CN103102627B - A kind of high filler content PTFE base material, preparation method and its usage - Google Patents
A kind of high filler content PTFE base material, preparation method and its usage Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of high filler content PTFE copper-clad plate, first fluororesin powder is mixed with mineral filler, then add lubricant, stir into dough object, then carry out extruding, the operation such as calendering, obtain sheet material, this sheet material is heat-treated, then floods this sheet material with fluoro-resin dispersion emulsion, and carry out drying, bake and bank up with earth, sinter, obtain the sheet material that hole is few, one deck resin molding has been covered on surface, with the copper-clad plate that this sheet material makes, there is good over-all properties.
Description
Technical field
The present invention relates to a kind of PTFE base material, preparation method and its usage, particularly, the present invention relates to a kind of high filler content PTFE base material, preparation method and its usage.
Background technology
Information electronic product is gradually towards high frequency, high speed future development.Traditional baseplate material will be replaced by high speed, high reliability baseplate material gradually.In recent years, scientific worker conducts in-depth research the selection of high frequency, high speed baseplate material and performance, is intended to find the excellent baseplate material of dielectric properties, mechanical property and thermal characteristics, the requirement used with satisfied reality.
Polytetrafluoroethylene (PTFE) from 1945 by since E.I.Du Pont Company's merchandized handling, due to physicals and the chemical property of this material uniqueness, people just constantly open up the application of this material in every field, and result of study shows, tetrafluoroethylene has excellent electric property, resistance to chemical attack, heat-resisting, use temperature scope is wide, and water-absorbent is low, specific inductivity in high-frequency range, dielectric loss factor are with low uncertainty, are highly suitable for the matrix resin as high-speed digitization and high frequency substrate material.The outstanding dielectric properties of PTFE material (low-k and low dielectric loss) are utilized to manufacture the existing history for many years of copper-clad plate of frequency applications.
The most conventional is that the technique making dipping glass-fiber-fabric as FR-4 manufactures without glass-fiber-fabric enhancement type PTFE copper-clad plate, but when manufacturing the PTFE copper-clad plate of high filler content (filler content >=50%), and the technique of dipping glass-fiber-fabric is also inapplicable.US Patent No. 4335180 describes a kind of preparation method of PTFE copper-clad plate of high filler content: by fluoropolymer emulsion, filler, blending in of fibers, stir into soup compound (slurry), then flocculation agent (flocculant) is added, make fluorinated resin particle, filler and fiber etc. are condensed into dough/pasta shape (dough-like) object, this object is filtered, drying treatment (160 DEG C/24 hours), obtain the mixture (chunk) of shred, again lubricant is joined in this shred mixture, be uniformly mixed fully, and by extruding, the operations such as calendering make certain thickness sheet material, this sheet material carries out toasting (246 DEG C/24 hours) again, cover Copper Foil more afterwards, carry out lamination, namely the PTFE copper-clad plate with high filler content is obtained.This method can produce a large amount of waste water, complex process, and manufacturing cost is high; And after lubricant dried, can there is more cavity in base material inside, cause the water-intake rate of sheet material large.
Summary of the invention
An object of the present invention is a kind of preparation method of high filler content PTFE base material, the method operation is relatively simple, waste water can not be produced, there is not cavity in the base material inside obtained, the water-intake rate of base material also declines greatly, can obtain the good high filler content PTFE base material of over-all properties by the method.
In order to achieve the above object, present invention employs following technical scheme:
A preparation method for high filler content PTFE base material, described method comprises the steps:
(1) fluororesin powder is mixed with mineral filler, obtain the mixture of fluororesin powder and mineral filler, then add lubricant, continue to stir, obtain dough;
(2) extruded by the dough that step (1) obtains, calendering, obtains sheet material;
(3) sheet material that step (2) obtains is heat-treated, to remove lubricant;
(4) sheet material after thermal treatment is infiltrated fluoro-resin dispersion emulsion, after leaving standstill, dry, cure, sintering, obtains high filler content PTFE base material.
Utilize fluororesin powder and the direct dry mixed mode of mineral filler, by carrying out the PTFE base material of obtained high filler content to the post-processed of sheet material, base material internal voids rate diminishes, the water-intake rate of base material also declines greatly, over-all properties is very excellent, solve previous art process complexity, not environmentally, the problem such as production efficiency is low.
