WO2021026988A1 - Substrate material, preparation method for substrate material, and related substrates - Google Patents

Substrate material, preparation method for substrate material, and related substrates Download PDF

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Publication number
WO2021026988A1
WO2021026988A1 PCT/CN2019/104829 CN2019104829W WO2021026988A1 WO 2021026988 A1 WO2021026988 A1 WO 2021026988A1 CN 2019104829 W CN2019104829 W CN 2019104829W WO 2021026988 A1 WO2021026988 A1 WO 2021026988A1
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WIPO (PCT)
Prior art keywords
substrate material
coupling agent
ceramic
fluoropolymer
laminate
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PCT/CN2019/104829
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French (fr)
Chinese (zh)
Inventor
王和志
黄国创
恽振阳
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瑞声声学科技(深圳)有限公司
瑞声科技（南京）有限公司
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Publication of WO2021026988A1 publication Critical patent/WO2021026988A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards

Definitions

  • the present invention relates to the technical field of copper clad laminates, in particular to a substrate material and a preparation method of the substrate material, a laminate using the substrate material and the preparation method of the substrate material, a copper clad laminate and a printed circuit board.
  • Polytetrafluoroethylene (PTFE for short) has excellent dielectric properties (low dielectric constant and low dielectric loss), as well as good chemical and thermal stability, so PTFE copper clad laminates are used in satellite communications, Mobile radio communications, satellite radio and television radar equipment, and computers have potential application values.
  • the thermal expansion coefficient of pure PTFE is large, the specific value is 106 ppm/°C, which is quite different from the thermal expansion coefficient of copper (specific value is 16 ppm/°C), and direct copper coating is prone to thermal adaptation failure; in addition,
  • the thermal conductivity of pure polytetrafluoroethylene is low, the specific value is 0.20 ⁇ 0.25 W/mk; at the same time, pure polytetrafluoroethylene has poor fluidity and is difficult to mold, and it is easy to deform and crack due to large shrinkage during molding; and pure polytetrafluoroethylene Due to the extremely low surface energy of fluoroethylene, its adhesion ability is extremely poor; and pure PTFE has poor pressure resistance and low strength.
  • the purpose of the present invention is to provide a substrate material with good compatibility and uniform dispersibility of fluoropolymer and ceramic filler, low water absorption of substrate material, compact structure, good dielectric performance, simple process and low cost.
  • the present invention provides a substrate material, the substrate material includes a fluoropolymer and a ceramic filler material, the ceramic filler material is made of ceramic powder modified by a coupling agent, and the coupling agent includes Any one or more of silane coupling agent, titanate coupling agent and zirconate coupling agent.
  • the fluoropolymer includes any one or more of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and perfluoroalkyl vinyl ether.
  • the fluoropolymer is polytetrafluoroethylene.
  • the ceramic filling material includes any one or more of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide, and barium oxide.
  • the ceramic filler material is silica.
  • the ceramic filler material is fused amorphous silica.
  • the silane coupling agent includes dimethyldimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, methacryloylpropyltrimethoxysilane, 3-(2-amino Ethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -aminopropyltriethyl Oxysilane, p-chloromethylphenyltrimethoxysilane, aminoethylaminotrimethoxysilane, tridecafluorooctyltriethoxysilane, (3,3,3-trifluoropropyl)trichlorosilane , (3,3,3-trifluoropropyl)dimethylchlorosilane, (3,3,3-trifluoropropyl)
  • the coupling agent is dimethyldimethoxysilane.
  • the titanate coupling agent includes neopentyl(diallyl)oxytridecanoyl titanate, neopentyl(diallyl)oxytri(dodecyl)benzenesulfonyl titanium Any one or more of acid ester, neopentyl(diallyl)oxytris(dioctyl)phosphate titanate and isopropyl tris(dioctylpyrophosphate acyloxy) titanate.
  • the zirconate coupling agent includes neopentyl(diallyl)oxytris(dioctyl) zirconium pyrophosphate, neopentyl(diallyl)oxytris(N-ethylenediamine) Any one or more of ethyl zirconate.
  • the present invention also provides a laminate, which is made of the substrate material as described in any one of the above.
  • the present invention also provides a copper clad laminate.
  • the copper clad laminate includes at least one copper foil on one or both sides of the laminate as described above.
  • the present invention also provides a printed circuit board, which includes at least one laminate as described above.
  • the present invention also provides a method for preparing a substrate material.
  • the method includes the following steps:
  • the coupling agent is hydrolyzed. Mix 0.5 ⁇ 3 parts of water and 8 ⁇ 30 parts of absolute ethanol, drip into the pH adjusting solution and stir well, adjust the pH to 3 ⁇ 6, and then add 0.5-3 parts as claimed in claim 1. Or any one or more of the coupling agents from 7 to 10, adjust the temperature at 20 to 50 °C, and fully stir for 0.5 to 3 hours to obtain the coupling agent hydrolysate;
  • hydrophobic ceramic material For the preparation of hydrophobic ceramic material, add 40-60 parts of ceramic powder to the coupling agent hydrolysate, stir thoroughly for 0.5-2 hours and then put it in an ultrasonic cleaner for dispersion for 0.5-2 hours, remove the solvent to obtain hydrophobicity Ceramic material;
  • substrate material preparation For substrate material preparation, add 50-80 parts of fluoropolymer emulsion to the container and stir, and the system temperature is 20-50°C; slowly add 50-70 parts of the hydrophobic ceramic material to the fluoropolymer emulsion, Stir fully for 1 to 5 hours to obtain the substrate material.
  • the fluoropolymer is polytetrafluoroethylene.
  • the method further includes the following steps:
  • the film is sintered in a hot press, the sintering rate is 1 ⁇ 5°C/min, the holding temperature is 350 ⁇ 390°C, the holding time is 1 ⁇ 3 hours, and the temperature drop rate is 0.5 ⁇ 3°C/min;
  • the molded substrate material is sintered in a hot press, the sintering rate is 1 ⁇ 5°C/min, the holding temperature is 350 ⁇ 390°C, the holding time is 1 ⁇ 3 hours, and the temperature drop rate is 0.5 ⁇ 3°C/min;
  • the molded substrate material is sintered in a hot press, the sintering rate is 1 ⁇ 5°C/min, the holding temperature is 350 ⁇ 390°C, the holding time is 1 ⁇ 3 hours, and the temperature drop rate is 0.5 ⁇ 3°C/min;
  • the molded substrate material is sintered in a hot press, the sintering rate is 1 ⁇ 5°C/min, the holding temperature is 350 ⁇ 390°C, the holding time is 1 ⁇ 3 hours, and the temperature drop rate is 0.5 ⁇ 3
  • the present invention also provides a laminate, which is made of the substrate material preparation method described in any one of the above.
  • the present invention also provides a copper clad laminate.
  • the copper clad laminate includes at least one copper foil on one or both sides of the laminate as described above.
  • the present invention also provides a printed circuit board, which includes at least one laminate as described above.
  • the ceramic powder of the substrate material of the present invention is modified by a coupling agent to make the ceramic filling material, wherein the coupling agent includes a silane coupling agent, a titanate coupling agent, and zirconic acid Any one or more of the salt coupling agents are modified to increase the surface tension of the ceramic powder, so that the ceramic filling material has hydrophobicity.
  • the ceramic filler material is compounded with the fluoropolymer, so that the substrate material, the preparation method of the substrate material, the laminate and the copper clad laminate using the substrate material and the preparation method of the substrate material of the present invention
  • the fluoropolymer and ceramic filling material of the printed circuit board have good compatibility and uniform dispersion, low water absorption of the substrate material, compact structure, good dielectric performance, simple process and low cost.
  • Fig. 1 is a flow chart of a method for preparing a substrate material of the present invention
  • FIG. 2 is a flow chart of an embodiment of a method for preparing a substrate material of the present invention
  • step S1 of the method for preparing a substrate material of the present invention is a sub-flow block diagram of step S1 of the method for preparing a substrate material of the present invention
  • step S2 is a sub-flow block diagram of step S2 of the method for preparing a substrate material of the present invention
  • step S3 is a sub-flow block diagram of step S3 of the method for preparing a substrate material of the present invention
  • Figure 6 is a scanning electron microscope image of modified silica
  • Fig. 7 is a scanning electron microscope image of the substrate material of the present invention.
  • the present invention provides a substrate material.
  • the substrate material includes a fluoropolymer and a ceramic filler.
  • the ceramic filler is made of ceramic powder modified by a coupling agent.
  • the coupling agent includes a silane coupling agent, Any one or more of titanate coupling agent and zirconate coupling agent.
  • the fluoropolymer includes any one or more of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and perfluoroalkyl vinyl ether.
  • the fluoropolymer is polytetrafluoroethylene.
  • Polytetrafluoroethylene (PTFE for short) has excellent dielectric properties (low dielectric constant and low dielectric loss), as well as good chemical and thermal stability.
  • the thermal expansion coefficient of the fluoropolymer In order to reduce the thermal expansion coefficient of the fluoropolymer and increase its thermal conductivity, it is necessary to composite the fluoropolymer with ceramics.
  • the ceramic powder since the surface energy of the fluoropolymer is extremely low, and the ceramic powder often contains hydroxyl groups and has a high surface energy, it is necessary to modify the ceramic powder to reduce its surface energy and increase its hydrophobicity.
  • Most of the ceramic powders sold on the market are hydrophilic ceramics that are not modified by coupling agents; a small number of modified ceramics have either average modification effect, that is, average hydrophobicity, or lack of particle size or types of ceramic powder.
  • the sex effect and powder model are less optional; therefore, the ceramic powder needs to be modified with coupling agent.
  • the ceramic filling material is modified by the coupling agent to increase the surface tension of the ceramic powder and change it from hydrophilic to hydrophobic, thereby significantly reducing the water absorption rate of the substrate made of the substrate material.
  • the ceramic filling material includes any one or more of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide, and barium oxide.
  • the ceramic filler material is silicon dioxide.
  • the ceramic filler material is fused amorphous silica.
  • the ceramics used in the substrate material, including silicon dioxide, titanium dioxide and other ceramic powders, are usually hydrophilic materials.
  • the silane coupling agent includes dimethyldimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, methacryloylpropyltrimethoxysilane, 3-(2-aminoethylamino) )Propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane , P-chloromethylphenyltrimethoxysilane, aminoethylaminotrimethoxysilane, tridecafluorooctyltriethoxysilane, (3,3,3-trifluoropropyl)trichlorosilane, (3 ,3,3-Trifluoropropyl)dimethylchlorosilane, (3,3,3-trifluoropropyl)methyldich
