CN115071226A

CN115071226A - Fluorine-containing resin copper-clad plate and multilayer circuit board

Info

Publication number: CN115071226A
Application number: CN202210790497.6A
Authority: CN
Inventors: 柴颂刚; 刘潜发; 梁伟; 许永静
Original assignee: Shengyi Technology Co Ltd
Current assignee: Shengyi Technology Co Ltd
Priority date: 2022-07-05
Filing date: 2022-07-05
Publication date: 2022-09-20
Also published as: WO2024007535A1

Abstract

The invention provides a fluorine-containing resin copper-clad plate and a multilayer circuit board, wherein the fluorine-containing resin copper-clad plate comprises a copper foil, one or the combination of two of at least one prepreg layer of fluorine-containing resin glass fiber cloth and at least one resin film layer of fluorine-containing resin, and at least one prepreg layer of fluorine-containing resin non-woven fabric, wherein the prepreg of the fluorine-containing resin non-woven fabric comprises fluorine-containing resin adhesive non-woven fabric and a fluorine-containing resin composition. The fluorine-containing resin copper-clad plate has excellent dielectric property and lower size shrinkage, can meet the requirements of high-frequency electronic circuit substrates on the comprehensive properties of low dielectric constant, low dielectric loss, low insertion loss, high reliability and the like, and can be applied to electronic products as a circuit board.

Description

Fluorine-containing resin copper-clad plate and multilayer circuit board

Technical Field

The invention belongs to the technical field of laminated boards, and relates to a fluorine-containing resin copper-clad board and a multilayer circuit board.

Background

The copper-clad plate is widely applied to the fields of mobile phones, computers, vending machines, communication base stations, satellites, wearable equipment, unmanned vehicles, unmanned aerial vehicles, intelligent robots and the like as one of key basic materials in the electronic communication and information industries. Because of the excellent properties of low dielectric loss, high thermal stability, chemical stability and the like, the fluorine-containing resin represented by Polytetrafluoroethylene (PTFE) is an ideal matrix material for preparing the copper-clad plate. Since the 50 s of the last century, researchers gradually perfected the manufacturing process of the PTFE-based copper-clad plate through continuous optimization of the formula and parameters.

The fluorine-containing resin has high polymer chain flexibility, and an inorganic material is usually required to be introduced to improve the mechanical strength of the fluorine-containing resin-based copper-clad plate. The addition of inorganic filler, the use of woven glass fiber cloth, and the use of random glass fiber mats (also known as non-woven fabrics, glass fiber paper) are three common ways in the industry to improve the mechanical strength of fluorine-containing resins. The fluorine-containing film prepared by adding inorganic filler into fluorine-containing resin is modified by adopting high-purity low-loss ceramic filler and surface treatment, so that the film has the best electrical property and the optimal dielectric loss; the disadvantages are poor mechanical strength and poor dimensional stability of the film. The fluorine-containing lacquer cloth prepared by impregnating and weaving the glass fiber cloth with the fluorine-containing resin has the best mechanical strength and good dimensional stability; the disadvantages are that the dielectric loss caused by the glass fiber is poor and the uniformity of the dielectric constant of the material at different positions caused by the weaving structure is poor. The prepreg prepared by impregnating the traditional non-woven fabric with the fluorine-containing resin is large in dielectric loss due to the fact that the traditional non-woven fabric generally adopts epoxy binders, acrylate binders, melamine binders or polyvinyl alcohol binders; meanwhile, random glass fibers in the non-woven fabric have no directionality, so that the uniformity of dielectric constants of different positions of the prepreg is good. The three structures of the fluorine-containing resin materials have the characteristics of performance.

Therefore, the development of a fluorine-containing resin copper-clad plate with excellent dielectric property, mechanical strength and low dimensional expansion and contraction is a problem to be solved in the field.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a fluorine-containing resin copper-clad plate and a multilayer circuit board, wherein the fluorine-containing resin copper-clad plate has excellent dielectric property, mechanical strength and low dimensional expansion and contraction, can meet the requirements of high-frequency electronic circuit substrates on comprehensive properties such as low dielectric constant, low dielectric loss, low insertion loss, high reliability and the like, and can be used as a circuit board in electronic products.