Described fluororesin powder is selected from the mixture of any one or at least two kinds in PTFE toner (teflon resin powder), PFA toner (tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer resin cosmetics) or FEP toner (fluorinated ethylene propylene copolymer toner).The mixture of described mixture such as PTFE toner and PFA toner, the mixture of PFA toner and FEP toner, the mixture of FEP toner and PTFE toner, the mixture of FEP toner, PFA toner and PTFE toner, preferred PTFE toner.
The particle diameter of described fluororesin powder is within 50 μm, preferably within 45 μm, further preferably within 40 μm.The particle diameter of described fluororesin powder is such as 2 μm, 5 μm, 9 μm, 15 μm, 22 μm, 27 μm, 25 μm, 38 μm, 42 μm, 46 μm, 49 μm.
Described mineral filler is selected from aluminium hydroxide, silicon-dioxide, titanium dioxide, barium titanate, talcum powder, mica, barium sulfate, zinc sulfide white, calcium carbonate, wollastonite, kaolin, brucite, diatomite, wilkinite, the mixture of any one or at least two kinds in silicon powder or pumice sand, the mixture of described mixture such as aluminium hydroxide and silicon-dioxide, silicon-dioxide and talcous mixture, the mixture of mica and barium sulfate, zinc sulfide white and talcous mixture, the mixture of calcium carbonate and wollastonite, the mixture of kaolin and brucite, diatomite and bentonitic mixture, wilkinite and talcous mixture, silicon-dioxide, aluminium hydroxide and talcous mixture, mica, barium sulfate, the mixture of zinc sulfide white and calcium carbonate, kaolin, brucite, diatomite and bentonitic mixture, preferred silicon-dioxide, the mixture of any one or at least two kinds in titanium dioxide or barium titanate, further preferably silicon-dioxide or/and titanium dioxide.
Adopt coupling agent treatment inorganic filler surface.The kind of coupling agent has: silicane class, titanate ester, phosphoric acid ester, aluminate, borate ester, aluminium titanium complex class etc.Application coupling agent not only can improve the affinity between mineral filler and polymkeric substance, reduce its surface tension, promote good moistening and coating function, and on interface, set up chemical bonding structure, thus forming firm and the most stable compound system, the effect of therefore inorganic filler surface process is embodied by the cohesive strength improved between polymkeric substance and the combination forming the various factors complexity such as special interfacial layer.The method adopting coupling agent treatment inorganic filler surface is prior art, those skilled in the art can carry out mineral filler coupling processing of the present invention according to the method for mineral filler coupling processing disclosed in prior art, to obtain the mineral filler after coupling processing, then the mineral filler after coupling processing is mixed with fluororesin powder, carry out subsequent step.
The particle diameter of described mineral filler is within 20 μm, such as 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, preferably within 17 μm, further preferably within 15 μm.
After fluororesin powder is mixed with mineral filler, stir, obtain the mixture of fluororesin powder and mineral filler.The time those skilled in the art of described stirring can determine according to the mixing situation of fluororesin powder and mineral filler, guarantees that both mix.Exemplary churning time as 0.5 ~ 1.5 hour, such as 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, preferably 1 hour.
Add lubricant can improve the dispersing property of mineral filler and improve the workability of mixture, lubricant of the present invention is selected from fat hydrocarbon, metal soap, aliphatic amide type, aliphatics acids, the mixture of any one or at least two kinds in aliphatic ester or aliphatics alcohols, the arbitrary fat hydrocarbon that those skilled in the art can be known, metal soap, aliphatic amide type, aliphatics acids, aliphatic ester, fatty alcohol series lubricant agent all can realize the present invention, preferably, described lubricant preferred fat hydro carbons, the mixture of any one or at least two kinds in aliphatics alcohols or aliphatic ester, preferred dipropylene glycol (dipropylene glycol further, DPG), polyisobutene (polyisobutylene, or dioctyl phthalate (DOP) (dioctylphthalate PIB), the mixture of any one or at least two kinds DOP).The mixture of described mixture such as DPG and PIB, the mixture of DPG and DOP, the mixture of PIB and DOP, the mixture of DPG, PIB and DOP.
