CN110591255B - Substrate material, substrate material preparation method and related substrate - Google Patents
Substrate material, substrate material preparation method and related substrate Download PDFInfo
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- CN110591255B CN110591255B CN201910743150.4A CN201910743150A CN110591255B CN 110591255 B CN110591255 B CN 110591255B CN 201910743150 A CN201910743150 A CN 201910743150A CN 110591255 B CN110591255 B CN 110591255B
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- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- 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
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- 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
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- 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
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- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B32B2307/00—Properties of the layers or laminate
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Abstract
The invention provides a substrate material which comprises a fluoropolymer and a ceramic filling material, wherein the ceramic filling material is prepared by modifying ceramic powder through 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. The invention also provides a preparation method of the substrate material, and a laminated board, a copper clad laminated board and a printed circuit board which use the substrate material and the preparation method of the substrate material. Compared with the prior art, the substrate material, the preparation method of the substrate material, the laminated board, the copper-clad laminated board and the fluorine polymer and ceramic filling material of the printed circuit board have the advantages of good compatibility, uniform dispersibility, low water absorption of the substrate material, compact structure, good dielectric property, simple process and low cost.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of copper clad plates, in particular to a substrate material, a preparation method of the substrate material, a laminated plate using the substrate material and the preparation method of the substrate material, a copper clad laminated plate and a printed circuit board.
[ background of the invention ]
With the coming of the 5G era, the development of electronic products tends to be multifunctional, parts are continuously developed in the directions of lightness, thinness, shortness, smallness and the like, and particularly, the wide application of high-density integrated circuit technology puts forward the requirements of high performance, high reliability and high safety on civil electronic products; the requirements of good technical performance, low cost and high energy consumption are provided for industrial electronic products. However, the conventional inorganic substrate has a high dielectric constant, which affects signal transmission speed and response time. The pure organic substrate has high thermal expansion coefficient, low thermal conductivity and poor thermal stability. Therefore, a material with excellent dielectric, mechanical and thermal properties is urgently needed to meet the requirements of high-speed and low-delay integrated circuits.
Polytetrafluoroethylene (PTFE for short) has excellent dielectric properties (low dielectric constant and low dielectric loss) and good chemical stability and thermal stability, so that the PTFE has potential application values in the fields of satellite communication, mobile radio communication, satellite broadcast television radar equipment, computers and the like.
However, pure polytetrafluoroethylene has a large thermal expansion coefficient, specifically 106 ppm/DEG C, and has a large difference with the thermal expansion coefficient of copper (specifically 16 ppm/DEG C), so that direct copper-clad is prone to thermal adaptation failure; in addition, the pure polytetrafluoroethylene has low thermal conductivity, and the specific value is 0.20-0.25W/mk; meanwhile, pure polytetrafluoroethylene has poor fluidity and is difficult to mold, and deformation and cracking are easily caused due to large shrinkage rate during molding; moreover, the pure polytetrafluoroethylene has extremely poor adhesion capability due to extremely low surface energy; and the pure polytetrafluoroethylene has poor compression resistance, low strength and the like.
Therefore, there is a need to provide a new substrate material, a method for manufacturing the same, and a related substrate to solve the above-mentioned problems.
[ summary of the invention ]
The invention aims to provide a substrate material, a substrate material preparation method, a laminated board, a copper-clad laminated board and a printed circuit board, wherein the substrate material has the advantages of good compatibility and uniform dispersibility of a fluoropolymer and a ceramic filling material, low water absorption rate of the substrate material, compact structure, good dielectric property, simple process and low cost.
In order to achieve the above purpose, the present invention provides a substrate material, which comprises a fluoropolymer and a ceramic filler, wherein the ceramic filler is prepared by modifying ceramic powder with 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.
Preferably, the fluoropolymer comprises any one or more of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene, and perfluoroalkyl vinyl ether.
Preferably, the fluoropolymer is polytetrafluoroethylene.
Preferably, the ceramic filling material comprises any one or more of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide and barium oxide.
Preferably, the ceramic filler material is silica.
Preferably, the ceramic filler material is fused amorphous silica.