In order to achieve the purpose, the invention adopts the following technical scheme:

in one aspect, the invention provides a fluorine-containing resin copper-clad plate which comprises a copper foil, at least one prepreg layer of fluorine-containing resin glass fiber cloth, at least one resin film layer of fluorine-containing resin, or a combination of the two, and at least one prepreg layer of fluorine-containing resin non-woven fabric, wherein the prepreg of the fluorine-containing resin non-woven fabric comprises fluorine-containing resin adhesive non-woven fabric and a fluorine-containing resin composition.

In the invention, the copper-clad plate comprises a prepreg layer of fluorine-containing resin non-woven fabric, and one or two of the prepreg layer of fluorine-containing resin glass fiber cloth and a resin film layer of fluorine-containing resin. That is, the copper-clad plate may include a prepreg layer of fluorine-containing resin non-woven fabric and a prepreg layer of fluorine-containing resin glass fiber cloth; the copper-clad plate can also comprise a prepreg layer of fluorine-containing resin non-woven fabric and a resin film layer of fluorine-containing resin; the copper-clad plate can also comprise a prepreg layer of fluorine-containing resin non-woven fabric, a prepreg layer of fluorine-containing resin glass fiber cloth and a resin film layer of fluorine-containing resin. The copper clad laminate is formed by the copper foil and at least one or the combination of two of the prepreg layer of at least one piece of fluorine-containing resin non-woven fabric, the prepreg layer of at least one piece of fluorine-containing resin glass fiber cloth and at least one piece of resin film layer of fluorine-containing resin, so that the copper clad laminate has low dielectric constant and dielectric loss and low size expansion and contraction.

In the invention, the Dk dielectric constant of the fluorine-containing resin copper-clad plate under the frequency of 10GHz is 2.2-10.2, and the dielectric loss tangent Df is less than 0.003.

Preferably, the non-woven fabric of the fluorine-containing resin adhesive consists of inorganic fibers and a binder, wherein the binder is fluorine-containing resin emulsion. The nonwoven fabric composed of the binder and the inorganic fibers has low dielectric loss, good uniformity, uniform thickness, uniform fiber isotropic distribution, and high specific tensile strength with respect to the resin film layer of the fluorine-containing resin.

Preferably, the fluororesin adhesive nonwoven has 60-95% (e.g., 60%, 62%, 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, 88%, 90%, 93%, or 95%) by weight of inorganic fibers and 5-40% (e.g., 5%, 8%, 10%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33%, 35%, 38%, or 40%) by weight of binder. In the invention, if the weight percentage of the binder is too low, the binder cannot continuously form a film, so that the strength of the non-woven fabric is low, and if the weight percentage of the binder is too high, the non-woven fabric has many internal cavities and many defects, so that the strength of the non-woven fabric is low, and further the dielectric loss and the cohesiveness are influenced.

Preferably, the fluorine-containing resin emulsion is selected from any one of or a combination of at least two of polytetrafluoroethylene emulsion, fluorinated ethylene propylene emulsion, polyvinylidene fluoride emulsion, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, ethylene-tetrafluoroethylene copolymer emulsion, polychlorotrifluoroethylene emulsion, or ethylene-chlorotrifluoroethylene copolymer emulsion.

Preferably, the fluorine-containing resin emulsion has a solids content of 30 to 70%, such as 30%, 35%, 38%, 40%, 45%, 50%, 55%, 60%, 65%, or 70%.

Preferably, the fluororesin particle size in the fluororesin emulsion is 0.10 to 0.40. mu.m.

The particle size of the fluorine-containing resin emulsion is tested by a laser diffraction method, and a testing instrument is a Markov laser particle size analyzer, model MS 3000. The dielectric constant and dielectric loss were measured by the SPDR (split post dielectric resonator) method at a frequency of 10 GHz.

Preferably, the binder further comprises any one or a combination of at least two of a defoamer, a dispersant or a thickener.

Preferably, the inorganic fiber is selected from any one of E glass fiber, NE glass fiber, L glass fiber, quartz fiber, alumina fiber, boron nitride fiber, silicon carbide fiber, zinc oxide fiber, magnesium oxide fiber, silicon nitride fiber, boron carbide fiber, aluminum nitride fiber, alumina whisker, boron nitride whisker, silicon carbide whisker, zinc oxide whisker, magnesium oxide whisker, silicon nitride whisker, boron carbide whisker or aluminum nitride whisker or a combination of at least two thereof.

Preferably, the inorganic fibers have an average diameter of less than 13 microns, such as 12 microns, 9 microns, 8 microns, 7 microns, 6 microns, 5 microns, 4 microns, 3 microns, 2 microns, 1 micron, or the like, preferably 0.5 to 5 microns.