After step (1) adds lubricant, stir and obtain dough.
The described heat treated temperature of step (3) is 250 ~ 350 DEG C, such as 255 DEG C, 260 DEG C, 270 DEG C, 275 DEG C, 285 DEG C, 295 DEG C, 305 DEG C, 315 DEG C, 325 DEG C, 335 DEG C, 345 DEG C, preferably 270 ~ 320 DEG C, preferably 300 DEG C further.
The described heat treated time is 1 ~ 6 hour, such as 1.2 hours, 1.4 hours, 1.8 hours, 2.2 hours, 2.6 hours, 3.2 hours, 3.8 hours, 4.2 hours, 4.6 hours, 4.8 hours, 5.2 hours, 5.6 hours, 5.8 hours, preferably 1.5 ~ 5.5 hours, preferably 2 ~ 5 hours further.
After the sheet cools after thermal treatment to normal temperature, infiltrate fluoro-resin dispersion emulsion.
Described fluoro-resin dispersion emulsion is selected from the mixture of any one or at least two kinds in PTFE emulsion, PFA emulsion or FEP emulsion, the mixture of described mixture such as FEP emulsion and PFA emulsion, the mixture of PFA emulsion and PTFE emulsion, the mixture of FEP emulsion and PTFE emulsion, the mixture of FEP emulsion, PFA emulsion and PTFE emulsion.
Solid content the present invention of described fluoro-resin dispersion emulsion is not construed as limiting this, and those skilled in the art can rule of thumb decide in its sole discretion.The solid content of described fluoro-resin dispersion emulsion can regulate by adding deionized water.
Sheet material after thermal treatment is infiltrated fluoro-resin dispersion emulsion tool to have the following advantages: after (1) thermal treatment, lubricant is removed, fluoro-resin dispersion emulsion can fill the hole and cavity that bring because lubricant removal is rear; (2) sheet material infiltrates fluoro-resin emulsion, can form layer of surface film, improve the interface binding power of PTFE base material and Copper Foil in PTFE copper-clad plate in sheet surface.
Time of repose described in step (4) is 2 ~ 7 minutes, such as 2.3 minutes, 2.7 minutes, 3.2 minutes, 3.6 minutes, 3.9 minutes, 4.3 minutes, 4.7 minutes, 5.1 minutes, 5.5 minutes, 5.9 minutes, 6.3 minutes, 6.7 minutes, 6.9 minutes, preferably 3 ~ 6 minutes, preferably 3 ~ 5 minutes further.
After leaving standstill, sheet material is taken out lentamente from fluoro-resin dispersion emulsion, then carries out drying.
The temperature of described drying is 80 ~ 150 DEG C, such as 80 DEG C, 90 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, preferably 90 ~ 120 DEG C, preferably 95 ~ 110 DEG C further.
The time of described drying is 4 ~ 12 minutes, such as 4.3 minutes, 4.6 minutes, 4.9 minutes, 5.5 minutes, 6.2 minutes, 7 minutes, 7.5 minutes, 8 minutes, 8.5 minutes, 9 minutes, 9.5 minutes, 10.2 minutes, 10.5 minutes, 11 minutes, 11.5 minutes, 11.8 minutes, preferably 5 ~ 11 minutes, preferably 5 ~ 10 minutes further.
Described temperature of curing is 200 ~ 300 DEG C, such as 205 DEG C, 210 DEG C, 215 DEG C, 221 DEG C, 225 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245 DEG C, 250 DEG C, 255 DEG C, 260 DEG C, 265 DEG C, 270 DEG C, 275 DEG C, 280 DEG C, 285 DEG C, 290 DEG C, 295 DEG C, preferably 220 ~ 280 DEG C, preferably 250 DEG C further.
The described time of curing is 4 ~ 12 minutes, such as 4.3 minutes, 4.6 minutes, 4.9 minutes, 5.5 minutes, 6.2 minutes, 7 minutes, 7.5 minutes, 8 minutes, 8.5 minutes, 9 minutes, 9.5 minutes, 10.2 minutes, 10.5 minutes, 11 minutes, 11.5 minutes, 11.8 minutes, preferably 5 ~ 11 minutes, preferably 5 ~ 10 minutes further.