  • the coupling agent is dimethyldimethoxysilane.
  • the cost of dimethyldimethoxysilane is lower, much lower than that of fluorine-containing silane coupling agents. Therefore, the cost of the substrate material is low.
  • the effect of dimethyldimethoxysilane on ceramic powder modification is comparable to that of fluorine-containing silane coupling agents.
  • the titanate coupling agent includes neopentyl(diallyl)oxytridecanoyl titanate, neopentyl(diallyl)oxytri(dodecyl)benzenesulfonyl titanate, Any one or more of neopentyl(diallyl)oxytris(dioctyl)phosphate titanate and isopropyl tris(dioctylpyrophosphate acyloxy) titanate.
  • the zirconate coupling agent includes neopentyl (diallyl) oxytris (dioctyl) zirconium pyrophosphate or neopentyl (diallyl) oxytris (N-ethylenediamine) ethyl zirconium Any one or more of acid salts.
  • the fluoropolymer and the ceramic powder are compounded, and then the fluoropolymer is allowed to fully encapsulate the ceramic powder, and the modified ceramic powder has a better effect in the fluoropolymer emulsion.
  • Good compatibility and uniform dispersibility, and the obtained ceramic-filled fluoropolymer produces the substrate material with uniform composition and compact structure.
  • the present invention also provides a laminate, which is made of the substrate material as described in any one of the above.
  • the present invention also provides a copper clad laminate.
  • the copper clad laminate includes at least one copper foil on one or both sides of the laminate as described above.
  • the present invention also provides a printed circuit board, which includes at least one laminate as described above.
  • FIG. 1 is a flow chart of a method for preparing a substrate material of the present invention
  • FIG. 2 is a flow chart of an embodiment of a method for preparing a substrate material of the present invention.
  • the present invention also provides a method for preparing a substrate material. The method includes the following steps:
  • the step S1 includes the following sub-steps:
  • step S11 0.5 to 3 parts of water and 8 to 30 parts of absolute ethanol are mixed as a solvent for hydrolysis of the silane coupling agent to provide hydroxyl groups for the hydrolysis of the silane coupling agent to generate silanol.
  • the pH adjusting solution is dropped and stirred sufficiently, and the dropping speed cannot be too high, otherwise it is easy to form a gel-like substance. Adjust the pH value to 3 ⁇ 6.
  • the hydrolysis process of the silane coupling agent is accompanied by the silanol Condensation reaction and adjusting the pH value can control the hydrolysis rate of the silane coupling agent to manipulate its dominant reaction. If the pH is too high or too low, the condensation rate of the silanol will be greater than the hydrolysis rate of the silane, or the hydrolysis rate is too slow, resulting in The concentration of silanol is too low, which will affect the modification effect
  • step S13 add 0.5-3 parts of the coupling agent as described in any one of the above, adjust the temperature at 20-50 °C, and fully stir for 0.5-3 hours to obtain the coupling agent hydrolyzate.
  • the silanol of the hydrolyzate The hydroxyl groups react with the hydroxyl groups on the surface of silica to improve the hydrophobic properties of silica. Temperature is a key factor in regulating the hydrolysis of the silane coupling agent. Too high a temperature will increase the condensation rate of silanol and form a gel core. Even precipitation occurs, and the temperature is too low, the hydrolysis reaction rate is too low.
  • Step S2 preparation of hydrophobic ceramic material
  • step S2 includes the following sub-steps:
  • step S21 40-60 parts of ceramic powder is added to the coupling agent hydrolyzate.
  • step S22 it is fully stirred for 0.5 to 2 hours and then placed in an ultrasonic cleaner for dispersion for 0.5 to 2 hours.
  • step S23 the solvent is removed to obtain a hydrophobic ceramic material.
  • step S3 includes the following sub-steps:
  • step S31 50-80 parts of fluoropolymer emulsion is added to the container and stirred, and the temperature of the system is 20-50°C.
  • step S32 50-70 parts of the hydrophobic ceramic material is slowly added to the fluoropolymer emulsion.
  • step S33 fully agitate for 1 to 5 hours to obtain the substrate material.
  • the fluoropolymer is polytetrafluoroethylene.
  • Step S4 making the substrate material into a film with a certain thickness in a film forming equipment.
  • Step S5. The film is sintered in a hot press.
  • the sintering temperature rise rate is 1 ⁇ 5°C/min
  • the holding temperature is 350 ⁇ 390°C
  • the holding time is 1 ⁇ 3 hours
  • the temperature drop rate is 0.5 ⁇ 3°C/min. Minutes; to obtain the molded substrate material.
  • the present invention also provides a laminate, which is made of the substrate material preparation method described in any one of the above.
  • the present invention also provides a copper clad laminate.
  • the copper clad laminate includes at least one copper foil on one or both sides of the laminate as described above.
  • the present invention also provides a printed circuit board, which includes at least one laminate as described above.
  • the substrate material includes 56.1 g of silicon dioxide and 73.2 g of polytetrafluoroethylene.
  • the preparation method of the copper clad laminate is as follows:
  • Copper-clad laminate preparation the mixture obtained above is formed into a film in a film-forming equipment to obtain a sheet of desired thickness, copper foil is attached to the upper and lower surfaces of the laminate, and the copper-clad laminate is obtained by hot pressing and sintering.
  • the substrate material includes 56.1 g of silicon dioxide, 73.2 g of polytetrafluoroethylene, and 1.0 g of dimethyl dimethoxysilane.
  • the preparation method of the copper clad laminate is as follows:
  • silica powder weigh 100g of silica powder, weigh 1.0g of dimethyldimethoxysilane as the coupling agent, add the silica powder and coupling agent to the mixture of deionized water and alcohol, ultrasonically treat and Stir for 3 hours.
  • the modified silica ceramic powder is obtained.
  • Copper-clad laminate preparation the mixture obtained above is formed into a film in a film-forming equipment to obtain a sheet of desired thickness, copper foil is attached to the upper and lower surfaces of the laminate, and the copper-clad laminate is obtained by hot pressing and sintering.
  • the substrate material includes 56.1 g of silicon dioxide, 73.2 g of polytetrafluoroethylene, and 1.0 g of phenyltrimethoxysilane.
  • the preparation method of the copper clad laminate is as follows:
  • silica powder weigh 100g of silica powder, weigh 1.0g of phenyltrimethoxysilane as coupling agent, add silica powder and coupling agent to the mixture of deionized water and alcohol, ultrasonically treat and stir 3 hour.
  • the modified silica ceramic powder is obtained.
  • Copper-clad laminate preparation the mixture obtained above is formed into a film in a film-forming equipment to obtain a sheet of desired thickness, copper foil is attached to the upper and lower surfaces of the laminate, and the copper-clad laminate is obtained by hot pressing and sintering.
  • the substrate material includes 56.1 g of silicon dioxide, 73.2 g of polytetrafluoroethylene, and 1.0 g of tridecafluorooctyl triethoxysilane.
  • the preparation method of the copper clad laminate is as follows:
  • silica powder weigh 100g of silica powder, weigh 1.0g of tridecafluorooctyltriethoxysilane as coupling agent, add silica powder and coupling agent to the mixture of deionized water and alcohol, ultrasonic Process and stir for 3 hours.
  • the modified silica ceramic powder is obtained.
  • Copper-clad laminate preparation the mixture obtained above is formed into a film in a film-forming equipment to obtain a sheet of desired thickness, copper foil is attached to the upper and lower surfaces of the laminate, and the copper-clad laminate is obtained by hot pressing and sintering.
  • Example 1 and Example 2-4 have the same parts by weight of silicon dioxide and the same parts by weight of polytetrafluoroethylene, so the test data, the dielectric constant and dielectric loss data of Examples 1-4 indicate the substrate material of the present invention And copper clad laminates have excellent dielectric properties.
  • Example 2-4 has different silane coupling agents to modify its ceramic powder compared to Example 1, so that the powder contact angle parameters of Example 2-4 are 140°, 123° and 143°, respectively.
  • the water absorption rates are respectively 0.02, 0.04 and 0.02, indicating that the ceramic powders of the substrate materials of the present invention in Examples 2-4 have low water absorption rates. Since Example 1 does not contain a silane coupling agent, the contact angle parameter of the substrate material powder shows hydrophilicity, and the water absorption rate of 0.24 is much greater than that of Example 2-4.
  • the ceramic powder of the present invention is modified by a silane coupling agent, the surface tension is improved, the hydrophilicity is changed to the hydrophobicity, the substrate material and the copper-clad laminate have excellent dielectric properties and low water absorption.
  • a silane coupling agent dimethyldimethoxysilane and tridecafluorooctyltriethoxysilane have the best modification effects, and phenyltrimethoxysilane has relatively general modification effects. From the perspective of dimethyldimethoxysilane and phenyltrimethoxysilane, the cost is the lowest, and the cost of tridecafluorooctyltriethoxysilane is the highest. Therefore, from the perspective of cost performance, dimethyldimethoxysilane is compared It is suitable as a modified coupling agent for silica.
  • Titanate coupling agents and zirconate coupling agents are also a class of materials containing bifunctional groups, including organic functional groups and hydrolysis functional groups.
  • the titanate coupling agent and zirconate coupling agent generate hydroxyl-containing compounds during the hydrolysis process, which can interact with the surface of silica, titanium dioxide, aluminum oxide and other particles to partially coat organic functional groups On the outer surface of the particles, thereby improving the dispersion and hydrophobicity of the particles in the system, improving the mixing effect of PTFE and ceramic particles, and ultimately enhancing the mechanical properties of the composite material, improving the dielectric properties, and reducing water absorption.
  • FIG. 6 is a scanning electron microscope image of the modified silica
  • FIG. 7 is a scanning electron microscope image of the substrate material of the present invention. It can be seen from the figure that the fluoropolymer and ceramic filler of the substrate material of the present invention have good compatibility and uniform dispersion, and the substrate material has a uniform composition and a dense structure.
  • the ceramic powder of the substrate material of the present invention is modified by a coupling agent to make the ceramic filling material, wherein the coupling agent includes a silane coupling agent, a titanate coupling agent, and zirconic acid Any one or more of the salt coupling agents are modified to increase the surface tension of the ceramic powder, so that the ceramic filling material has hydrophobicity.
  • the ceramic filler material is compounded with the fluoropolymer, so that the substrate material, the preparation method of the substrate material, the laminate and the copper clad laminate using the substrate material and the preparation method of the substrate material of the present invention
  • the fluoropolymer and ceramic filling material of the printed circuit board have good compatibility and uniform dispersion, low water absorption of the substrate material, compact structure, good dielectric performance, simple process and low cost.

