight, 50 parts of polyphenylene sulfide resin, 10 parts of phenolphthalein polyaryletherketone, 2 parts of polyether sulfone, 10 parts of modified glass fiber-1, 10 parts of silicon dioxide, 1 part of EMA, and 3 parts of triphenyl phosphate.

[0070] A method for preparing a polyphenylene sulfide-based copper-clad plate, comprising the following steps:

[0071] (1) Put polyphenylene sulfide resin, phenolphthalein polyaryletherketone, polyether sulfone, EMA, and TPP into a high-speed mixer, set the paddle rotation speed at 200 RPM / min, mix for 5 min, and obtain a premix;

[0072] (2) Put the premix prepared in step (1) into a main feeder, and put modified glass fiber-1 into a side feeder; set the feeding zone temperature of the twin-screw extruder at 50°C, the melting zone temperature at 300°C, the mixing zone temperature at 320°C, and the dispersion zone temperature at 300°C; set the rotation speed of the twin-screw extruder at 300 RPM, and the total extrusion speed at 15 kg / h for modified granulation, to obtain polyphenylene sulfide composition pellets;

[0073] (3) Put the polyphenylene sulfide composition pellets obtained in step (2) into an extrusion casting machine, set the cylinder temperature at 300°C, the roller temperature at 150°C, and the linear speed at 0.3 m / min, to prepare a resin layer with a thickness of 0.2 mm;

[0074] (4) Stack the resin layer obtained in step (3) and the copper foil according to the copper foil layer-resin layer, then cover both sides with steel plates and kraft paper, and put them into a vacuum press, set the vacuum degree at 0.1 Bar A, the hot table temperature at 280°C, the heating rate at 8°C / min, the pressure at 5 Mpa, and keep for 10 min, then slowly cool to 50°C, release the pressure, and take out, to obtain a polyphenylene sulfide-based copper-clad plate.

[0075] Example 3

[0076] A polyphenylene sulfide-based copper clad plate, comprising a resin layer and a copper foil layer covering a single side of the resin layer, wherein the resin layer comprises, by weight parts, 70 parts of polyphenylene sulfide resin, 20 parts of phenolphthalein polyaryletherketone, 4 parts of polyether sulfone, 40 parts of modified glass fiber-1, 30 parts of silicon dioxide, 3 parts of EMA, and 10 parts of triphenyl phosphate.

[0077] A method for preparing a polyphenylene sulfide-based copper clad plate, comprising the following steps:

[0078] (1) Put polyphenylene sulfide resin, phenolphthalein polyaryletherketone, polyether sulfone, silicon dioxide, EMA, and TPP into a high-speed mixer, set the paddle rotation speed to 500 RPM / min, and mix for 8 min to obtain a premix;

[0079] (2) Place the premix prepared in step (1) in a main feeder and place modified glass fiber-1 in a side feeder; set the feeding zone temperature of the double screw extruder to 80°C, the melting zone temperature to 320°C, the mixing zone temperature to 330°C, and the dispersion zone temperature to 320°C; set the rotation speed of the double screw extruder to 350 RPM, and the total extrusion speed to 30 kg / h to perform modification and granulation, and obtain polyphenylene sulfide composition granules;

[0080] (3) Put the polyphenylene sulfide composition granules obtained in step (2) into an extrusion caster, set the cylinder temperature to 330°C, the roller temperature to 220°C, and the linear speed to 4.5 m / min to prepare a resin layer with a thickness of 1.6 mm;

[0081] (4) Stack the resin layer obtained in step (3) and a copper foil according to the order of copper foil layer-resin layer, then cover both sides with steel plates and kraft paper, and place them in a vacuum press, set the vacuum degree to 0.2 BarA, the hot table temperature to 300°C, the heating rate to 10°C / min, the pressure to 15 Mpa, and maintain for 30 min, then slowly cool to below 120°C, release the pressure, and take out to obtain a polyphenylene sulfide-based copper clad plate.

[0082] Example 4

[0083] A polyphenylene sulfide-based copper clad plate and a method for preparing the same, the specific implementation manner being the same as that of Example 1, except that modified glass fiber-1 is replaced by modified glass fiber-2.

[0084] Example 5

[0085] A polyphenylene sulfide-based copper clad plate and a method for preparing the same, the specific implementation manner being the same as that of Example 1, except that modified glass fiber-1 is replaced by modified glass fiber-3.

[0086] Comparative Example 1

[0087] A polyphenylene sulfide-based copper clad laminate and its preparation method are described. The specific implementation method is the same as in Example 1, except that polyethersulfone is not added.

[0088] Comparative Example 2

[0089] A polyphenylene sulfide-based copper clad laminate and its preparation method are described. The specific implementation method is the same as in Example 1, except that phenolphthalein-type polyarylether ketone is not added.