The temperature of described sintering is 340 ~ 400 DEG C, such as 340 DEG C, 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C, 400 DEG C, preferably 350 ~ 390 DEG C, preferably 380 DEG C further.
The time of described sintering is 4 ~ 12 minutes, such as 4.3 minutes, 4.6 minutes, 4.9 minutes, 5.5 minutes, 6.2 minutes, 7 minutes, 7.5 minutes, 8 minutes, 8.5 minutes, 9 minutes, 9.5 minutes, 10.2 minutes, 10.5 minutes, 11 minutes, 11.5 minutes, 11.8 minutes, preferably 5 ~ 11 minutes, preferably 5 ~ 10 minutes further.
Two of object of the present invention is to provide a kind of high filler content PTFE base material, and described high filler content PTFE base material is prepared by method described above.Described high filler content PTFE base material internal voids rate is little, and water-intake rate is low, excellent combination property, can be used for preparing high filler content PTFE copper-clad plate.
Three of object of the present invention is to provide a kind of high filler content PTFE copper-clad plate, and described high filler content PTFE copper-clad plate comprises at least one high filler content PTFE base material as above, and be overlying on superimposed after the side of PTFE base material or the Copper Foil of both sides.
Four of object of the present invention is to provide a kind of high filler content PTFE preparation method of copper-clad plate, described method is: Copper Foil is covered in the side of high filler content PTFE base material as above or both sides, then lamination, can obtain high filler content PTFE copper-clad plate.
The preparation method of described high filler content PTFE copper-clad plate, comprises the steps:
(1) fluororesin powder is mixed with mineral filler, obtain the mixture of fluororesin powder and mineral filler, then add lubricant, continue to stir, obtain dough;
(2) extruded by the dough that step (1) obtains, calendering, obtains sheet material;
(3) sheet material that step (2) obtains is heat-treated, to remove lubricant;
(4) sheet material after thermal treatment is infiltrated fluoro-resin dispersion emulsion, after leaving standstill, dry, cure, sintering, obtains high filler content PTFE base material;
(5) Copper Foil is covered, then lamination in side or the both sides of PTFE base material step (4) obtained, and can obtain high filler content PTFE copper-clad plate.
Described fluororesin powder is selected from PTFE toner (teflon resin powder), the mixture of any one or at least two kinds in PFA toner (tetrafluoroethylene-perfluoro alkoxy vinyl ethers copolymer resin cosmetics) or FEP toner (fluorinated ethylene propylene copolymer toner), the mixture of described mixture such as PTFE toner and PFA toner, the mixture of PFA toner and FEP toner, the mixture of FEP toner and PTFE toner, FEP toner, the mixture of PFA toner and PTFE toner, preferred PTFE toner.
The particle diameter of described fluororesin powder is within 50 μm, preferably within 45 μm, further preferably within 40 μm.The particle diameter of described fluororesin powder is such as 2 μm, 5 μm, 9 μm, 15 μm, 22 μm, 27 μm, 25 μm, 38 μm, 42 μm, 46 μm, 49 μm.
Described mineral filler is selected from aluminium hydroxide, silicon-dioxide, titanium dioxide, barium titanate, talcum powder, mica, barium sulfate, zinc sulfide white, calcium carbonate, wollastonite, kaolin, brucite, diatomite, wilkinite, or the mixture of any one or at least two kinds in pumice sand, the mixture of described mixture such as aluminium hydroxide and silicon-dioxide, silicon-dioxide and talcous mixture, the mixture of mica and barium sulfate, zinc sulfide white and talcous mixture, the mixture of calcium carbonate and wollastonite, the mixture of kaolin and brucite, diatomite and bentonitic mixture, wilkinite and talcous mixture, silicon-dioxide, aluminium hydroxide and talcous mixture, mica, barium sulfate, the mixture of zinc sulfide white and calcium carbonate, kaolin, brucite, diatomite and bentonitic mixture, preferred silicon-dioxide, the mixture of any one or at least two kinds in titanium dioxide or barium titanate, preferred silicon-dioxide is or/and titanium dioxide further.