Abstract

Provided in the present invention is a substrate material. The substrate material comprises a fluoropolymer and a ceramic filling material, wherein the ceramic filling material is prepared by modifying a ceramic powder by means of a coupling agent, and the coupling agent comprises any one or more of a silane coupling agent, a titanate coupling agent and a zirconate coupling agent. Further provided in the present invention are a preparation method for the substrate material, and a laminated board, a copper-clad laminated board and a printed circuit board which use the substrate material and apply the preparation method for the substrate material. Compared with the prior art, the fluoropolymer and ceramic filling material of the substrate material, the preparation method for the substrate material, the laminated board, the copper-clad laminated board and the printed circuit board of the present invention have a good compatibility and a uniform dispersity, and the substrate material has a low water absorption rate, a compact structure, a good dielectric property, a simple process and a low cost.

Description

基板材料、基板材料制备方法及相关基板Substrate material, substrate material preparation method and related substrate 技术领域Technical field
本发明涉及覆铜板技术领域，尤其涉及一种基板材料和基板材料制备方法及使用所述基板材料和应用所述基板材料制备方法的层压板、覆铜箔层压板以及印制电路板。The present invention relates to the technical field of copper clad laminates, in particular to a substrate material and a preparation method of the substrate material, a laminate using the substrate material and the preparation method of the substrate material, a copper clad laminate and a printed circuit board.
背景技术Background technique
随着5G时代的来临，电子产品的发展趋向多功能化，零部件不断向轻、薄、短、小等方向发展，尤其是高密度集成电路技术的广泛应用，对民用电子产品提出高性能化、高可靠性和高安全性的要求；对工业用电子产品提出技术性能良好、低成本、高能耗的要求。然而，传统的无机基板介电常数高，影响信号传输速度和响应时间。纯有机基板的热膨胀系数高、热导率低、热稳定性差。因此，急需一种介电、力学、热学等性能均优异的材料来满足高传速低延时的集成电路的要求。With the advent of the 5G era, the development of electronic products tends to be multi-functional, and parts and components continue to develop in the direction of light, thin, short, and small, especially the wide application of high-density integrated circuit technology, which proposes high performance for civilian electronic products , High reliability and high safety requirements; high technical performance, low cost and high energy consumption requirements are put forward for industrial electronic products. However, traditional inorganic substrates have a high dielectric constant, which affects signal transmission speed and response time. Pure organic substrates have high thermal expansion coefficient, low thermal conductivity and poor thermal stability. Therefore, there is an urgent need for a material with excellent dielectric, mechanical, thermal and other properties to meet the requirements of integrated circuits with high transmission speed and low delay.
聚四氟乙烯(Polytetrafluoroethylene，简称PTFE)具有优秀的介电性能（低介电常数和低介电损耗），以及良好的化学稳定性和热稳定性，所以聚四氟乙烯覆铜板在卫星通讯、移动无线电通讯、卫星广播电视雷达设备以及计算机等领域具有潜在的应用价值。Polytetrafluoroethylene (PTFE for short) has excellent dielectric properties (low dielectric constant and low dielectric loss), as well as good chemical and thermal stability, so PTFE copper clad laminates are used in satellite communications, Mobile radio communications, satellite radio and television radar equipment, and computers have potential application values.
技术问题technical problem
但是，纯聚四氟乙烯的热膨胀系数大，具体值为106 ppm/℃，与铜(具体值为16 ppm/℃)的热膨胀系数相差较大，直接覆铜容易发生热适配失效；另外，纯聚四氟乙烯的热导率低，具体值为0.20~0.25 W/mk；同时纯聚四氟乙烯的流动性差，难以成型，成型时由于大的收缩率易导致变形开裂；而且纯聚四氟乙烯由于表面能极低，导致其附着能力极差；还有纯聚四氟乙烯的抗压能力差，强度不高等。However, the thermal expansion coefficient of pure PTFE is large, the specific value is 106 ppm/℃, which is quite different from the thermal expansion coefficient of copper (specific value is 16 ppm/℃), and direct copper coating is prone to thermal adaptation failure; in addition, The thermal conductivity of pure polytetrafluoroethylene is low, the specific value is 0.20~0.25 W/mk; at the same time, pure polytetrafluoroethylene has poor fluidity and is difficult to mold, and it is easy to deform and crack due to large shrinkage during molding; and pure polytetrafluoroethylene Due to the extremely low surface energy of fluoroethylene, its adhesion ability is extremely poor; and pure PTFE has poor pressure resistance and low strength.
因此，实有必要提供一种新的基板材料、制备方法及相关基板解决上述技术问题。Therefore, it is necessary to provide a new substrate material, preparation method and related substrate to solve the above technical problems.
技术解决方案Technical solutions
本发明的目的在于提供一种具有氟聚合物和陶瓷填充材料相容性较好且均匀分散性、基板材料吸水率低且结构致密、介电性能好、工艺简单且成本较低的基板材料、基板材料制备方法、层压板、覆铜箔层压板以及印制电路板。The purpose of the present invention is to provide a substrate material with good compatibility and uniform dispersibility of fluoropolymer and ceramic filler, low water absorption of substrate material, compact structure, good dielectric performance, simple process and low cost. Substrate material preparation method, laminate, copper clad laminate and printed circuit board.
为达到上述目的，本发明提供了一种基板材料，所述基板材料包括氟聚合物和陶瓷填充材料，所述陶瓷填充材料由陶瓷粉末通过偶联剂改性制成，所述偶联剂包括硅烷偶联剂、钛酸盐偶联剂及锆酸盐偶联剂中的任意一种或多种。To achieve the above object, the present invention provides a substrate material, the substrate material includes a fluoropolymer and a ceramic filler material, the ceramic filler material is made of ceramic powder modified by a coupling agent, and the coupling agent includes Any one or more of silane coupling agent, titanate coupling agent and zirconate coupling agent.
优选的，所述氟聚合物包括聚四氟乙烯、六氟丙烯、四氟乙烯以及全氟烷基乙烯基醚中任意一种或多种。Preferably, the fluoropolymer includes any one or more of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and perfluoroalkyl vinyl ether.
优选的，所述氟聚合物为聚四氟乙烯。Preferably, the fluoropolymer is polytetrafluoroethylene.
优选的，所述陶瓷填充材料包括二氧化硅、二氧化钛、三氧化二铝、氮化铝、氧化镁、氧化钙、氧化锌以及氧化钡中的任意一种或多种。Preferably, the ceramic filling material includes any one or more of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide, and barium oxide.
优选的，所述陶瓷填充材料为二氧化硅。Preferably, the ceramic filler material is silica.
优选的，所述陶瓷填充材料为熔融无定形二氧化硅。Preferably, the ceramic filler material is fused amorphous silica.
优选的，所述硅烷偶联剂包括二甲基二甲氧基硅烷、苯基三甲氧基硅烷、乙烯基三甲氧基硅烷、甲基丙烯酰基丙基三甲氧基硅烷、3-(2-氨基乙基氨基)丙基三甲氧基硅烷、 3-(2-氨基乙氨基)丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、对氯甲基苯基三甲氧基硅烷、氨基乙基氨基三甲氧基硅烷、十三氟辛基三乙氧基硅烷、(3,3,3-三氟丙基)三氯硅烷、(3,3,3-三氟丙基)二甲基氯硅烷、(3,3,3-三氟丙基)甲基二氯硅烷、 (3,3,3-三氟丙基)甲基二甲氧基硅烷、 (三氟-1,1,2,2-四氢）辛基)-1-三氯硅烷、 (三氟-1,1,2,2-四氢辛基)-1-甲基二氯硅烷、 (三氟-1,1,2,2-四氢辛基)-1-二甲基氯硅烷、 (庚氟-1,1,2,2-四氢癸基)-1-甲基二氯硅烷、 (庚氟-1,1,2,2-四氢癸基)-1-三氯硅烷、 (庚二氟-1,1,2)2-(2-四氢癸基)-1-二甲氧基氯硅烷(庚氟异丙氧基)丙基甲基二氯硅烷、 3-(庚氟异丙氧基)丙基三氯硅烷以及 3-(庚氟异丙氧基)丙基三乙氧基硅烷中的任意一种或多种。Preferably, the silane coupling agent includes dimethyldimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, methacryloylpropyltrimethoxysilane, 3-(2-amino Ethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethyl Oxysilane, p-chloromethylphenyltrimethoxysilane, aminoethylaminotrimethoxysilane, tridecafluorooctyltriethoxysilane, (3,3,3-trifluoropropyl)trichlorosilane , (3,3,3-trifluoropropyl)dimethylchlorosilane, (3,3,3-trifluoropropyl)methyldichlorosilane, (3,3,3-trifluoropropyl)methyl Dimethoxysilane, (trifluoro-1,1,2,2-tetrahydro)octyl)-1-trichlorosilane, (trifluoro-1,1,2,2-tetrahydrooctyl)- 1-methyldichlorosilane, (trifluoro-1,1,2,2-tetrahydrooctyl)-1-dimethylchlorosilane, (heptafluoro-1,1,2,2-tetrahydrodecyl )-1-methyldichlorosilane, (heptafluoro-1,1,2,2-tetrahydrodecyl)-1-trichlorosilane, (heptafluoro-1,1,2)2-(2- Tetrahydrodecyl)-1-dimethoxychlorosilane (heptafluoroisopropoxy) propylmethyldichlorosilane, 3-(heptafluoroisopropoxy) propyltrichlorosilane and 3-(hepta Any one or more of fluoroisopropoxy)propyltriethoxysilane.
优选的，所述偶联剂为二甲基二甲氧基硅烷。Preferably, the coupling agent is dimethyldimethoxysilane.
优选的，所述钛酸盐偶联剂包括新戊基(二烯丙基)氧基三癸酰基钛酸酯、新戊(二烯丙基)氧三(十二烷基)苯磺酰基钛酸酯、新戊基(二烯丙基)氧三(二辛基)磷酸钛酸酯以及异丙基三(二辛基焦磷酸酰氧基)钛酸酯中的任意一种或多种。Preferably, the titanate coupling agent includes neopentyl(diallyl)oxytridecanoyl titanate, neopentyl(diallyl)oxytri(dodecyl)benzenesulfonyl titanium Any one or more of acid ester, neopentyl(diallyl)oxytris(dioctyl)phosphate titanate and isopropyl tris(dioctylpyrophosphate acyloxy) titanate.
优选的，所述锆酸盐偶联剂包括新戊基(二烯丙基)氧三(二辛基)焦磷酸锆、新戊基(二烯丙基)氧三(N-乙二胺)乙基锆酸盐的任意一种或多种。Preferably, the zirconate coupling agent includes neopentyl(diallyl)oxytris(dioctyl) zirconium pyrophosphate, neopentyl(diallyl)oxytris(N-ethylenediamine) Any one or more of ethyl zirconate.
本发明还提供一种层压板，所述层压板由如上中的任意一项所述的基板材料制成。The present invention also provides a laminate, which is made of the substrate material as described in any one of the above.