Preferably, the silane coupling agent includes dimethyldimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-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, dimethyldimethoxysilane, phenyltrimethoxysilane, 3- (2-aminoethylamino) propyltriethoxysilane, n-methacryloxypropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, p-chloromethyltrimethoxysilane, aminoethylaminotrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltrimet, (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, (heptofluoro-1, 1,2, 2-tetrahydrodecyl) -1-methyldichlorosilane, any one or more of (heptofluoro-1, 1,2, 2-tetrahydrodecyl) -1-trichlorosilane, (heptofluoro-1, 1,2)2- (2-tetrahydrodecyl) -1-dimethoxychlorosilane (heptofluoroisopropoxy) propylmethyldichlorosilane, 3- (heptofluoroisopropoxy) propyltrichlorosilane, and 3- (heptofluoroisopropoxy) propyltriethoxysilane.
Preferably, the coupling agent is dimethyldimethoxysilane.
Preferably, the titanate coupling agent comprises any one or more of neopentyl (diallyl) oxytridecanoyl titanate, neopentyl (diallyl) oxytridodecyl benzenesulfonyl titanate, neopentyl (diallyl) oxytrioctyl phosphate titanate, and isopropyl tri (dioctyl pyrophosphato) titanate.
Preferably, the zirconate coupling agent comprises any one or more of neopentyl (diallyl) oxy tris (dioctyl) zirconium pyrophosphate, neopentyl (diallyl) oxy tris (N-ethylenediamine) ethyl zirconate.
The present invention also provides a laminate made of the substrate material as described in any one of the above.
The invention also provides a copper clad laminate comprising at least one copper foil on one or both sides of the laminate as described above.
The invention also provides a printed circuit board comprising at least one laminate as described above.
The invention also provides a preparation method of the substrate material, which comprises the following steps:
hydrolyzing a coupling agent, mixing 0.5-3 parts of water and 8-30 parts of absolute ethyl alcohol, dripping a pH regulating solution, fully stirring, regulating the pH value to 3-6, then adding 0.5-3 parts of one or more coupling agents as claimed in any one of claims 1 or 7-10, regulating the temperature to 20-50 ℃, and fully stirring for 0.5-3 hours to obtain a coupling agent hydrolysate;
preparing a hydrophobic ceramic material, namely adding 40-60 parts of ceramic powder into the coupling agent hydrolysate, fully stirring for 0.5-2 hours, then putting into an ultrasonic cleaner for dispersing for 0.5-2 hours, and removing the solvent to obtain the hydrophobic ceramic material;
preparing a substrate material, namely adding 50-80 parts of fluoropolymer emulsion into a container and stirring, wherein the system temperature is 20-50 ℃; and slowly adding 50-70 parts of the hydrophobic ceramic material into the fluoropolymer emulsion, and fully stirring for 1-5 hours to obtain the substrate material.
Preferably, the fluoropolymer is polytetrafluoroethylene.
Preferably, after the substrate material preparation step, the method further comprises the following steps:
preparing the substrate material into a thin film with a certain thickness in a film forming device;
sintering the film in a hot press, wherein the heating rate of sintering is 1-5 ℃/min, the heat preservation temperature is 350-390 ℃, the heat preservation time is 1-3 hours, and the cooling rate is 0.5-3 ℃/min; and obtaining the molded substrate material.
The invention also provides a laminated plate, which is prepared by the preparation method of the substrate material.
The invention also provides a copper clad laminate comprising at least one copper foil on one or both sides of the laminate as described above.
The invention also provides a printed circuit board comprising at least one laminate as described above.
Compared with the prior art, the ceramic filling material is prepared by modifying the ceramic powder of the substrate material through the coupling agent, wherein the coupling agent comprises any one or more of silane coupling agent, titanate coupling agent and zirconate coupling agent, and the surface tension of the ceramic powder is improved through modification, so that the ceramic filling material has hydrophobicity. And compounding the ceramic filling material with the fluoropolymer, so that the substrate material, the substrate material preparation method, and the fluoropolymer and the ceramic filling material of the laminated board, the copper-clad laminated board and the printed circuit board using the substrate material and the substrate material preparation method have the advantages of good compatibility, uniform dispersibility, low substrate material water absorption rate, compact structure, good dielectric property, simple process and low cost.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
FIG. 1 is a flow chart of a method of preparing a substrate material according to the present invention;
FIG. 2 is a block flow diagram of an embodiment of a method of preparing a substrate material of the present invention;
FIG. 3 is a block diagram of a sub-flow of step S1 of the method for preparing a substrate material according to the present invention;
FIG. 4 is a block diagram of a sub-flow of step S2 of the method of preparing a substrate material according to the present invention;
FIG. 5 is a block diagram of a sub-flow of step S3 of the method for preparing a substrate material according to the present invention;
FIG. 6 is a scanning electron microscope image of modified silica;
FIG. 7 is a scanning electron microscope photograph of a substrate material of the present invention.