Preferably, the inorganic fibers have an average length of 1 to 100 mm, such as 100 mm, 90 mm, 80mm, 70 mm, 60 mm, 50 mm, 40 mm, 30 mm, 20 mm, 10 mm, 5 mm, preferably 1 to 10 mm.

The average diameter and the average length of the inorganic fibers are obtained by adopting a scanning electron microscope observation test.

Preferably, the non-woven cloth of the fluorine-containing resin adhesive is subjected to surface treatment.

Preferably, the adhesive can be diluted to a suitable viscosity by adding a solvent as needed to disperse the fibers and the binder uniformly, wherein the solvent exemplarily comprises deionized water and the like. The solvent can volatilize along with the drying and sintering of the non-woven fabric preparation process.

Preferably, the fluororesin adhesive nonwoven has a basis weight (also referred to as mass per unit area) of 20 to 200 g/m, for example 20 g/m, 25 g/m, 30 g/m, 35 g/m, 40 g/m, 50 g/m, 60 g/m, 80 g/m, 100 g/m, 120 g/m, 150 g/m, 180 g/m or 200 g/m, preferably 20 to 100 g/m.

In the invention, the non-woven cloth containing the fluorine resin adhesive can be prepared by the following method: and mixing inorganic fibers with a binder, soaking, papermaking forming, drying and sintering to obtain the low dielectric loss non-woven fabric.

In the present invention, the laboratory prepared nonwoven fabrics of different basis weights by adjusting the weight of the inorganic fiber and the adhesive. The industrial production can prepare the non-woven fabrics with different single weights by adjusting the solubility of inorganic fibers, adhesives and solvents and the vehicle speed.

Preferably, the time of the immersion is 40-50 min, such as 40min, 43min, 45min, 48min or 50 min.

Preferably, the drying temperature is 120-150 ℃, such as 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃, and the drying time is 1-30 min, such as 5min, 8min, 10min, 15min, 20min, 25min or 30 min.

Preferably, the sintering temperature is 250-350 ℃, such as 260 ℃, 270 ℃, 290 ℃, 300 ℃, 320 ℃ or 340 ℃, and the sintering time is 1-20 min, such as 1min, 3min, 5min, 8min, 10min, 13min, 15min, 18min or 20 min.

Preferably, the prepreg of the fluororesin nonwoven fabric comprises a fluororesin adhesive nonwoven fabric and a fluororesin composition attached thereto by impregnation.

Preferably, the prepreg of the fluorine-containing resin glass fiber cloth comprises glass fiber cloth and a fluorine-containing resin composition.

Preferably, the resin film of fluorine-containing resin is prepared by coating a fluorine-containing resin composition on a release material.

Preferably, the fluororesin composition in the prepreg of the fluororesin nonwoven fabric, the prepreg of the fluororesin glass fiber cloth, and the fluororesin resin film each independently comprises a fluororesin emulsion.

Preferably, the fluorine-containing resin emulsion in the prepreg of the fluorine-containing resin non-woven fabric, the prepreg of the fluorine-containing resin glass fiber cloth and the resin film of the fluorine-containing resin is independently selected from any one or a combination of at least two of polytetrafluoroethylene emulsion, fluorinated ethylene propylene emulsion, polyvinylidene fluoride emulsion, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, ethylene-tetrafluoroethylene copolymer emulsion, polychlorotrifluoroethylene emulsion and ethylene-chlorotrifluoroethylene copolymer emulsion.

Preferably, the fluororesin composition in the prepreg of the fluororesin nonwoven fabric, the prepreg of the fluororesin glass fiber cloth, and the fluororesin resin film each independently further contains a filler selected from any one or a combination of at least two of silica, hollow microspheres, titanium dioxide, boron nitride, aluminum nitride, silicon carbide, alumina, barium titanate, strontium titanate, magnesium titanate, calcium titanate, barium strontium titanate, barium calcium titanate, lead zirconate titanate, chopped glass fiber powder, and chopped quartz fiber powder.

Preferably, the fluorine-containing resin composition in the prepreg of the fluorine-containing resin non-woven fabric, the prepreg of the fluorine-containing resin glass fiber cloth and the resin film of the fluorine-containing resin each independently further comprises a coupling agent.