本发明还提供一种覆铜箔层压板，所述覆铜箔层压板包括至少一张如上所述的层压板的一侧或两侧的铜箔。The present invention also provides a copper clad laminate. The copper clad laminate includes at least one copper foil on one or both sides of the laminate as described above.
本发明还提供一种印制电路板，所述印制电路板包括至少一张如上所述的层压板。The present invention also provides a printed circuit board, which includes at least one laminate as described above.
本发明还提供一种基板材料制备方法，该方法包括如下步骤：The present invention also provides a method for preparing a substrate material. The method includes the following steps:
偶联剂水解，将0.5~3份的水和8~30份的无水乙醇混合，滴入pH调节液并充分搅拌，调节pH值至3~6，再加入0.5-3份如权利要求1或7~10中的任意一种或多种所述的偶联剂，调节温度在20~50 ℃，充分搅拌0.5~3小时，得到偶联剂水解液；The coupling agent is hydrolyzed. Mix 0.5~3 parts of water and 8~30 parts of absolute ethanol, drip into the pH adjusting solution and stir well, adjust the pH to 3~6, and then add 0.5-3 parts as claimed in claim 1. Or any one or more of the coupling agents from 7 to 10, adjust the temperature at 20 to 50 ℃, and fully stir for 0.5 to 3 hours to obtain the coupling agent hydrolysate;
疏水性陶瓷材料制备，将40~60份的陶瓷粉末加入所述偶联剂水解液中，充分搅拌0.5~2小时后放入至超声清洗器中进行分散0.5~2小时，除去溶剂得到疏水性陶瓷材料；For the preparation of hydrophobic ceramic material, add 40-60 parts of ceramic powder to the coupling agent hydrolysate, stir thoroughly for 0.5-2 hours and then put it in an ultrasonic cleaner for dispersion for 0.5-2 hours, remove the solvent to obtain hydrophobicity Ceramic material;
基板材料制备，将50~80份的氟聚合物乳液加入容器中搅拌，其体系温度为20~50℃；将50-70份的所述疏水性陶瓷材料缓慢加入所述氟聚合物乳液中，充分搅拌1~5小时，得到所述基板材料。For substrate material preparation, add 50-80 parts of fluoropolymer emulsion to the container and stir, and the system temperature is 20-50°C; slowly add 50-70 parts of the hydrophobic ceramic material to the fluoropolymer emulsion, Stir fully for 1 to 5 hours to obtain the substrate material.
优选的，所述氟聚合物为聚四氟乙烯。Preferably, the fluoropolymer is polytetrafluoroethylene.
优选的，所述基板材料制备步骤之后，还包括如下步骤：Preferably, after the substrate material preparation step, the method further includes the following steps:
将所述基板材料在成膜设备中制成一定厚度的薄膜；Making the substrate material into a film with a certain thickness in a film forming device;
将所述薄膜在热压机中烧结，烧结的升温速率为1~5 ℃/分钟，保温温度为350~390℃，保温时间为1~3 小时，降温速度为0.5~3℃/分钟；得到成型的所述基板材料。The film is sintered in a hot press, the sintering rate is 1~5°C/min, the holding temperature is 350~390°C, the holding time is 1~3 hours, and the temperature drop rate is 0.5~3°C/min; The molded substrate material.
本发明还提供一种层压板，所述层压板由如上中的任意一项所述的基板材料制备方法制成。The present invention also provides a laminate, which is made of the substrate material preparation method described in any one of the above.
本发明还提供一种覆铜箔层压板，所述覆铜箔层压板包括至少一张如上所述的层压板的一侧或两侧的铜箔。The present invention also provides a copper clad laminate. The copper clad laminate includes at least one copper foil on one or both sides of the laminate as described above.
本发明还提供一种印制电路板，所述印制电路板包括至少一张如上所述的层压板。The present invention also provides a printed circuit board, which includes at least one laminate as described above.
有益效果Beneficial effect
与相关技术相比，本发明的基板材料的陶瓷粉末通过偶联剂改性制成所述陶瓷填充材料，其中，所述偶联剂包括硅烷偶联剂、钛酸盐偶联剂及锆酸盐偶联剂中的任意一种或多种，通过改性，提高了陶瓷粉末的表面张力，从而使所述陶瓷填充材料具有疏水性。再将所述陶瓷填充材料与氟聚合物复合，从而使本发明的所述基板材料、基板材料制备方法及使用所述基板材料和应用所述基板材料制备方法的层压板、覆铜箔层压板以及印制电路板的氟聚合物和陶瓷填充材料相容性较好且均匀分散性、基板材料吸水率低且结构致密、介电性能好，工艺简单且成本较低。Compared with the related art, the ceramic powder of the substrate material of the present invention is modified by a coupling agent to make the ceramic filling material, wherein the coupling agent includes a silane coupling agent, a titanate coupling agent, and zirconic acid Any one or more of the salt coupling agents are modified to increase the surface tension of the ceramic powder, so that the ceramic filling material has hydrophobicity. The ceramic filler material is compounded with the fluoropolymer, so that the substrate material, the preparation method of the substrate material, the laminate and the copper clad laminate using the substrate material and the preparation method of the substrate material of the present invention And the fluoropolymer and ceramic filling material of the printed circuit board have good compatibility and uniform dispersion, low water absorption of the substrate material, compact structure, good dielectric performance, simple process and low cost.
附图说明Description of the drawings
为了更清楚地说明本实用新型实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本实用新型的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图，其中：In order to more clearly describe the technical solutions in the embodiments of the present utility model, the following will briefly introduce the drawings needed in the description of the embodiments. Obviously, the drawings in the following description are only some implementations of the present utility model. For example, for those of ordinary skill in the art, without creative work, other drawings can be obtained based on these drawings, among which:
图1为本发明的基板材料制备方法的流程框图；Fig. 1 is a flow chart of a method for preparing a substrate material of the present invention;
图2为本发明的基板材料制备方法的实施例的流程框图；2 is a flow chart of an embodiment of a method for preparing a substrate material of the present invention;
图3为本发明的基板材料制备方法的步骤S1的子流程框图；3 is a sub-flow block diagram of step S1 of the method for preparing a substrate material of the present invention;
图4为本发明的基板材料制备方法的步骤S2的子流程框图；4 is a sub-flow block diagram of step S2 of the method for preparing a substrate material of the present invention;
图5为本发明的基板材料制备方法的步骤S3的子流程框图；5 is a sub-flow block diagram of step S3 of the method for preparing a substrate material of the present invention;
图6为改性的二氧化硅的扫描电子显微镜图；Figure 6 is a scanning electron microscope image of modified silica;
图7为本发明的基板材料的扫描电子显微镜图。Fig. 7 is a scanning electron microscope image of the substrate material of the present invention.
本发明的实施方式Embodiments of the invention
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
本发明提供了一种基板材料，所述基板材料包括氟聚合物和陶瓷填充材料，所述陶瓷填充材料由陶瓷粉末通过偶联剂改性制成，所述偶联剂包括硅烷偶联剂、钛酸盐偶联剂及锆酸盐偶联剂中的任意一种或多种。The present invention provides a substrate material. The substrate material includes a fluoropolymer and a ceramic filler. The ceramic filler is made of ceramic powder modified by a coupling agent. The coupling agent includes a silane coupling agent, Any one or more of titanate coupling agent and zirconate coupling agent.
所述氟聚合物包括聚四氟乙烯、六氟丙烯、四氟乙烯以及全氟烷基乙烯基醚中任意一种或多种。The fluoropolymer includes any one or more of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and perfluoroalkyl vinyl ether.
所述氟聚合物为聚四氟乙烯。聚四氟乙烯(Polytetrafluoroethylene，简称PTFE)具有优秀的介电性能（低介电常数和低介电损耗），以及良好的化学稳定性和热稳定性。The fluoropolymer is polytetrafluoroethylene. Polytetrafluoroethylene (PTFE for short) has excellent dielectric properties (low dielectric constant and low dielectric loss), as well as good chemical and thermal stability.
为了降低所述氟聚合物的热膨胀系数，提高其热导率，需要将所述氟聚合物与陶瓷做复合。但是由于，所述氟聚合物表面能极低，而陶瓷粉末往往含有羟基，表面能较高，因此需要对陶瓷粉末做改性处理，降低其表面能，增加其疏水性。市面上出售的陶瓷粉末大多是不经过偶联剂改性的，属亲水性陶瓷；少部分改性陶瓷，要么改性效果一般，即疏水性一般，要么颗粒尺寸或者陶瓷粉末种类匮乏，改性效果及粉末型号的可选性较少；因此需要对陶瓷粉末做偶联剂的改性。所述陶瓷填充材料通过所述偶联剂进行改性，提高陶瓷粉末的表面张力，使其由亲水性变为疏水性，明显降低所述基板材料制成的基板的吸水率。In order to reduce the thermal expansion coefficient of the fluoropolymer and increase its thermal conductivity, it is necessary to composite the fluoropolymer with ceramics. However, since the surface energy of the fluoropolymer is extremely low, and the ceramic powder often contains hydroxyl groups and has a high surface energy, it is necessary to modify the ceramic powder to reduce its surface energy and increase its hydrophobicity. Most of the ceramic powders sold on the market are hydrophilic ceramics that are not modified by coupling agents; a small number of modified ceramics have either average modification effect, that is, average hydrophobicity, or lack of particle size or types of ceramic powder. The sex effect and powder model are less optional; therefore, the ceramic powder needs to be modified with coupling agent. The ceramic filling material is modified by the coupling agent to increase the surface tension of the ceramic powder and change it from hydrophilic to hydrophobic, thereby significantly reducing the water absorption rate of the substrate made of the substrate material.
所述陶瓷填充材料包括二氧化硅、二氧化钛、三氧化二铝、氮化铝、氧化镁、氧化钙、氧化锌以及氧化钡中的任意一种或多种。The ceramic filling material includes any one or more of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide, and barium oxide.
所述陶瓷填充材料为二氧化硅。优选的，所述陶瓷填充材料为熔融无定形二氧化硅。所述基板材料所用的陶瓷，包括二氧化硅、二氧化钛以及其他陶瓷粉末通常为亲水性材料。The ceramic filler material is silicon dioxide. Preferably, the ceramic filler material is fused amorphous silica. The ceramics used in the substrate material, including silicon dioxide, titanium dioxide and other ceramic powders, are usually hydrophilic materials.