[ detailed description ] embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a substrate material which comprises a fluoropolymer and a ceramic filling material, wherein the ceramic filling material is prepared by modifying ceramic powder through 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.
The fluorine polymer comprises one or more of polytetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene and perfluoroalkyl vinyl ether.
The fluoropolymer is polytetrafluoroethylene. Polytetrafluoroethylene (PTFE) has excellent dielectric properties (low dielectric constant and low dielectric loss), and good chemical and thermal stability.
In order to lower the thermal expansion coefficient of the fluoropolymer and increase the thermal conductivity thereof, it is necessary to compound the fluoropolymer with ceramic. However, since the surface energy of the fluoropolymer is very low, and the ceramic powder often contains hydroxyl groups and has high surface energy, the ceramic powder needs to be modified to reduce the surface energy and increase the hydrophobicity. Most of the ceramic powder sold in the market is not modified by a coupling agent, and belongs to hydrophilic ceramic; a small part of modified ceramic has common modification effect, namely common hydrophobicity, or lacks in particle size or ceramic powder type, and has less selectable modification effect and powder type; therefore, the ceramic powder needs to be modified by a coupling agent. The ceramic filling material is modified by the coupling agent, so that the surface tension of the ceramic powder is improved, the ceramic powder is changed from hydrophilicity to hydrophobicity, and the water absorption of the substrate made of the substrate material is obviously reduced.
The ceramic filling material comprises any one or more of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide and barium oxide.
The ceramic filling material is silicon dioxide. Preferably, the ceramic filler material is fused amorphous silica. The ceramic used for the substrate material, including silica, titania, and other ceramic powders, is typically a hydrophilic material.
The silane coupling agent comprises dimethyl dimethoxy silane, phenyl trimethoxy silane, vinyl trimethoxy silane, methacryloxypropyl trimethoxy silane, 3- (2-aminoethylamino) propyl triethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, p-chloromethylphenyl trimethoxy silane, aminoethylaminotrimethoxy silane, tridecafluorooctyl triethoxy silane, (3,3, 3-trifluoropropyl) trichlorosilane, (3,3, 3-trifluoropropyl) dimethylchlorosilane, (3,3, 3-trifluoropropyl) methyldichlorosilane, (3,3, 3-trifluoropropyl) methyldimethoxy silane, (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, (heptofluoro-1, 1,2, 2-tetrahydrodecyl) -1-methyldichlorosilane, any one or more of (heptofluoro-1, 1,2, 2-tetrahydrodecyl) -1-trichlorosilane, (heptofluoro-1, 1,2)2- (2-tetrahydrodecyl) -1-dimethoxychlorosilane (heptofluoroisopropoxy) propylmethyldichlorosilane, 3- (heptofluoroisopropoxy) propyltrichlorosilane, and 3- (heptofluoroisopropoxy) propyltriethoxysilane.
The coupling agent is dimethyl dimethoxy silane. The cost of the dimethyl dimethoxy silane is lower and far lower than that of the fluorine-containing silane coupling agent. Therefore, the substrate material is low in cost. The effect of dimethyl dimethoxy silane on the modification of ceramic powder is comparable to that of fluorine-containing silane coupling agent.
The titanate coupling agent comprises one or more of neopentyl (diallyl) oxytridecanoyl titanate, neopentyl (diallyl) oxytridodecyl benzenesulfonyl titanate, neopentyl (diallyl) oxytrioctyl phosphate titanate and isopropyl tri (dioctyl pyrophosphato acyloxy) titanate.
The zirconate coupling agent comprises any one or more of neopentyl (diallyl) oxytris (dioctyl) zirconium pyrophosphate or neopentyl (diallyl) oxytris (N-ethylenediamine) ethyl zirconate.