Preferably, the fluorine-containing resin composition in the prepreg of the fluorine-containing resin non-woven fabric, the prepreg of the fluorine-containing resin glass fiber cloth and the resin film of the fluorine-containing resin each independently further comprises a surfactant.

As a preferred technical scheme, the fluorine-containing resin copper-clad plate sequentially comprises the following layers from top to bottom:

a first copper foil layer;

at least one first fluororesin film layer;

at least one prepreg layer of a fluorine-containing resin non-woven fabric;

at least one second fluororesin film layer;

a second copper foil layer.

In this preferred structure, the resin film layer of the fluorine-containing resin is in contact with the copper foil layer, and the prepreg layer of the fluorine-containing resin nonwoven fabric is interposed, so that the copper foil does not directly contact the inorganic fibers, thereby maintaining high adhesion.

Preferably, the individual layer thicknesses of the first fluorine-containing resin film layer and the second fluorine-containing resin film layer are independently 20 to 200 μm, for example 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 130 μm, 150 μm, 180 μm or 200 μm.

Preferably, the prepreg layer of the fluorine-containing resin nonwoven fabric has a single layer thickness of 100-2000. mu.m, such as 100. mu.m, 150. mu.m, 200. mu.m, 300. mu.m, 500. mu.m, 800. mu.m, 1000. mu.m, 1300. mu.m, 1500. mu.m, 1800. mu.m, or 2000. mu.m.

As another preferred technical scheme, the fluorine-containing resin copper-clad plate sequentially comprises the following layers from top to bottom:

a first copper foil layer;

at least one prepreg layer of a first fluorine-containing resin non-woven fabric;

at least one prepreg layer of fluororesin glass fiber cloth;

at least one prepreg layer of a second fluorine-containing resin non-woven fabric;

a second copper foil layer.

In the preferable structure, the prepreg layer of the fluorine-containing resin non-woven fabric is in contact with the copper foil layer, and the prepreg layer of the fluorine-containing resin glass fiber cloth is arranged in the middle of the structure, so that the copper-clad plate has excellent dimensional stability due to the fact that the prepreg layer of the glass fiber plate is arranged in the middle of the structure; meanwhile, the prepreg layer of the outer fluorine-containing resin non-woven fabric has good dielectric constant uniformity, so that the copper-clad plate has uniform dielectric constant.

In this preferred structure, the single layer thickness of the prepreg layer of the first fluorine-containing resin nonwoven fabric and the prepreg layer of the second fluorine-containing resin nonwoven fabric are independently 100-2000 micrometers, for example, 100 micrometers, 150 micrometers, 200 micrometers, 300 micrometers, 500 micrometers, 800 micrometers, 1000 micrometers, 1300 micrometers, 1500 micrometers, 1800 micrometers, or 2000 micrometers.

In this preferred construction, the prepreg layer of the fluororesin fiberglass cloth has a single layer thickness of 30 to 300 microns, such as 30 microns, 50 microns, 80 microns, 100 microns, 150 microns, 200 microns, 250 microns, or 300 microns.

In another aspect, the invention provides a multilayer circuit board, which comprises the fluorine-containing resin copper-clad plate.

Compared with the prior art, the invention has the following beneficial effects:

the fluorine-containing resin copper-clad plate has excellent dielectric property and lower size shrinkage, can meet the requirements of high-frequency electronic circuit substrates on the comprehensive properties of low dielectric constant, low dielectric loss, low insertion loss, high reliability and the like, and can be applied to electronic products as a circuit board.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The experimental materials used in the examples and comparative examples of the present invention were as follows:

non-woven fabric, made of epoxy binder and E glass fibers with an average diameter of 13 μm, Shaanxi walt.

A nonwoven fabric made from an acrylate binder and E glass fibers with an average diameter of 13 μm, Shaanxi walt.

Non-woven fabric, made of melamine binder and E glass fibers with an average diameter of 13 μm, Shaanxi walter.

Preparation example 1 fluorine-containing resin composition preparation

45 parts by weight of a polytetrafluoroethylene emulsion (PTFE emulsion, particle size 0.25 μm, solids content 55%, D210C from Dajin Japan) and 25 parts by weight of silica (average particle size 10 μm, available from Murray, Jiangsu Co., Ltd.) were added, stirred and mixed for 2 hours to obtain a fluororesin composition A-1.