[0090] Performance testing

[0091] The test items and test methods are shown in Table 1:

[0092] Table 1

[0093]

[0094]

[0095] Table 2

[0096]

[0097] Table 3

[0098]

[0099]

[0100] As shown in Tables 2 and 3, the copper-clad laminates prepared in Examples 1-3 have good dielectric properties, excellent flame retardancy, and low water absorption. They can withstand three thermal shock tests with a 10-second tin-bleaching effect and a T260 > 30 min. Furthermore, due to their low coefficient of thermal expansion, they can be used in HDI processes with narrower line widths and spacings. A comparison of Example 4 and Example 1 shows that the introduction of trifluorovinyl ether can mitigate the negative effects of compatibilizer segments on the dielectric properties of glass fibers, while also improving the dielectric properties of the copper-clad laminate. A comparison of Example 5 and Example 1 shows that glass fibers using conventional grafted silane coupling agents cannot effectively increase the toughness of polyphenylene sulfide, and the phenomenon of board bursting still occurs. A comparison of Comparative Example 1 and Example 1 shows that although adding only phenolphthalein-type polyarylether ketone can promote the crosslinking of polyphenylene sulfide, giving it excellent water absorption and peel strength, its toughening effect is poor, and the phenomenon of board bursting still occurs. A comparison of Comparative Example 2 and Example 1 shows that adding only polyethersulfone has insufficient toughening effect and poor heat resistance, and the phenomenon of board bursting also occurs, indicating that phenolphthalein-type polyarylether ketone promotes the thermal oxidative crosslinking of polyphenylene sulfide.

[0101] The above embodiments are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the present application and implement it, and cannot limit the protection scope of the present application, and any equivalent changes or modifications made according to the spirit and principle of the present application shall be covered within the protection scope of the present application.

Claims

1. A polyphenylene sulfide-based copper clad laminate, characterized by, The resin layer comprises the following raw materials in parts by weight: polyphenylene sulfide resin 50-70 parts, phenolphthalein type polyaryletherketone 10-20 parts, polyether sulfone 2-4 parts, modified glass fiber 10-40 parts, inorganic filler 10-30 parts, toughening agent 1-3 parts, and flame retardant 3-10 parts. The preparation method of the modified glass fiber comprises the following steps: (1) adding silane coupling agent and 40-60% mass fraction of ethanol aqueous solution into a reaction kettle, then adding cleaned glass fiber, and then stirring at 50-80°C for 1-2h, and then drying after filtration to obtain pretreated glass fiber; (2) mixing the pretreated glass fiber obtained in step (1) with trifluorovinyl ether, glycidyl methacrylate, ethylene, octene, four kinds of monomers and toluene, adding benzoyl peroxide, and then reacting at 90-110°C for 4-5h, and then drying after filtration to obtain modified glass fiber; The silane coupling agent is vinyltriethoxysilane and / or vinyltrimethoxysilane.

2. The polyphenylene sulfide-based copper-clad plate according to claim 1, wherein The polyphenylene sulfide resin has a molecular weight Mw≥55000 and a chlorine element content ≤1200ppm.

3. The polyphenylene sulfide-based copper-clad plate according to claim 1, wherein The copper foil layer adopts low-roughness copper foil, and the thickness of the low-roughness copper foil is 12-36μm, and the surface roughness Rz of the bonding surface is 0.5-12μm.

4. The polyphenylene sulfide-based copper-clad plate according to claim 1, wherein The glass fiber is E glass fiber or LD glass fiber, and has a Dk of 4.0-6.6 and a single-filament diameter ≥10μm.

5. The polyphenylene sulfide-based copper-clad plate according to claim 1, wherein The weight ratio of the pretreated glass fiber, trifluorovinyl ether, glycidyl methacrylate, ethylene and octene is 9-11. 0.05-0.1:0.05-0.1:0.1-0.2:0.1-0.2。 6. The polyphenylene sulfide-based copper-clad plate according to claim 1, wherein The inorganic filler is one or more of magnesium oxide, zinc oxide, titanium dioxide, barium titanate, strontium titanate, barium strontium titanate, aluminum oxide, kaolin, talc, silica, hollow glass microspheres and boehmite.

7. The polyphenylene sulfide-based copper-clad plate according to claim 1, wherein The toughening agent is one or more of a terpolymer of ethylene, maleic anhydride and glycidyl methacrylate, a block copolymer of hydrogenated styrene, butadiene and styrene, and a terpolymer of ethylene, methyl acrylate and glycidyl methacrylate.

8. A method of producing a polyphenylene sulfide-based copper-clad plate according to any one of claims 1 to 7, characterized by, The method comprises the following steps: (1) placing polyphenylene sulfide resin, phenolphthalein type polyaryletherketone, polyether sulfone, inorganic filler, toughening agent and flame retardant into a high-speed mixer, setting the paddle rotation speed to 200-500r / min, and mixing for 5-8min to obtain premix; (2) placing the premix prepared in step (1) in a main feeder, placing modified glass fiber in a side feeder, setting the feeding zone temperature of a double-screw extruder to 50-80°C, the melting zone temperature to 300-320°C, the mixing zone temperature to 320-330°C, and the dispersion zone temperature to 300-320°C, setting the rotation speed of the double-screw extruder to 300-350RPM, and the total extrusion speed to 15-30kg / h to perform modification and granulation, and obtaining polyphenylene sulfide composition granules; (3) Put the polyphenylene sulfide composition pellets obtained in step (2) into an extrusion casting machine, set the cylinder temperature at 300-330°C, the roller temperature at 150-220°C, and the linear speed at 0.3-4.5 m / min, to obtain a resin layer with a thickness of 0.2 mm-1.6 mm; (4) Stack the resin layer obtained in step (3) and the copper foil according to copper foil layer-resin layer or copper foil layer-resin layer-copper foil layer, then cover both sides with steel plates and kraft paper, and put into a vacuum press, set the vacuum degree at 0.1-0.2 Bar A, the hot table temperature at 280-300°C, the heating rate at 8-10°C / min, the pressure at 5-15 Mpa, and the duration at 10-30 min, then slowly cool to below 120°C, release the pressure, and take out, to obtain a polyphenylene sulfide-based copper-clad plate.

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