In summary, the fluoropolymer and the ceramic powder are compounded, then the ceramic powder is fully wrapped by the fluoropolymer, the modified ceramic powder has better compatibility and uniform dispersibility in the fluoropolymer emulsion, and the substrate material generated by the fluoropolymer filled with the ceramic has uniform components and compact structure.
The present invention also provides a laminate made of the substrate material as described in any one of the above.
The invention also provides a copper clad laminate comprising at least one copper foil on one or both sides of the laminate as described above.
The invention also provides a printed circuit board comprising at least one laminate as described above.
Referring to fig. 1-2, fig. 1 is a flow chart of a method for preparing a substrate material according to 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 invention also provides a preparation method of the substrate material, which comprises the following steps:
step S1, hydrolysis of coupling agent
Referring to fig. 3, the step S1 includes the following sub-steps:
and S11, mixing 0.5-3 parts of water and 8-30 parts of absolute ethyl alcohol to serve as a solvent for hydrolysis of the silane coupling agent, and providing hydroxyl groups for hydrolysis of the silane coupling agent to generate silanol.
S12, dripping pH adjusting liquid and fully stirring, wherein the dripping speed cannot be too high, otherwise, gel-like substances are easily generated, the pH value is adjusted to 3-6, the hydrolysis process of the silane coupling agent is accompanied by condensation reaction of silanol, the pH value is adjusted, the hydrolysis speed of the silane coupling agent can be controlled, so that the dominant reaction is controlled, the pH value is too high or too low, the condensation speed of the silanol is larger than the hydrolysis speed of the silane, or the hydrolysis speed is too low, the concentration of the silanol is too low, and the modification effect is influenced
And S13, adding 0.5-3 parts of any one of the coupling agents, adjusting the temperature to 20-50 ℃, and fully stirring for 0.5-3 hours to obtain a coupling agent hydrolysate, wherein silanol hydroxyl groups of the hydrolysate react with hydroxyl groups on the surface of silicon dioxide, so that the hydrophobic property of the silicon dioxide is improved, the temperature is a key factor for adjusting the hydrolysis of the silane coupling agent, the condensation speed of silanol is increased due to overhigh temperature, a glue nucleus is formed, even precipitation occurs, and the hydrolysis reaction speed is too low due to overlow temperature.
Step S2, preparation of hydrophobic ceramic material
Referring to fig. 4, the step S2 includes the following sub-steps:
and S21, adding 40-60 parts of ceramic powder into the coupling agent hydrolysate.
And S22, fully stirring for 0.5-2 hours, and then putting into an ultrasonic cleaner for dispersing for 0.5-2 hours.
And S23, removing the solvent to obtain the hydrophobic ceramic material.
Step S3, preparing substrate material
Referring to fig. 5, the step S3 includes the following sub-steps:
and S31, adding 50-80 parts of the fluoropolymer emulsion into a container and stirring, wherein the system temperature is 20-50 ℃.
The step S32, slowly adding 50-70 parts of the hydrophobic ceramic material into the fluoropolymer emulsion.
And S33, fully stirring for 1-5 hours to obtain the substrate material.
In this embodiment, the fluoropolymer is polytetrafluoroethylene.
And step S4, making the substrate material into a thin film with a certain thickness in the film forming equipment.
S5, sintering the film in a hot press, wherein the heating rate of sintering is 1-5 ℃/min, the heat preservation temperature is 350-390 ℃, the heat preservation time is 1-3 hours, and the cooling rate is 0.5-3 ℃/min; and obtaining the molded substrate material.
The invention also provides a laminated plate, which is prepared by the preparation method of the substrate material.
The invention also provides a copper clad laminate comprising at least one copper foil on one or both sides of the laminate as described above.
The invention also provides a printed circuit board comprising at least one laminate as described above.
In order to verify the implementation effect of the substrate material, four groups of embodiments are used for verifying the implementation effect of the substrate material, the substrate material is made into a copper clad laminate, and the copper clad laminate is tested, wherein the abbreviation of the material for experiment is described in the following, and the abbreviation of other abbreviation which is not specifically described is the abbreviation of a product well known by those skilled in the art.
| Material | For short |
| Polytetrafluoroethylene | PTFE |
| Silicon dioxide | SiO2 |
The invention is illustrated by the following 4 specific examples, detailed in table 1:
TABLE 1 component data of examples and comparative examples
The method specifically comprises the following steps:
example one
The substrate material includes: 56.1g of silica and 73.2g of polytetrafluoroethylene.