50 parts by weight of a polytetrafluoroethylene emulsion (PTFE emulsion, particle diameter 0.25 μm, solid content 55%, D210C from Dajin, Japan) and 5 parts by weight of an FEP resin emulsion (solid content 50 wt%, manufactured by Dajin, Japan, trade name: ND-110) and 20 parts of boron nitride (average particle diameter 10 μm, available from Anhui Yishitong), 3 parts of titanium dioxide (average particle diameter 10 μm, available from Wuxinuoao) and 15 parts of silica (average particle diameter 10 μm, available from Jiangsu Birao) were stirred and mixed for 2 hours to obtain a fluorine-containing resin composition A-2.

Preparation example 2 preparation of fluorine-containing resin nonwoven Fabric

Mixing and soaking inorganic fibers, an adhesive and a solvent, placing the mixture into a round standard sheet machine (Kumagaya Riki Kogyo Co., Ltd.), fully stirring and filtering, and obtaining the round non-woven fabric with the diameter of 80mm through paper making molding, drying and sintering. The non-woven fabrics with different single weights are prepared by adjusting the weight of the inorganic fiber and the adhesive. The method comprises the following specific steps:

95 parts by weight of E glass fiber (average diameter of 5 microns, China giant Stone Co., Ltd.), 5 parts by weight of FEP resin emulsion (solid content of 50 wt%, manufactured by Japan Dajin Co., Ltd.; trade mark: ND-110) and a proper amount of deionized water were dipped for 45min, formed by papermaking, dried in a 150 ℃ oven, sintered for 15min in a high temperature oven at 270 ℃, and cooled to obtain a 20 g/m single-weight nonwoven fabric A.

70 parts by weight of quartz fiber (average diameter of 0.5 mu m and 5 mu m, weight ratio of 1:4, China spirit), 30 parts by weight of ETFE emulsion (solid content of 50 wt%, Shandong Yue sample) and a proper amount of deionized water are soaked for 45min, paper making and forming are carried out, drying is carried out in a 140 ℃ oven, sintering is carried out for 25min in a high temperature oven at 280 ℃, and the non-woven fabric B with the single weight of 75 g/square meter is obtained after taking out and cooling.

Preparation example 3 preparation of prepreg of fluororesin nonwoven Fabric

Impregnating the non-woven fabric A with the fluorine-containing resin composition A-1, drying for 1h in a 100 ℃ oven, sintering for 0.5h in a 360 ℃ oven, and adjusting the impregnation times to respectively obtain the fluorine-containing resin non-woven fabric prepreg A with the thickness of 130 mu m and 150 mu m.

Impregnating the non-woven fabric B with the fluorine-containing resin composition A-2, drying for 1h in a 100 ℃ oven, sintering for 0.5h in a 360 ℃ oven, and adjusting the impregnation times to respectively obtain the fluorine-containing resin non-woven fabric prepreg B with the thickness of 130 mu m and 150 mu m.

Preparation example 4 preparation of fluororesin film

Coating the fluorine-containing resin composition A-1 on a steel plate with a clean and smooth surface, drying for 1h in a vacuum oven at 100 ℃, removing water, baking for 1h at 260 ℃ to remove an auxiliary agent, baking for 10min at 350 ℃, cooling, peeling the filler-containing resin film from the steel plate, and adjusting different coating gaps to obtain resin films A of the fluorine-containing resin with the thicknesses of 50 mu m, 100 mu m and 150 mu m respectively.

Coating the fluorine-containing resin composition A-2 on a steel plate with a clean and smooth surface, drying for 1h in a vacuum oven at 100 ℃, removing water, baking for 1h at 260 ℃ to remove an auxiliary agent, baking for 10min at 350 ℃, cooling, peeling the filler-containing resin film from the steel plate, and adjusting different coating gaps to obtain the fluorine-containing resin film B with the thicknesses of 50 microns, 100 microns and 150 microns respectively.

Preparation example 5 preparation of fluorine-containing resin woven glass fiber varnished cloth

The method comprises the following steps:

impregnating the glass fiber cloth with the fluorine-containing resin composition A-1, drying for 1h in a drying oven at 100 ℃, sintering for 0.5h in the drying oven at 360 ℃, and adjusting a coating gap to obtain fluorine-containing resin woven glass fiber varnished cloth A with the thickness of 50 mu m;

impregnating the fluorine-containing resin composition A-2 on the glass fiber cloth, drying for 1h in a drying oven at 100 ℃, sintering for 0.5h in a drying oven at 360 ℃, and adjusting the coating gap to obtain fluorine-containing resin woven glass fiber varnished cloth B with the thickness of 50 microns;

preparation of comparative example 1

The fluorine-containing resin composition A-1 was impregnated into an epoxy adhesive nonwoven fabric (prepared from an epoxy adhesive and E glass fibers having an average diameter of 13 μm), dried in an oven at 100 ℃ for 1 hour, sintered in an oven at 360 ℃ for 0.5 hour, and applied to a gap by adjusting the coating gap, to obtain a prepreg having a thickness of 130 μm.