所述硅烷偶联剂包括二甲基二甲氧基硅烷、苯基三甲氧基硅烷、乙烯基三甲氧基硅烷、甲基丙烯酰基丙基三甲氧基硅烷、3-(2-氨基乙基氨基)丙基三甲氧基硅烷、 3-(2-氨基乙氨基)丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、对氯甲基苯基三甲氧基硅烷、氨基乙基氨基三甲氧基硅烷、十三氟辛基三乙氧基硅烷、(3,3,3-三氟丙基)三氯硅烷、(3,3,3-三氟丙基)二甲基氯硅烷、(3,3,3-三氟丙基)甲基二氯硅烷、 (3,3,3-三氟丙基)甲基二甲氧基硅烷、 (三氟-1,1,2,2-四氢）辛基)-1-三氯硅烷、 (三氟-1,1,2,2-四氢辛基)-1-甲基二氯硅烷、 (三氟-1,1,2,2-四氢辛基)-1-二甲基氯硅烷、 (庚氟-1,1,2,2-四氢癸基)-1-甲基二氯硅烷、 (庚氟-1,1,2,2-四氢癸基)-1-三氯硅烷、 (庚二氟-1,1,2)2-(2-四氢癸基)-1-二甲氧基氯硅烷(庚氟异丙氧基)丙基甲基二氯硅烷、 3-(庚氟异丙氧基)丙基三氯硅烷以及 3-(庚氟异丙氧基)丙基三乙氧基硅烷中的任意一种或多种。The silane coupling agent includes dimethyldimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, methacryloylpropyltrimethoxysilane, 3-(2-aminoethylamino) )Propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane , P-chloromethylphenyltrimethoxysilane, aminoethylaminotrimethoxysilane, tridecafluorooctyltriethoxysilane, (3,3,3-trifluoropropyl)trichlorosilane, (3 ,3,3-Trifluoropropyl)dimethylchlorosilane, (3,3,3-trifluoropropyl)methyldichlorosilane, (3,3,3-trifluoropropyl)methyldimethyl Oxysilane, (trifluoro-1,1,2,2-tetrahydro)octyl)-1-trichlorosilane, (trifluoro-1,1,2,2-tetrahydrooctyl)-1-methyl Dichlorosilane, (trifluoro-1,1,2,2-tetrahydrooctyl)-1-dimethylchlorosilane, (heptafluoro-1,1,2,2-tetrahydrodecyl)-1 -Methyldichlorosilane, (heptafluoro-1,1,2,2-tetrahydrodecyl)-1-trichlorosilane, (heptafluoro-1,1,2)2-(2-tetrahydrodecyl) Yl)-1-dimethoxychlorosilane (heptafluoroisopropoxy) propylmethyldichlorosilane, 3-(heptafluoroisopropoxy) propyltrichlorosilane and 3-(heptafluoroisopropoxy) Any one or more of oxy)propyltriethoxysilane.
所述偶联剂为二甲基二甲氧基硅烷。二甲基二甲氧基硅烷的成本较低，远低于含氟类硅烷偶联剂。所以，所述基板材料成本较低。二甲基二甲氧基硅烷对陶瓷粉改性的效果可以媲美于含氟类硅烷偶联剂。The coupling agent is dimethyldimethoxysilane. The cost of dimethyldimethoxysilane is lower, much lower than that of fluorine-containing silane coupling agents. Therefore, the cost of the substrate material is low. The effect of dimethyldimethoxysilane on ceramic powder modification is comparable to that of fluorine-containing silane coupling agents.
所述钛酸盐偶联剂包括新戊基(二烯丙基)氧基三癸酰基钛酸酯、新戊(二烯丙基)氧三(十二烷基)苯磺酰基钛酸酯、新戊基(二烯丙基)氧三(二辛基)磷酸钛酸酯以及异丙基三(二辛基焦磷酸酰氧基)钛酸酯中的任意一种或多种。The titanate coupling agent includes neopentyl(diallyl)oxytridecanoyl titanate, neopentyl(diallyl)oxytri(dodecyl)benzenesulfonyl titanate, Any one or more of neopentyl(diallyl)oxytris(dioctyl)phosphate titanate and isopropyl tris(dioctylpyrophosphate acyloxy) titanate.
所述锆酸盐偶联剂包括新戊基(二烯丙基)氧三(二辛基)焦磷酸锆或新戊基(二烯丙基)氧三(N-乙二胺)乙基锆酸盐的任意一种或多种。The zirconate coupling agent includes neopentyl (diallyl) oxytris (dioctyl) zirconium pyrophosphate or neopentyl (diallyl) oxytris (N-ethylenediamine) ethyl zirconium Any one or more of acid salts.
综合上述,将所述氟聚合物与所述陶瓷粉末进行复合，再使所述氟聚合物将所述陶瓷粉末进行充分包裹，改性的所述陶瓷粉末在所述氟聚合物乳液中具有较好的相容性和均匀分散性，得到的所述陶瓷填充的所述氟聚合物生成的所述基板材料成分均匀且结构致密。In summary, the fluoropolymer and the ceramic powder are compounded, and then the fluoropolymer is allowed to fully encapsulate the ceramic powder, and the modified ceramic powder has a better effect in the fluoropolymer emulsion. Good compatibility and uniform dispersibility, and the obtained ceramic-filled fluoropolymer produces the substrate material with uniform composition and compact structure.
本发明还提供一种层压板，所述层压板由如上中的任意一项所述的基板材料制成。The present invention also provides a laminate, which is made of the substrate material as described in any one of the above.
本发明还提供一种覆铜箔层压板，所述覆铜箔层压板包括至少一张如上所述的层压板的一侧或两侧的铜箔。The present invention also provides a copper clad laminate. The copper clad laminate includes at least one copper foil on one or both sides of the laminate as described above.
本发明还提供一种印制电路板，所述印制电路板包括至少一张如上所述的层压板。The present invention also provides a printed circuit board, which includes at least one laminate as described above.
请参阅图1-2，图1为本发明的基板材料制备方法的流程框图；图2为本发明的基板材料制备方法的实施例的流程框图。本发明还提供一种基板材料制备方法，该方法包括如下步骤：Please refer to FIGS. 1-2. FIG. 1 is a flow chart of a method for preparing a substrate material of the present invention; FIG. 2 is a flow chart of an embodiment of a method for preparing a substrate material of the present invention. The present invention also provides a method for preparing a substrate material. The method includes the following steps:
步骤S1、偶联剂水解Step S1, coupling agent hydrolysis
请参阅图3，所述步骤S1包括如下子步骤：Please refer to Figure 3. The step S1 includes the following sub-steps:
所述步骤S11、将0.5~3份的水和8~30份的无水乙醇混合，作为硅烷偶联剂水解的溶剂，为硅烷偶联剂的水解提供羟基，生成硅醇。In step S11, 0.5 to 3 parts of water and 8 to 30 parts of absolute ethanol are mixed as a solvent for hydrolysis of the silane coupling agent to provide hydroxyl groups for the hydrolysis of the silane coupling agent to generate silanol.
所述步骤S12、滴入pH调节液并充分搅拌，滴入速度不能过大，否则易生成凝胶状物质，调节pH值至3~6，硅烷偶联剂的水解过程中伴随着硅醇的缩合反应，调节pH值，可以控制硅烷偶联剂的水解速度，从而操纵其主导反应，pH过高或者过低，会使硅醇的缩合速度大于硅烷的水解速度，或者水解速度过慢，导致硅醇的浓度过低，影响改性效果In the step S12, the pH adjusting solution is dropped and stirred sufficiently, and the dropping speed cannot be too high, otherwise it is easy to form a gel-like substance. Adjust the pH value to 3~6. The hydrolysis process of the silane coupling agent is accompanied by the silanol Condensation reaction and adjusting the pH value can control the hydrolysis rate of the silane coupling agent to manipulate its dominant reaction. If the pH is too high or too low, the condensation rate of the silanol will be greater than the hydrolysis rate of the silane, or the hydrolysis rate is too slow, resulting in The concentration of silanol is too low, which will affect the modification effect
所述步骤S13、再加入0.5-3份如上任意一项所述的偶联剂，调节温度在20~50 ℃，充分搅拌0.5~3小时，得到偶联剂水解液，该水解液的硅醇羟基与二氧化硅表面的羟基发生反应，从而改善二氧化硅的疏水性能，温度是调节硅烷偶联剂的水解的关键因素，温度过高会使硅醇的缩合速度增大，形成胶核，甚至出现沉淀，温度过低，则水解反应速率过低。In the step S13, add 0.5-3 parts of the coupling agent as described in any one of the above, adjust the temperature at 20-50 ℃, and fully stir for 0.5-3 hours to obtain the coupling agent hydrolyzate. The silanol of the hydrolyzate The hydroxyl groups react with the hydroxyl groups on the surface of silica to improve the hydrophobic properties of silica. Temperature is a key factor in regulating the hydrolysis of the silane coupling agent. Too high a temperature will increase the condensation rate of silanol and form a gel core. Even precipitation occurs, and the temperature is too low, the hydrolysis reaction rate is too low.
步骤S2、疏水性陶瓷材料制备Step S2, preparation of hydrophobic ceramic material
请参阅图4，所述步骤S2包括如下子步骤：Please refer to FIG. 4, the step S2 includes the following sub-steps:
所述步骤S21、将40~60份的陶瓷粉末加入所述偶联剂水解液中。In the step S21, 40-60 parts of ceramic powder is added to the coupling agent hydrolyzate.
所述步骤S22、充分搅拌0.5~2小时后放入至超声清洗器中进行分散0.5~2小时。In step S22, it is fully stirred for 0.5 to 2 hours and then placed in an ultrasonic cleaner for dispersion for 0.5 to 2 hours.
所述步骤S23、除去溶剂，得到疏水性陶瓷材料。In step S23, the solvent is removed to obtain a hydrophobic ceramic material.
步骤S3、基板材料制备Step S3, substrate material preparation
请参阅图5，所述步骤S3包括如下子步骤：Please refer to Figure 5, the step S3 includes the following sub-steps:
所述步骤S31、将50~80份的氟聚合物乳液加入容器中搅拌，其体系温度为20~50℃。In step S31, 50-80 parts of fluoropolymer emulsion is added to the container and stirred, and the temperature of the system is 20-50°C.
所述步骤S32、将50-70份的所述疏水性陶瓷材料缓慢加入所述氟聚合物乳液中。In step S32, 50-70 parts of the hydrophobic ceramic material is slowly added to the fluoropolymer emulsion.
所述步骤S33、充分搅拌1~5小时，得到所述基板材料。In the step S33, fully agitate for 1 to 5 hours to obtain the substrate material.
在本实施方式中，所述氟聚合物为聚四氟乙烯。In this embodiment, the fluoropolymer is polytetrafluoroethylene.
步骤S4、将所述基板材料在成膜设备中制成一定厚度的薄膜。Step S4, making the substrate material into a film with a certain thickness in a film forming equipment.
步骤S5、将所述薄膜在热压机中烧结，烧结的升温速率为1~5 ℃/分钟，保温温度为350~390℃，保温时间为1~3 小时，降温速度为0.5~3℃/分钟；得到成型的所述基板材料。Step S5. The film is sintered in a hot press. The sintering temperature rise rate is 1~5°C/min, the holding temperature is 350~390°C, the holding time is 1~3 hours, and the temperature drop rate is 0.5~3°C/min. Minutes; to obtain the molded substrate material.
本发明还提供一种层压板，所述层压板由如上中的任意一项所述的基板材料制备方法制成。The present invention also provides a laminate, which is made of the substrate material preparation method described in any one of the above.
本发明还提供一种覆铜箔层压板，所述覆铜箔层压板包括至少一张如上所述的层压板的一侧或两侧的铜箔。The present invention also provides a copper clad laminate. The copper clad laminate includes at least one copper foil on one or both sides of the laminate as described above.
本发明还提供一种印制电路板，所述印制电路板包括至少一张如上所述的层压板。The present invention also provides a printed circuit board, which includes at least one laminate as described above.
[根据细则26改正13.11.2019]　
为了验证本发明所述基板材料的实施效果进行以四组实施例来验证，本发明所述基板材料制成覆铜箔层压板，并对所述覆铜箔层压板进行测试,其中实验用的材料的简称，详见如下描述，其他没有具体说明的简称均为本领域内技术人员熟知的产品简称。