The preparation method of the copper clad laminate comprises the following steps:
preparing a substrate material: 56.1g of unmodified SiO2 powder was weighed out and mixed with 73.2g of PTFE dispersion emulsion by ultrasonic stirring for 3 hours. Wherein, the content proportion has the following relation: PTFE SiO2＝43.9:56.1。
Preparing a copper clad laminate: and (3) forming a film on the obtained mixture in a film forming device to obtain a sheet with a required thickness, respectively attaching copper foils to the upper surface and the lower surface of the sheet, and performing hot-pressing sintering to obtain the copper-clad laminate.
Example two
The substrate material includes: 56.1g of silica, 73.2g of polytetrafluoroethylene and 1.0g of dimethyldimethoxysilane.
The preparation method of the copper clad laminate comprises the following steps:
preparing a substrate material:
100g of silica powder was weighed, 1.0g of dimethyldimethoxysilane was weighed as a coupling agent, and the silica powder and the coupling agent were added to a mixed solution of deionized water and alcohol, and subjected to ultrasonic treatment and stirred for 3 hours. Obtaining the modified silicon dioxide ceramic powder. Wherein, the content proportion has the following relation: coupling agent: SiO22＝1.5:100。
56.1g of modified SiO were weighed again2Powder was sonicated and stirred with 73.2g of PTFE dispersion emulsion for 3 hours. The content ratio has the following relationship: PTFE SiO2＝43.9:56.1。
Preparing a copper clad laminate: and (3) forming a film on the obtained mixture in a film forming device to obtain a sheet with a required thickness, respectively attaching copper foils to the upper surface and the lower surface of the sheet, and performing hot-pressing sintering to obtain the copper-clad laminate.
EXAMPLE III
The substrate material includes: 56.1g of silica, 73.2g of polytetrafluoroethylene and 1.0g of phenyltrimethoxysilane.
The preparation method of the copper clad laminate comprises the following steps:
preparing a substrate material:
100g of silica powder was weighed, 1.0g of phenyltrimethoxysilane was weighed as a coupling agent, and the silica powder and the coupling agent were added to a mixed solution of deionized water and alcohol, and subjected to ultrasonic treatment and stirred for 3 hours. Obtaining the modified silicon dioxide ceramic powder. Wherein, the content proportion has the following relation: coupling agent: SiO22＝1.5:100。
56.1g of modified SiO were weighed again2Powder was sonicated and stirred with 73.2g of PTFE dispersion emulsion for 3 hours. The content ratio has the following relationship: PTFE SiO2＝43.9:56.1。
Preparing a copper clad laminate: and (3) forming a film on the obtained mixture in a film forming device to obtain a sheet with a required thickness, respectively attaching copper foils to the upper surface and the lower surface of the sheet, and performing hot-pressing sintering to obtain the copper-clad laminate.
Example four
The substrate material includes: 56.1g of silica, 73.2g of polytetrafluoroethylene and 1.0g of tridecafluorooctyltriethoxysilane.
The preparation method of the copper clad laminate comprises the following steps:
preparing a substrate material:
100g of silica powder was weighed, 1.0g of tridecafluorooctyltriethoxysilane was weighed as a coupling agent, and the silica powder and the coupling agent were added to a mixed solution of deionized water and alcohol, and subjected to ultrasonic treatment and stirred for 3 hours. Obtaining the modified silicon dioxide ceramic powder. Wherein, the content proportion has the following relation: coupling agent: SiO22＝1.5:100。
56.1g of modified SiO were weighed again2Powder was sonicated and stirred with 73.2g of PTFE dispersion emulsion for 3 hours. The content ratio has the following relationship: PTFE SiO2＝43.9:56.1。
Preparing a copper clad laminate: and (3) forming a film on the obtained mixture in a film forming device to obtain a sheet with a required thickness, respectively attaching copper foils to the upper surface and the lower surface of the sheet, and performing hot-pressing sintering to obtain the copper-clad laminate.
The above are only a few embodiments, the combination of which is not limited to the above examples.