Preparation of comparative example 2

The same applies to the preparation of comparative example 1 except that the nonwoven fabric with an epoxy binder was replaced with the nonwoven fabric with an acrylate binder.

Preparation of comparative example 3

The same applies to the preparation of comparative example 1 except that the epoxy-bonded nonwoven fabric was replaced with the melamine-bonded nonwoven fabric.

Example 1

The fluorine-containing resin copper-clad plate provided by the embodiment sequentially comprises the following layers from top to bottom:

1 sheet of 1OZ copper foil layer, HVLP, Jiangxi copper;

1 resin film layer A of fluorine-containing resin with the thickness of 50 mu m;

1 prepreg A of fluorine-containing resin non-woven fabric with the thickness of 150 mu m;

1 sheet of 1OZ copper foil, HVLP, Jiangxi copper.

And (3) putting the laminated structure into a press for curing, applying pressure of about 400PSI, keeping the maximum temperature at 380 ℃ for 90min, and laminating to obtain the copper-clad plate.

Example 2

1 piece of 1OZ copper foil layer of fluorine-containing resin copper-clad plate, HVLP, Jiangxi copper industry;

1 resin film layer B of fluorine-containing resin, the thickness is 100 μm;

2 prepreg layers B of fluorine-containing resin non-woven fabrics, and the single-layer thickness is 130 mu m;

1 resin film layer B of fluorine-containing resin, the thickness is 100 μm;

1 sheet of 1OZ copper foil, HVLP, Jiangxi copper.

Example 3

The fluorine-containing resin copper-clad plate provided by the embodiment sequentially comprises the following layers from top to bottom: fluorine-containing resin copper-clad plate

1 sheet of 1OZ copper foil layer, HVLP, Jiangxi copper;

2 resin film layers A containing fluorine resin, the single-layer thickness is 150 mu m;

1 prepreg layer B of fluorine-containing resin non-woven fabric, the thickness is 130 μm;

1 sheet of 1OZ copper foil, HVLP, Jiangxi copper.

Example 4

1 prepreg layer A of fluorine-containing resin non-woven fabric, the thickness is 130 μm;

1 piece of fluorine-containing resin woven glass fiber varnished cloth A with the thickness of 50 mu m;

1 sheet of 1OZ copper foil, HVLP, Jiangxi copper.

Example 5

2 pieces of fluorine-containing resin woven glass fiber varnished cloth B with the single-layer thickness of 50 mu m;

1 sheet of 1OZ copper foil, HVLP, Jiangxi copper.

Example 6

1 sheet of 1OZ copper foil layer, HVLP, Jiangxi copper;

1 resin film layer A of fluorine-containing resin, the single-layer thickness is 150 μm;

1 piece of fluorine-containing resin woven glass fiber varnished cloth A with the single-layer thickness of 50 mu m;

1 sheet of 1OZ copper foil, HVLP, Jiangxi copper.

Comparative example 1

The fluorine-containing resin copper-clad plate provided by the comparative example sequentially comprises the following layers from top to bottom:

1 sheet of 1OZ copper foil layer, HVLP, Jiangxi copper industry;

3 prepreg layers of comparative example 1 were prepared, with a monolayer thickness of 130 μm;

1 sheet of 1OZ copper foil, HVLP, Jiangxi copper.

Comparative example 2

The polytetrafluoroethylene copper-clad plate provided by the comparative example sequentially comprises the following layers from top to bottom:

1 sheet of 1OZ copper foil layer, HVLP, Jiangxi copper industry;

3 pieces of fluorine-containing resin woven glass fiber varnished cloth A with the single-layer thickness of 50 mu m;

1 sheet of 1OZ copper foil, HVLP, Jiangxi copper.

Comparative example 3

1 sheet of 1OZ copper foil layer, HVLP, Jiangxi copper;

5 resin film layers A containing fluorine resin, the single-layer thickness of which is 50 mu m;

1 sheet of 1OZ copper foil, HVLP, Jiangxi copper.