Preferably, coupling agent treatment inorganic filler surface is adopted.The kind of coupling agent has: silicane, titanate ester, phosphoric acid ester, aluminate, borate ester, aluminium titanium complex class etc.Application coupling agent not only can improve the affinity between mineral filler and polymkeric substance, reduce its surface tension, promote good moistening and coating function, and on interface, set up chemical bonding structure, thus forming firm and the most stable compound system, the effect of therefore inorganic filler surface process is embodied by the cohesive strength improved between polymkeric substance and the combination forming the various factors complexity such as special interfacial layer.The method adopting coupling agent treatment inorganic filler surface is prior art, those skilled in the art can carry out mineral filler coupling processing of the present invention according to the method for mineral filler coupling processing disclosed in prior art, to obtain the mineral filler after coupling processing, then the mineral filler after coupling processing is mixed with fluororesin powder, carry out subsequent step.
The particle diameter of described mineral filler is within 20 μm, such as 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, preferably within 17 μm, further preferably within 15 μm.
After fluororesin powder is mixed with mineral filler, stir, obtain the mixture of fluororesin powder and mineral filler.The time those skilled in the art of described stirring can determine according to the mixing situation of fluororesin powder and mineral filler, guarantees that both mix.Exemplary churning time as 0.5 ~ 1.5 hour, such as 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, preferably 1 hour.
Add the dispersing property that lubricant can improve mineral filler, lubricant of the present invention is selected from fat hydrocarbon, metal soap, aliphatic amide type, aliphatics acids, the mixture of any one or at least two kinds in aliphatic ester or aliphatics alcohols, the arbitrary fat hydrocarbon that those skilled in the art can be known, metal soap, aliphatic amide type, aliphatics acids, aliphatic ester, fatty alcohol series lubricant agent all can realize the present invention, preferably, described lubricant preferred fat hydro carbons, the mixture of any one or at least two kinds in aliphatics alcohols or aliphatic ester, preferred dipropylene glycol (dipropyleneglycol further, DPG), polyisobutene (polyisobutylene, or dioctyl phthalate (DOP) (dioctylphthalate PIB), the mixture of any one or at least two kinds DOP).The mixture of described mixture such as DPG and PIB, the mixture of DPG and DOP, the mixture of PIB and DOP, the mixture of DPG, PIB and DOP.
After step (1) adds lubricant, stir to obtain dough.
The described heat treated temperature of step (3) is 250 ~ 350 DEG C, such as 255 DEG C, 260 DEG C, 270 DEG C, 275 DEG C, 285 DEG C, 295 DEG C, 305 DEG C, 315 DEG C, 325 DEG C, 335 DEG C, 345 DEG C, preferably 270 ~ 320 DEG C, preferably 300 DEG C further.
The described heat treated time is 1 ~ 6 hour, such as 1.2 hours, 1.4 hours, 1.8 hours, 2.2 hours, 2.6 hours, 3.2 hours, 3.8 hours, 4.2 hours, 4.6 hours, 4.8 hours, 5.2 hours, 5.6 hours, 5.8 hours, preferably 1.5 ~ 5.5 hours, preferably 2 ~ 5 hours further.
After the sheet cools after thermal treatment to normal temperature, infiltrate fluoro-resin dispersion emulsion.
Described fluoro-resin dispersion emulsion is selected from the mixture of any one or at least two kinds in PTFE emulsion, PFA emulsion or FEP emulsion, the mixture of described mixture such as FEP emulsion and PFA emulsion, the mixture of PFA emulsion and PTFE emulsion, the mixture of FEP emulsion and PTFE emulsion, the mixture of FEP emulsion, PFA emulsion and PTFE emulsion.Solid content the present invention of described fluoro-resin dispersion emulsion is not construed as limiting this, and those skilled in the art can rule of thumb decide in its sole discretion.The solid content of described fluoro-resin dispersion emulsion can regulate by adding deionized water.
Sheet material after thermal treatment is infiltrated fluoro-resin dispersion emulsion tool to have the following advantages: after (1) thermal treatment, lubricant is removed, fluoro-resin dispersion emulsion can fill the hole and cavity that bring because lubricant removal is rear; (2) sheet material infiltrates fluoro-resin emulsion, can form layer of surface film, can improve the interface binding power of PTFE base material and Copper Foil in PTFE copper-clad plate in sheet surface.