After the substrate material is prepared, a copper clad laminate is prepared, and the copper clad laminate is tested, and the following experimental results are obtained, which are detailed in table 2:
table 2 test data of the substrate materials of examples and comparative examples
| Test items | Example 1 | Example 2 | Example 3 | Example 4 |
| Dielectric constant | 2.75 | 2.76 | 2.76 | 2.75 |
| Dielectric loss | 0.003 | 0.001 | 0.001 | 0.001 |
| Powder contact angle | Hydrophilicity | 140° | 123° | 143° |
| Water absorption (%) | 0.24 | 0.02 | 0.04 | 0.02 |
By comparing 4 sets of specific examples in table 2 to illustrate:
example 1 and examples 2-4 have the same parts by mass of silica and the same parts by mass of polytetrafluoroethylene, so that the data are tested, and the dielectric constant and dielectric loss data of examples 1-4 show that the substrate material and the copper clad laminate of the present invention are excellent in dielectric properties.
However, the ceramic powders of examples 2 to 4 were modified with different silane coupling agents from those of example 1 so that the powder contact angle parameters of examples 2 to 4 were 140 °, 123 ° and 143 °, respectively, and the water absorptions were 0.02, 0.04 and 0.02, respectively, indicating that the ceramic powders of the inventive substrate materials of examples 2 to 4 had low water absorptions. In contrast, since example 1 does not contain a silane coupling agent, the substrate material shows hydrophilicity in terms of powder contact angle parameter, and the water absorption of 0.24 is much higher than that of examples 2 to 4.
The ceramic powder is modified by the silane coupling agent, the surface tension is improved, the hydrophilicity is changed into hydrophobicity, and the substrate material and the copper-clad laminate have excellent dielectric property and low water absorption. Among them, dimethyldimethoxysilane and tridecafluorooctyltriethoxysilane have the best modification effect, phenyltrimethoxysilane has the more general modification effect, dimethyldimethoxysilane and phenyltrimethoxysilane have the lowest cost, and tridecafluorooctyltriethoxysilane has the highest cost, so dimethyldimethoxysilane is more suitable as a silica modification coupling agent in terms of cost performance.
Titanate coupling agents and zirconate coupling agents are also a class of bifunctional species that include both organic functional groups and hydrolyzable functional groups. The titanate coupling agent and the zirconate coupling agent generate a compound containing hydroxyl in the hydrolysis process, and the compound can interact with the surfaces of particles such as silicon dioxide, titanium dioxide and aluminum oxide, so that organic functional groups are partially coated on the outer surfaces of the particles, thereby improving the dispersibility and hydrophobicity of the particles in a system, improving the mixing effect of PTFE and ceramic particles, and finally playing the effects of enhancing the mechanical property of the composite material, improving the dielectric property, reducing the water absorption rate and the like.
Referring to fig. 6-7, fig. 6 is a scanning electron microscope image of modified silica, and fig. 7 is a scanning electron microscope image of a substrate material according to the present invention. As can be seen from the figure, the fluoropolymer of the substrate material has good compatibility and uniform dispersibility with the ceramic filling material, and the substrate material has uniform components and compact structure.
Compared with the prior art, the ceramic filling material is prepared by modifying the ceramic powder of the substrate material through the coupling agent, wherein the coupling agent comprises any one or more of silane coupling agent, titanate coupling agent and zirconate coupling agent, and the surface tension of the ceramic powder is improved through modification, so that the ceramic filling material has hydrophobicity. And compounding the ceramic filling material with the fluoropolymer, so that the substrate material, the substrate material preparation method, and the fluoropolymer and the ceramic filling material of the laminated board, the copper-clad laminated board and the printed circuit board using the substrate material and the substrate material preparation method have the advantages of good compatibility, uniform dispersibility, low substrate material water absorption rate, compact structure, good dielectric property, simple process and low cost.
While the foregoing is directed to embodiments of the present invention, it will be understood by those skilled in the art that various changes may be made without departing from the spirit and scope of the invention.
Claims (11)
1. The substrate material is characterized by comprising a fluoropolymer and a ceramic filling material, wherein the ceramic filling material is prepared by modifying ceramic powder through a coupling agent, the coupling agent is a silane coupling agent, the silane coupling agent is dimethyl dimethoxysilane, the fluoropolymer is polytetrafluoroethylene, and the ceramic filling material comprises any one or more of silicon dioxide, titanium dioxide, aluminum oxide, aluminum nitride, magnesium oxide, calcium oxide, zinc oxide and barium oxide.