Comparative example 4

The prepreg of example 1 was replaced with the prepreg prepared in comparative example 1, except that the prepreg layer of 1 sheet of fluorine-containing resin nonwoven fabric in example 1 was used in the same manner as in example 1.

Comparative example 5

The prepreg of example 1 was replaced with the prepreg prepared in comparative example 2, and the same procedure as in example 1 was repeated, except that the prepreg layer of 1 sheet of the fluorine-containing resin nonwoven fabric in example 1 was replaced with the prepreg prepared in comparative example 1.

Comparative example 6

The prepreg of example 1 was replaced with the prepreg prepared in comparative example 3, except that the prepreg layer of 1 sheet of fluorine-containing resin nonwoven fabric in example 1 was used in the same manner as in example 1.

Comparative example 7

The prepreg layers of the fluororesin nonwoven fabric in example 4 were replaced with the prepreg prepared in comparative example 1, and the same procedure as in example 1 was repeated, except for the difference from example 4.

Comparative example 8

The same procedure as in example 1 was repeated, except that the prepreg layers of the fluororesin nonwoven fabric in example 4 were replaced with the prepreg prepared in comparative example 2.

Comparative example 9

The same procedure as in example 1 was repeated, except that the prepreg layers of the fluororesin nonwoven fabric in example 4 were replaced with the prepreg prepared in comparative example 3.

Performance test

Aiming at the copper-clad plates prepared by the embodiments and the comparative examples, the following performance tests are carried out:

(1) dk and Df test: testing by using an SPDR (split post dielectric resonator) method; the test condition is A state, and the frequency is 10 GHz;

(2) dimensional stability: the X/Y dimensional stability was tested using IPC-TM-6502.4.39.

The specific test results are shown in table 1:

TABLE 1

As can be seen from examples 1 to 6, the copper-clad plate containing the non-woven fabric prepreg has a dielectric constant of 3.06 to 3.15, a dielectric loss of less than 0.002, and a dimensional stability of less than 1500ppm, and has both dielectric loss and dimensional stability. In contrast, it can be seen from comparative example 1 that the dielectric loss of the sheet prepared from the impregnant of the nonwoven fabric prepared entirely using the epoxy adhesive was high. Compared with the comparative example 2, the glass fiber varnished cloth is woven by the fluorine-containing resin, so that the dielectric loss of the plate is higher; by comparative example 3, in which the fluororesin film was entirely used, the dimensional stability of the plate material was the worst.

By using the nonwoven fabrics of comparative examples 4-6 with non-fluororesin adhesives, the dielectric loss of the board was higher and the dielectric constant was higher than in example 1.

With the nonwoven fabrics of comparative examples 7-9 using non-fluororesin adhesives, the dielectric loss of the sheet was higher and the dielectric constant was higher than that of example 4.

In summary, the copper clad laminate structure of the present invention has excellent dielectric properties and low dimensional expansion, and can be applied to the field of high frequency communication.

The applicant states that the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented depending on the above embodiments. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. The fluorine-containing resin copper-clad plate is characterized by comprising a copper foil, at least one prepreg layer of fluorine-containing resin glass fiber cloth, at least one resin film layer of fluorine-containing resin or a combination of the two, and at least one prepreg layer of fluorine-containing resin non-woven fabric, wherein the prepreg of the fluorine-containing resin non-woven fabric comprises fluorine-containing resin adhesive non-woven fabric and a fluorine-containing resin composition.

2. The fluororesin copper-clad plate according to claim 1, wherein the Dk dielectric constant of the fluororesin copper-clad plate at a frequency of 10GHz is 2.2 to 10.2, and the dielectric loss tangent Df is less than 0.003.

3. The fluororesin copper-clad plate according to claim 1 or 2, wherein the fluororesin adhesive non-woven fabric comprises inorganic fibers and a binder, and the binder is a fluororesin emulsion;

preferably, the weight percentage of the inorganic fiber in the non-woven fabric of the fluorine-containing resin adhesive is 60-95%, and the weight percentage of the adhesive is 5-40%;

preferably, the fluorine-containing resin emulsion is selected from any one of or a combination of at least two of polytetrafluoroethylene emulsion, fluorinated ethylene propylene emulsion, polyvinylidene fluoride emulsion, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, ethylene-tetrafluoroethylene copolymer emulsion, polychlorotrifluoroethylene emulsion or ethylene-chlorotrifluoroethylene copolymer emulsion;

preferably, the fluorine-containing resin emulsion has a solid content of 30-70%;

preferably, the binder further comprises any one or a combination of at least two of a defoaming agent, a dispersing agent or a thickening agent.