Figure WO-DOC-FIGURE-1
[Corrected according to Rule 26 13.11.2019]
In order to verify the implementation effect of the substrate material of the present invention, four groups of examples are used to verify the substrate material of the present invention. For the abbreviations of the materials, see the following description for details. Other abbreviations that are not specified are product abbreviations well-known to those skilled in the art.

Figure WO-DOC-FIGURE-1
本发明提供以下4组具体实施例进行说明，详见表1：The present invention provides the following 4 sets of specific examples for description, see Table 1 for details:
[根据细则26改正13.11.2019]　
表1实施例和对照例的组分数据

Figure WO-DOC-FIGURE-2
Figure WO-DOC-FIGURE-3
[Corrected according to Rule 26 13.11.2019]
Table 1 Component data of Examples and Comparative Examples

Figure WO-DOC-FIGURE-2
Figure WO-DOC-FIGURE-3
其中，具体为：Among them, specifically:
实施例一Example one
所述基板材料包括：56.1g的二氧化硅和73.2g聚四氟乙烯。The substrate material includes 56.1 g of silicon dioxide and 73.2 g of polytetrafluoroethylene.
所述覆铜箔层压板制备方法如下：The preparation method of the copper clad laminate is as follows:
基板材料制备：称量56.1g未经过改性的SiO2粉末，将其与73.2g的PTFE分散乳液进行超声搅拌混合3h。其中，含量比例有以下关系：PTFE:SiO 2=43.9:56.1。 Substrate material preparation: weigh 56.1g of unmodified SiO2 powder, and mix it with 73.2g of PTFE dispersion emulsion under ultrasonic stirring for 3h. Among them, the content ratio has the following relationship: PTFE:SiO 2 =43.9:56.1.
覆铜箔层压板制备：将上述得到的混合物在成膜设备中进行成膜，得到所需厚度的薄片，在其上下表面分别附上铜箔，热压烧结得到覆铜箔层压板。Copper-clad laminate preparation: the mixture obtained above is formed into a film in a film-forming equipment to obtain a sheet of desired thickness, copper foil is attached to the upper and lower surfaces of the laminate, and the copper-clad laminate is obtained by hot pressing and sintering.
实施例二Example two
所述基板材料包括：56.1g的二氧化硅、73.2g聚四氟乙烯以及1.0g的二甲基二甲氧基硅烷。The substrate material includes 56.1 g of silicon dioxide, 73.2 g of polytetrafluoroethylene, and 1.0 g of dimethyl dimethoxysilane.
所述覆铜箔层压板制备方法如下：The preparation method of the copper clad laminate is as follows:
基板材料制备：Substrate material preparation:
称量100g的二氧化硅粉末，称量1.0g的二甲基二甲氧基硅烷作为偶联剂，将二氧化硅粉末和偶联剂加入去离子水和酒精的混合液中，超声波处理和搅拌3小时。得到改性的二氧化硅陶瓷粉。其中，含量比例有以下关系：偶联剂：SiO 2=1.5:100。 Weigh 100g of silica powder, weigh 1.0g of dimethyldimethoxysilane as the coupling agent, add the silica powder and coupling agent to the mixture of deionized water and alcohol, ultrasonically treat and Stir for 3 hours. The modified silica ceramic powder is obtained. Among them, the content ratio has the following relationship: coupling agent: SiO 2 =1.5:100.
再称量56.1g改性好的SiO 2粉末，将其与73.2g的PTFE分散乳液进行超声波处理和搅拌混合3小时。含量比例有以下关系：PTFE:SiO 2=43.9:56.1。 Weigh 56.1 g of the modified SiO 2 powder, and perform ultrasonic treatment with 73.2 g of PTFE dispersion emulsion and stir and mix for 3 hours. The content ratio has the following relationship: PTFE:SiO 2 =43.9:56.1.
覆铜箔层压板制备：将上述得到的混合物在成膜设备中进行成膜，得到所需厚度的薄片，在其上下表面分别附上铜箔，热压烧结得到覆铜箔层压板。Copper-clad laminate preparation: the mixture obtained above is formed into a film in a film-forming equipment to obtain a sheet of desired thickness, copper foil is attached to the upper and lower surfaces of the laminate, and the copper-clad laminate is obtained by hot pressing and sintering.
实施例三Example three
所述基板材料包括：56.1g的二氧化硅、73.2g聚四氟乙烯以及1.0g的苯基三甲氧基硅烷。The substrate material includes 56.1 g of silicon dioxide, 73.2 g of polytetrafluoroethylene, and 1.0 g of phenyltrimethoxysilane.
所述覆铜箔层压板制备方法如下：The preparation method of the copper clad laminate is as follows:
基板材料制备：Substrate material preparation:
称量100g的二氧化硅粉末，称量1.0g的苯基三甲氧基硅烷作为偶联剂，将二氧化硅粉末和偶联剂加入去离子水和酒精的混合液中，超声波处理和搅拌3小时。得到改性的二氧化硅陶瓷粉。其中，含量比例有以下关系：偶联剂：SiO 2=1.5:100。 Weigh 100g of silica powder, weigh 1.0g of phenyltrimethoxysilane as coupling agent, add silica powder and coupling agent to the mixture of deionized water and alcohol, ultrasonically treat and stir 3 hour. The modified silica ceramic powder is obtained. Among them, the content ratio has the following relationship: coupling agent: SiO 2 =1.5:100.
再称量56.1g改性好的SiO 2粉末，将其与73.2g的PTFE分散乳液进行超声波处理和搅拌混合3小时。含量比例有以下关系：PTFE:SiO 2=43.9:56.1。 Weigh 56.1 g of the modified SiO 2 powder, and perform ultrasonic treatment with 73.2 g of PTFE dispersion emulsion and stir and mix for 3 hours. The content ratio has the following relationship: PTFE:SiO 2 =43.9:56.1.
覆铜箔层压板制备：将上述得到的混合物在成膜设备中进行成膜，得到所需厚度的薄片，在其上下表面分别附上铜箔，热压烧结得到覆铜箔层压板。Copper-clad laminate preparation: the mixture obtained above is formed into a film in a film-forming equipment to obtain a sheet of desired thickness, copper foil is attached to the upper and lower surfaces of the laminate, and the copper-clad laminate is obtained by hot pressing and sintering.
实施例四Example four
所述基板材料包括：56.1g的二氧化硅、73.2g聚四氟乙烯以及1.0g的十三氟辛基三乙氧基硅烷。The substrate material includes 56.1 g of silicon dioxide, 73.2 g of polytetrafluoroethylene, and 1.0 g of tridecafluorooctyl triethoxysilane.
所述覆铜箔层压板制备方法如下：The preparation method of the copper clad laminate is as follows:
基板材料制备：Substrate material preparation:
称量100g的二氧化硅粉末，称量1.0g的十三氟辛基三乙氧基硅烷作为偶联剂，将二氧化硅粉末和偶联剂加入去离子水和酒精的混合液中，超声波处理和搅拌3小时。得到改性的二氧化硅陶瓷粉。其中，含量比例有以下关系：偶联剂：SiO 2=1.5:100。 Weigh 100g of silica powder, weigh 1.0g of tridecafluorooctyltriethoxysilane as coupling agent, add silica powder and coupling agent to the mixture of deionized water and alcohol, ultrasonic Process and stir for 3 hours. The modified silica ceramic powder is obtained. Among them, the content ratio has the following relationship: coupling agent: SiO 2 =1.5:100.
再称量56.1g改性好的SiO 2粉末，将其与73.2g的PTFE分散乳液进行超声波处理和搅拌混合3小时。含量比例有以下关系：PTFE:SiO 2=43.9:56.1。 Weigh 56.1 g of the modified SiO 2 powder, and perform ultrasonic treatment with 73.2 g of PTFE dispersion emulsion and stir and mix for 3 hours. The content ratio has the following relationship: PTFE:SiO 2 =43.9:56.1.
覆铜箔层压板制备：将上述得到的混合物在成膜设备中进行成膜，得到所需厚度的薄片，在其上下表面分别附上铜箔，热压烧结得到覆铜箔层压板。Copper-clad laminate preparation: the mixture obtained above is formed into a film in a film-forming equipment to obtain a sheet of desired thickness, copper foil is attached to the upper and lower surfaces of the laminate, and the copper-clad laminate is obtained by hot pressing and sintering.
以上仅为几种实施例，其组合并不限于上述举例。The above are only a few embodiments, and the combination is not limited to the above examples.
上述基板材料的配制后，制成覆铜箔层压板，并将覆铜箔层压板进行测试，并获得以下实验结果，详见表2：After the above-mentioned substrate materials are prepared, a copper-clad laminate is made, and the copper-clad laminate is tested, and the following experimental results are obtained, as shown in Table 2:
[根据细则26改正13.11.2019]　
表2实施例和对照例的所述基板材料的测试数据