2. The substrate material of claim 1, wherein the ceramic filler material is silicon dioxide.
3. The substrate material of claim 2, wherein the ceramic filler material is fused amorphous silica.
4. A method for producing a substrate material, wherein the substrate material according to claim 1 is applied, the method comprising the steps of:
hydrolyzing a coupling agent, mixing 0.5-3 parts of water and 8-30 parts of absolute ethyl alcohol, dripping a pH regulating solution, fully stirring, regulating the pH value to 3-6, adding 0.5-3 parts of the coupling agent, regulating the temperature to 20-50 ℃, and fully stirring for 0.5-3 hours to obtain a coupling agent hydrolysate;
preparing a hydrophobic ceramic material, namely adding 40-60 parts of ceramic powder into the coupling agent hydrolysate, fully stirring for 0.5-2 hours, then putting into an ultrasonic cleaner for dispersing for 0.5-2 hours, and removing the solvent to obtain the hydrophobic ceramic material;
preparing a substrate material, namely adding 50-80 parts of fluoropolymer emulsion into a container and stirring, wherein the system temperature is 20-50 ℃; and slowly adding 50-70 parts of the hydrophobic ceramic material into the fluoropolymer emulsion, and fully stirring for 1-5 hours to obtain the substrate material.
5. The method for preparing a substrate material according to claim 4, further comprising, after the step of preparing a substrate material, the steps of:
preparing the substrate material into a thin film with a certain thickness in a film forming device;
sintering the film in a hot press, wherein the heating rate of sintering is 1-5 ℃/min, the heat preservation temperature is 350-390 ℃, the heat preservation time is 1-3 hours, and the cooling rate is 0.5-3 ℃/min; and obtaining the molded substrate material.
6. A laminate made of a substrate material according to any one of claims 1 to 3.
7. A laminate produced by the method of producing a substrate material according to any one of claims 4 to 5.
8. A copper clad laminate comprising at least one copper foil on one or both sides of the laminate of claim 6.
9. A printed circuit board comprising at least one laminate of claim 6.
10. A copper clad laminate comprising at least one copper foil on one or both sides of the laminate of claim 7.
11. A printed circuit board comprising at least one laminate of claim 7.
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| CN111775527A (en) * | 2020-07-09 | 2020-10-16 | 瑞声科技（南京）有限公司 | Preparation method of composite medium copper-clad plate and printed circuit board |
| CN112248588B (en) * | 2020-09-10 | 2022-12-27 | 浙江华正新材料股份有限公司 | Circuit substrate, preparation method thereof and printed circuit board |
| CN112574521B (en) * | 2020-12-09 | 2022-04-26 | 广东生益科技股份有限公司 | Fluorine-containing resin composition, resin glue solution containing same, fluorine-containing medium sheet, laminated board, copper-clad plate and printed circuit board |
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| CN107474312A (en) * | 2017-06-12 | 2017-12-15 | 电子科技大学 | The preparation method of ceramic filled polytetrafluoroethylglass microwave composite medium substrate |
| CN108189520A (en) * | 2017-12-28 | 2018-06-22 | 浙江华正新材料股份有限公司 | A kind of production method of modified polytetrafluoroethylcopper copper clad plate |
| CN110039852A (en) * | 2019-04-19 | 2019-07-23 | 中国电子科技集团公司第四十六研究所 | A kind of preparation method of PTFE copper-clad plate |
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| CN102731941A (en) * | 2012-06-13 | 2012-10-17 | 浙江大学 | Preparation method of teflon composite material |
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| CN107474312A (en) * | 2017-06-12 | 2017-12-15 | 电子科技大学 | The preparation method of ceramic filled polytetrafluoroethylglass microwave composite medium substrate |
| CN108189520A (en) * | 2017-12-28 | 2018-06-22 | 浙江华正新材料股份有限公司 | A kind of production method of modified polytetrafluoroethylcopper copper clad plate |
| CN110039852A (en) * | 2019-04-19 | 2019-07-23 | 中国电子科技集团公司第四十六研究所 | A kind of preparation method of PTFE copper-clad plate |
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