4. The fluororesin copper-clad plate according to any one of claims 1 to 3, wherein the inorganic fibers are selected from any one or a combination of at least two of E glass fibers, NE glass fibers, L glass fibers, quartz fibers, alumina fibers, boron nitride fibers, silicon carbide fibers, zinc oxide fibers, magnesium oxide fibers, silicon nitride fibers, boron carbide fibers, aluminum nitride fibers, alumina whiskers, boron nitride whiskers, silicon carbide whiskers, zinc oxide whiskers, magnesium oxide whiskers, silicon nitride whiskers, boron carbide whiskers or aluminum nitride whiskers;

preferably, the inorganic fibers have an average diameter of less than 13 microns, preferably 0.5 to 5 microns;

preferably, the inorganic fibers have an average length of 1 to 100 mm, preferably 1 to 10 mm;

preferably, the non-woven cloth of the fluorine-containing resin adhesive is subjected to surface treatment;

preferably, the single weight of the non-woven cloth of the fluorine-containing resin adhesive is 20 to 200 g/square meter.

5. The fluororesin copper-clad plate according to any one of claims 1 to 4, wherein the prepreg of fluororesin glass fiber cloth comprises glass fiber cloth and a fluororesin composition.

6. The fluororesin copper-clad plate according to any one of claims 1 to 5, wherein the fluororesin resin film is prepared by coating a fluororesin composition on a release material.

7. The fluororesin copper-clad plate according to any one of claims 1 to 6, wherein the fluororesin composition in the prepreg of the fluororesin non-woven fabric, the prepreg of the fluororesin glass fiber cloth and the fluororesin resin film each independently comprises a fluororesin emulsion;

preferably, the fluorine-containing resin emulsion in the prepreg of the fluorine-containing resin non-woven fabric, the prepreg of the fluorine-containing resin glass fiber cloth and the resin film of the fluorine-containing resin is independently selected from any one or a combination of at least two of polytetrafluoroethylene emulsion, fluorinated ethylene propylene emulsion, polyvinylidene fluoride emulsion, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer emulsion, ethylene-tetrafluoroethylene copolymer emulsion, polychlorotrifluoroethylene emulsion or ethylene-chlorotrifluoroethylene copolymer emulsion;

preferably, the fluorine-containing resin composition further comprises a filler selected from any one or a combination of at least two of silica, hollow microspheres, titanium dioxide, boron nitride, aluminum nitride, silicon carbide, alumina, barium titanate, strontium titanate, magnesium titanate, calcium titanate, barium strontium titanate, barium calcium titanate, lead zirconate titanate, chopped glass fiber powder or chopped quartz fiber powder;

preferably, the fluorine-containing resin composition further comprises a coupling agent;

preferably, the fluorine-containing resin composition further comprises a surfactant.

8. The fluororesin copper-clad plate according to any one of claims 1 to 7, wherein the fluororesin copper-clad plate comprises the following layers combined together in sequence from top to bottom:

a first copper foil layer;

at least one first fluororesin film layer;

at least one prepreg layer of fluorine-containing resin non-woven fabric;

at least one second fluororesin film layer;

a second copper foil layer;

preferably, the single layer thickness of the resin film layer of the first fluorine-containing resin and the resin film layer of the second fluorine-containing resin are independently 20 to 200 μm;

preferably, the prepreg layer of the fluorine-containing resin non-woven fabric has a single-layer thickness of 100-2000 μm.

9. The fluororesin copper-clad plate according to any one of claims 1 to 7, wherein the fluororesin copper-clad plate comprises the following layers combined together in sequence from top to bottom:

a first copper foil layer;

at least one prepreg layer of fluororesin glass fiber cloth;

a second copper foil layer;

preferably, the single-layer thickness of the prepreg layer of the first fluorine-containing resin non-woven fabric and the prepreg layer of the second fluorine-containing resin non-woven fabric is independently 100-2000 μm;

preferably, the prepreg layer of the fluorine-containing resin glass fiber cloth has a single-layer thickness of 30 to 300 μm.

10. A multilayer circuit board comprising the fluororesin copper-clad laminate according to any one of claims 1 to 9.