Figure WO-DOC-FIGURE-4
[Corrected according to Rule 26 13.11.2019]
Table 2 Test data of the substrate material of the embodiment and the comparative example

Figure WO-DOC-FIGURE-4
通过比较表2中的4组具体实施例以说明：To illustrate by comparing the 4 groups of specific examples in Table 2:
实施例1与实施例2-4具有相同质量份的二氧化硅和相同质量份的聚四氟乙烯，从而测试数据，实施例1-4的介电常数和介质损耗数据表明本发明的基板材料和覆铜箔层压板介电性能优。Example 1 and Example 2-4 have the same parts by weight of silicon dioxide and the same parts by weight of polytetrafluoroethylene, so the test data, the dielectric constant and dielectric loss data of Examples 1-4 indicate the substrate material of the present invention And copper clad laminates have excellent dielectric properties.
但是，实施例2-4相对于实施例1具有不同硅烷偶联剂对其的陶瓷粉末进行改性，从而使实施例2-4的粉末接触角参数分别为140°、123°及143°，而吸水率分别为0.02、0.04及0.02，表明实施例2-4的本发明基板材料的陶瓷粉末吸水率低。而实施例1因为不含硅烷偶联剂，故该基板材料粉末接触角参数显示亲水性，吸水率为0.24远大于实施例2-4的吸水率。However, Example 2-4 has different silane coupling agents to modify its ceramic powder compared to Example 1, so that the powder contact angle parameters of Example 2-4 are 140°, 123° and 143°, respectively. The water absorption rates are respectively 0.02, 0.04 and 0.02, indicating that the ceramic powders of the substrate materials of the present invention in Examples 2-4 have low water absorption rates. Since Example 1 does not contain a silane coupling agent, the contact angle parameter of the substrate material powder shows hydrophilicity, and the water absorption rate of 0.24 is much greater than that of Example 2-4.
本发明的陶瓷粉末通过硅烷偶联剂改性，表面张力得到提高，由亲水性变为疏水性，基板材料和覆铜箔层压板介电性能优且吸水率低。其中，从改性效果来看，二甲基二甲氧基硅烷和十三氟辛基三乙氧基硅烷的改性效果最佳，苯基三甲氧基硅烷的改性效果较一般，从成本来看二甲基二甲氧基硅烷与苯基三甲氧基硅烷的最低，十三氟辛基三乙氧基硅烷的成本最高，因此，从性价比上来看，二甲基二甲氧基硅烷比较适合作为二氧化硅的改性偶联剂。The ceramic powder of the present invention is modified by a silane coupling agent, the surface tension is improved, the hydrophilicity is changed to the hydrophobicity, the substrate material and the copper-clad laminate have excellent dielectric properties and low water absorption. Among them, from the perspective of modification effects, dimethyldimethoxysilane and tridecafluorooctyltriethoxysilane have the best modification effects, and phenyltrimethoxysilane has relatively general modification effects. From the perspective of dimethyldimethoxysilane and phenyltrimethoxysilane, the cost is the lowest, and the cost of tridecafluorooctyltriethoxysilane is the highest. Therefore, from the perspective of cost performance, dimethyldimethoxysilane is compared It is suitable as a modified coupling agent for silica.
钛酸盐偶联剂和锆酸盐偶联剂也是一类含有双官能团的物质，其中包括有机官能团和水解官能团。钛酸盐偶联剂和锆酸盐偶联剂在水解过程中生成含有羟基的化合物，该物质能与二氧化硅、二氧化钛、三氧化二铝等粒子表面发生相互作用，使有机官能团部分包覆在粒子的外表面，从而改善粒子在体系中的分散性和疏水性，提高PTFE与陶瓷颗粒的混合效果，最终起到增强复合材料的机械性能、提高介电性能、降低吸水率等效果。Titanate coupling agents and zirconate coupling agents are also a class of materials containing bifunctional groups, including organic functional groups and hydrolysis functional groups. The titanate coupling agent and zirconate coupling agent generate hydroxyl-containing compounds during the hydrolysis process, which can interact with the surface of silica, titanium dioxide, aluminum oxide and other particles to partially coat organic functional groups On the outer surface of the particles, thereby improving the dispersion and hydrophobicity of the particles in the system, improving the mixing effect of PTFE and ceramic particles, and ultimately enhancing the mechanical properties of the composite material, improving the dielectric properties, and reducing water absorption.
请参阅图6-7，图6为改性的二氧化硅的扫描电子显微镜图，图7为本发明的基板材料的扫描电子显微镜图。从图上可以看出，本发明的基板材料的氟聚合物和陶瓷填充材料相容性较好且均匀分散性，所述基板材料成分均匀且结构致密。Please refer to FIGS. 6-7. FIG. 6 is a scanning electron microscope image of the modified silica, and FIG. 7 is a scanning electron microscope image of the substrate material of the present invention. It can be seen from the figure that the fluoropolymer and ceramic filler of the substrate material of the present invention have good compatibility and uniform dispersion, and the substrate material has a uniform composition and a dense structure.
与相关技术相比，本发明的基板材料的陶瓷粉末通过偶联剂改性制成所述陶瓷填充材料，其中，所述偶联剂包括硅烷偶联剂、钛酸盐偶联剂及锆酸盐偶联剂中的任意一种或多种，通过改性，提高了陶瓷粉末的表面张力，从而使所述陶瓷填充材料具有疏水性。再将所述陶瓷填充材料与氟聚合物复合，从而使本发明的所述基板材料、基板材料制备方法及使用所述基板材料和应用所述基板材料制备方法的层压板、覆铜箔层压板以及印制电路板的氟聚合物和陶瓷填充材料相容性较好且均匀分散性、基板材料吸水率低且结构致密、介电性能好，工艺简单且成本较低。Compared with the related art, the ceramic powder of the substrate material of the present invention is modified by a coupling agent to make the ceramic filling material, wherein the coupling agent includes a silane coupling agent, a titanate coupling agent, and zirconic acid Any one or more of the salt coupling agents are modified to increase the surface tension of the ceramic powder, so that the ceramic filling material has hydrophobicity. The ceramic filler material is compounded with the fluoropolymer, so that the substrate material, the preparation method of the substrate material, the laminate and the copper clad laminate using the substrate material and the preparation method of the substrate material of the present invention And the fluoropolymer and ceramic filling material of the printed circuit board have good compatibility and uniform dispersion, low water absorption of the substrate material, compact structure, good dielectric performance, simple process and low cost.
以上所述的仅是本发明的实施方式，在此应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出改进，但这些均属于本发明的保护范围。The above are only the embodiments of the present invention. It should be pointed out here that for those of ordinary skill in the art, improvements can be made without departing from the inventive concept of the present invention, but these all belong to the present invention. The scope of protection.