Time of repose described in step (4) is 2 ~ 7 minutes, such as 2.3 minutes, 2.7 minutes, 3.2 minutes, 3.6 minutes, 3.9 minutes, 4.3 minutes, 4.7 minutes, 5.1 minutes, 5.5 minutes, 5.9 minutes, 6.3 minutes, 6.7 minutes, 6.9 minutes, preferably 3 ~ 6 minutes, preferably 3 ~ 5 minutes further.
After leaving standstill, sheet material is taken out lentamente from fluoro-resin dispersion emulsion, then carries out drying.
The temperature of described drying is 80 ~ 150 DEG C, such as 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, preferably 90 ~ 120 DEG C, preferably 95 ~ 110 DEG C further.
The time of described drying is 4 ~ 12 minutes, such as 4.3 minutes, 4.6 minutes, 4.9 minutes, 5.5 minutes, 6.2 minutes, 7 minutes, 7.5 minutes, 8 minutes, 8.5 minutes, 9 minutes, 9.5 minutes, 10.2 minutes, 10.5 minutes, 11 minutes, 11.5 minutes, 11.8 minutes, preferably 5 ~ 11 minutes, preferably 5 ~ 10 minutes further.
Described temperature of curing is 200 ~ 300 DEG C, such as 205 DEG C, 210 DEG C, 215 DEG C, 221 DEG C, 225 DEG C, 230 DEG C, 235 DEG C, 240 DEG C, 245,250 DEG C, 255 DEG C, 260 DEG C, 265 DEG C, 270 DEG C, 275 DEG C, 280 DEG C, 285 DEG C, 290 DEG C, 295 DEG C, preferably 220 ~ 280 DEG C, preferably 250 DEG C further.
The described time of curing is 4 ~ 12 minutes, such as 4.3 minutes, 4.6 minutes, 4.9 minutes, 5.5 minutes, 6.2 minutes, 7 minutes, 7.5 minutes, 8 minutes, 8.5 minutes, 9 minutes, 9.5 minutes, 10.2 minutes, 10.5 minutes, 11 minutes, 11.5 minutes, 11.8 minutes, preferably 5 ~ 11 minutes, preferably 5 ~ 10 minutes further.
The temperature of described sintering is 340 ~ 400 DEG C, such as 340 DEG C, 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C, preferably 350 ~ 390 DEG C, preferably 380 DEG C further.
The time of described sintering is 4 ~ 12 minutes, such as 4.3 minutes, 4.6 minutes, 4.9 minutes, 5.5 minutes, 6.2 minutes, 7 minutes, 7.5 minutes, 8 minutes, 8.5 minutes, 9 minutes, 9.5 minutes, 10.2 minutes, 10.5 minutes, 11 minutes, 11.5 minutes, 11.8 minutes, preferably 5 ~ 11 minutes, preferably 5 ~ 10 minutes further.
Describedly be laminated to prior art, those skilled in the art can carry out lamination according to lamination disclosed in prior art, obtains high filler content PTFE copper-clad plate.
A preparation method for high filler content PTFE copper-clad plate, described method comprises the steps:
Fluororesin powder mixes with mineral filler by (1 '), stirs 1 hour, obtains the mixture of fluororesin powder and mineral filler, then add lubricant, continues to stir, and obtains dough;
The dough that step (1) obtains is extruded by (2 '), and calendering, obtains sheet material;
(3 ') heat-treats the sheet material that step (2) obtains, and heat treated temperature is 300 DEG C, and heat treatment time is 2 ~ 5 hours, to remove lubricant;
Sheet material after thermal treatment is infiltrated fluoro-resin dispersion emulsion by (4 '), leaves standstill after 3 ~ 5 minutes, dry, cures, and sintering, obtains PTFE base material
Copper Foil is covered in the side of the PTFE base material that step (4 ') obtains by (5 ') or both sides, then lamination, can obtain high filler content PTFE copper-clad plate.
Five of object of the present invention is to provide a kind of printed circuit board, and described printed circuit board is prepared by least one high filler content PTFE copper-clad plate as above.