Claims (19)

  1. 一种基板材料，其特征在于，所述基板材料包括氟聚合物和陶瓷填充材料，所述陶瓷填充材料由陶瓷粉末通过偶联剂改性制成，所述偶联剂包括硅烷偶联剂、钛酸盐偶联剂及锆酸盐偶联剂中的任意一种或多种。A substrate material, characterized in that the substrate material includes a fluoropolymer and a ceramic filling material, the ceramic filling material is made of ceramic powder modified by a coupling agent, and the coupling agent includes a silane coupling agent, Any one or more of titanate coupling agent and zirconate coupling agent.
  2. 根据权利要求1所述的基板材料，其特征在于，所述氟聚合物包括聚四氟乙烯、六氟丙烯、四氟乙烯以及全氟烷基乙烯基醚中任意一种或多种。The substrate material according to claim 1, wherein the fluoropolymer includes any one or more of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and perfluoroalkyl vinyl ether.
  3. 根据权利要求2所述的基板材料，其特征在于，所述氟聚合物为聚四氟乙烯。The substrate material of claim 2, wherein the fluoropolymer is polytetrafluoroethylene.
  4. 根据权利要求1所述的基板材料，其特征在于，所述陶瓷填充材料包括二氧化硅、二氧化钛、三氧化二铝、氮化铝、氧化镁、氧化钙、氧化锌以及氧化钡中的任意一种或多种。The substrate material according to claim 1, wherein the ceramic filler material comprises any one of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide, and barium oxide Kind or more.
  5. 根据权利要求4所述的基板材料，其特征在于，所述陶瓷填充材料为二氧化硅。The substrate material according to claim 4, wherein the ceramic filler material is silicon dioxide.
  6. 根据权利要求5所述的基板材料，其特征在于，所述陶瓷填充材料为熔融无定形二氧化硅。The substrate material of claim 5, wherein the ceramic filler material is fused amorphous silica.
  7. 根据权利要求1所述的基板材料，其特征在于，所述硅烷偶联剂包括二甲基二甲氧基硅烷、苯基三甲氧基硅烷、乙烯基三甲氧基硅烷、甲基丙烯酰基丙基三甲氧基硅烷、3-(2-氨基乙基氨基)丙基三甲氧基硅烷、 3-(2-氨基乙氨基)丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、对氯甲基苯基三甲氧基硅烷、氨基乙基氨基三甲氧基硅烷、十三氟辛基三乙氧基硅烷、(3,3,3-三氟丙基)三氯硅烷、(3,3,3-三氟丙基)二甲基氯硅烷、(3,3,3-三氟丙基)甲基二氯硅烷、 (3,3,3-三氟丙基)甲基二甲氧基硅烷、 (三氟-1,1,2,2-四氢）辛基)-1-三氯硅烷、 (三氟-1,1,2,2-四氢辛基)-1-甲基二氯硅烷、 (三氟-1,1,2,2-四氢辛基)-1-二甲基氯硅烷、 (庚氟-1,1,2,2-四氢癸基)-1-甲基二氯硅烷、 (庚氟-1,1,2,2-四氢癸基)-1-三氯硅烷、 (庚二氟-1,1,2)2-(2-四氢癸基)-1-二甲氧基氯硅烷(庚氟异丙氧基)丙基甲基二氯硅烷、 3-(庚氟异丙氧基)丙基三氯硅烷以及 3-(庚氟异丙氧基)丙基三乙氧基硅烷中的任意一种或多种。The substrate material according to claim 1, wherein the silane coupling agent comprises dimethyldimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, methacryloyl propyl Trimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, γ-methacryloxypropyltrimethyl Oxysilane, γ-aminopropyltriethoxysilane, p-chloromethylphenyltrimethoxysilane, aminoethylaminotrimethoxysilane, tridecafluorooctyltriethoxysilane, (3,3 ,3-Trifluoropropyl)trichlorosilane, (3,3,3-trifluoropropyl)dimethylchlorosilane, (3,3,3-trifluoropropyl)methyldichlorosilane, (3,3,3-Trifluoropropyl)methyldimethoxysilane, (trifluoro-1,1,2,2-tetrahydro)octyl)-1-trichlorosilane, (trifluoro-1 ,1,2,2-Tetrahydrooctyl)-1-methyldichlorosilane, (trifluoro-1,1,2,2-tetrahydrooctyl)-1-dimethylchlorosilane, (heptafluoro -1,1,2,2-tetrahydrodecyl)-1-methyldichlorosilane, (heptafluoro-1,1,2,2-tetrahydrodecyl)-1-trichlorosilane, (hepta Fluoro-1,1,2)2-(2-tetrahydrodecyl)-1-dimethoxychlorosilane (heptafluoroisopropoxy) propylmethyldichlorosilane, 3-(heptafluoroisopropyl) Any one or more of oxy)propyltrichlorosilane and 3-(heptafluoroisopropoxy)propyltriethoxysilane.
  8. 根据权利要求7所述的基板材料，其特征在于，所述偶联剂为二甲基二甲氧基硅烷。The substrate material according to claim 7, wherein the coupling agent is dimethyldimethoxysilane.
  9. 根据权利要求1所述的基板材料，其特征在于，所述钛酸盐偶联剂包括新戊基(二烯丙基)氧基三癸酰基钛酸酯、新戊(二烯丙基)氧三(十二烷基)苯磺酰基钛酸酯、新戊基(二烯丙基)氧三(二辛基)磷酸钛酸酯以及异丙基三(二辛基焦磷酸酰氧基)钛酸酯中的任意一种或多种。The substrate material of claim 1, wherein the titanate coupling agent comprises neopentyl (diallyl) oxy tridecanoyl titanate, neopentyl (diallyl) oxygen Tris(dodecyl)benzenesulfonyl titanate, neopentyl(diallyl)oxytris(dioctyl)phosphate titanate and isopropyl tris(dioctylpyrophosphate acyloxy)titanium Any one or more of acid esters.
  10. 根据权利要求1所述的基板材料，其特征在于，所述锆酸盐偶联剂包括新戊基(二烯丙基)氧三(二辛基)焦磷酸锆、新戊基(二烯丙基)氧三(N-乙二胺)乙基锆酸盐的任意一种或多种。The substrate material according to claim 1, wherein the zirconate coupling agent comprises neopentyl (diallyl) oxygen tris(dioctyl) zirconium pyrophosphate, neopentyl (diallyl) Any one or more of oxytris(N-ethylenediamine) ethyl zirconate.
  11. 一种基板材料制备方法，其特征在于，该方法包括如下步骤：A method for preparing a substrate material is characterized in that the method includes the following steps:
    偶联剂水解，将0.5~3份的水和8~30份的无水乙醇混合，滴入pH调节液并充分搅拌，调节pH值至3~6，再加入0.5-3份如权利要求1或7~10中的任意一种或多种所述的偶联剂，调节温度在20~50 ℃，充分搅拌0.5~3小时，得到偶联剂水解液；The coupling agent is hydrolyzed. Mix 0.5~3 parts of water and 8~30 parts of absolute ethanol, drip into the pH adjusting solution and stir well, adjust the pH to 3~6, and then add 0.5-3 parts as claimed in claim 1. Or any one or more of the coupling agents from 7 to 10, adjust the temperature at 20 to 50 ℃, and fully stir for 0.5 to 3 hours to obtain the coupling agent hydrolysate;
    疏水性陶瓷材料制备，将40~60份的陶瓷粉末加入所述偶联剂水解液中，充分搅拌0.5~2小时后放入至超声清洗器中进行分散0.5~2小时，除去溶剂得到疏水性陶瓷材料；For the preparation of hydrophobic ceramic material, add 40-60 parts of ceramic powder to the coupling agent hydrolysate, stir thoroughly for 0.5-2 hours and then put it in an ultrasonic cleaner for dispersion for 0.5-2 hours, remove the solvent to obtain hydrophobicity Ceramic material;
    基板材料制备，将50~80份的氟聚合物乳液加入容器中搅拌，其体系温度为20~50℃；将50-70份的所述疏水性陶瓷材料缓慢加入所述氟聚合物乳液中，充分搅拌1~5小时，得到所述基板材料。For substrate material preparation, add 50-80 parts of fluoropolymer emulsion to the container and stir, and the system temperature is 20-50°C; slowly add 50-70 parts of the hydrophobic ceramic material to the fluoropolymer emulsion, Stir fully for 1 to 5 hours to obtain the substrate material.
  12. 根据权利要求11所述的基板材料制备方法，其特征在于，所述氟聚合物为聚四氟乙烯。The method for preparing a substrate material according to claim 11, wherein the fluoropolymer is polytetrafluoroethylene.
  13. 根据权利要求11所述的基板材料制备方法，其特征在于，所述基板材料制备步骤之后，还包括如下步骤：The method for preparing a substrate material according to claim 11, wherein after the substrate material preparation step, the method further comprises the following steps:
    将所述基板材料在成膜设备中制成一定厚度的薄膜；Making the substrate material into a film with a certain thickness in a film forming device;
    将所述薄膜在热压机中烧结，烧结的升温速率为1~5 ℃/分钟，保温温度为350~390℃，保温时间为1~3 小时，降温速度为0.5~3℃/分钟；得到成型的所述基板材料。The film is sintered in a hot press, the sintering rate is 1~5°C/min, the holding temperature is 350~390°C, the holding time is 1~3 hours, and the temperature drop rate is 0.5~3°C/min; The molded substrate material.
  14. 一种层压板，其特征在于，所述层压板由如权利要求1~10中的任意一项所述的基板材料制成。A laminated board, wherein the laminated board is made of the substrate material according to any one of claims 1 to 10.
  15. 一种层压板，其特征在于，所述层压板由如权利要求11~13中的任意一项所述的基板材料制备方法制成。A laminate, characterized in that the laminate is made by the method for preparing a substrate material according to any one of claims 11-13.
  16. 一种覆铜箔层压板，其特征在于，所述覆铜箔层压板包括至少一张如权利要求14所述的层压板的一侧或两侧的铜箔。A copper-clad laminate, wherein the copper-clad laminate includes at least one copper foil on one or both sides of the laminate according to claim 14.
  17. 一种印制电路板，其特征在于，所述印制电路板包括至少一张如权利要求14所述的层压板。A printed circuit board, wherein the printed circuit board comprises at least one laminate according to claim 14.
  18. 一种覆铜箔层压板，其特征在于，所述覆铜箔层压板包括至少一张如权利要求15所述的层压板的一侧或两侧的铜箔。A copper-clad laminate, wherein the copper-clad laminate comprises at least one copper foil on one or both sides of the laminate according to claim 15.
  19. 一种印制电路板，其特征在于，所述印制电路板包括至少一张如权利要求15所述的层压板。A printed circuit board, characterized in that, the printed circuit board comprises at least one laminate according to claim 15.
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