" high filler content " of the present invention, means, in the quality of mineral filler and fluororesin powder for 100wt%, and the quality >=50wt% of described mineral filler.
Compared with prior art, the present invention has following beneficial effect:
(1) present invention achieves the preparation of high loading content without glass-fiber-fabric enhancement type PTFE substrate and copper-clad plate thereof, compared with the prior art, operation of the present invention is relatively simple, waste water can not be produced, method environmental protection, cost is low, can obtain the good high filler content PTFE base material of over-all properties and copper-clad plate thereof by the method;
(2) sheet material after thermal treatment infiltrates fluoro-resin dispersion emulsion, fluoro-resin dispersion emulsion can fill the hole and cavity that bring because lubricant removal is rear, and, layer of surface film can be formed in sheet surface, improve the interface binding power of PTFE base material and Copper Foil in PTFE copper-clad plate, obtain the high filler content PTFE copper-clad plate of excellent combination property;
(3) described high filler content PTFE copper-clad plate hole is few, and water-intake rate is low, and stripping strength is high, and Dk/Df is low, and voltage breakdown is high, has the good market competitiveness.
Embodiment
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
PTFE toner, particle diameter about 38 μm, Daikin company produces.
Fluoro-resin dispersion emulsion proportion of composing: PTFE emulsion 100g, PFA emulsion 10g, FEP emulsion 10g, appropriate amount of deionized water, is adjusted to 50% by solid content.Emulsion is all Daikin company and produces.
Mineral filler: silicon powder, particle diameter about 2 ~ 10 μm, East Sea silicon powder factory.
Lubricant, DPG, commercially available.
Get above-mentioned PTFE toner 1000g, add 1000g silicon powder, carry out being uniformly mixed about 1 hour in high-speed mixer, add the lubricant DPG of 300g again, jogging speed mixes 20 minutes, forcing machine is sent by mixture, be extruded into the bar that diameter is about 5mm, this bar repeatedly rolls again, finally obtain the sheet material of 300 × 300 × 1.0mm specification, thermal treatment in 300 DEG C/120 minutes is carried out to this sheet material, after cooling, to immerse in above-mentioned fluoro-resin dispersion emulsion 3 ~ 5 minutes, baking oven is put into dry successively after taking-up, bake and bank up with earth and sinter, dry, cure and be followed successively by with sintering condition: 100 DEG C/10min, 300 DEG C/10min, 380 DEG C/10min.The Copper Foil that the both sides of gained base material cover 1OZ thick carries out lamination, and apply pressure about 300 ~ 500PSI, top temperature and retention time are 380 DEG C/60min, namely obtain PTFE copper-clad plate.Carry out performance test to this PTFE copper-clad plate, result is as shown in table 1:
PTFE copper-clad plate the performance test results described in table 1 embodiment 1
Embodiment 2
PTFE toner, particle diameter about 50 μm.
Fluoro-resin dispersion emulsion proportion of composing: PTFE emulsion 100g, PFA emulsion 10g, FEP emulsion 10g, appropriate amount of deionized water, is adjusted to 50% by solid content.Emulsion is all Daikin company and produces.
Mineral filler: titanium dioxide, particle diameter about 20 μm.
Lubricant, DOP, commercially available.
Get above-mentioned PTFE powder 800g, add 1200g titanium dioxide, carry out being uniformly mixed about 0.5 hour in high-speed mixer, add the lubricant DOG of 300g again, jogging speed mixes 20 minutes, forcing machine is sent by mixture, be extruded into the bar that diameter is about 5mm, this bar repeatedly rolls again, finally obtain the sheet material of 300 × 300 × 1.0mm specification, thermal treatment in 350 DEG C/60 minutes is carried out to this sheet material, after cooling, to immerse in above-mentioned fluoro-resin mark emulsion 2 minutes, baking oven is put into dry successively after taking-up, bake and bank up with earth and sinter, dry, cure and be followed successively by with sintering condition: 100 DEG C/12min, 200 DEG C/12min, 380 DEG C/12min.The Copper Foil that the both sides of gained base material cover 1OZ thick carries out lamination, and apply pressure about 300 ~ 500PSI, top temperature and retention time are 380 DEG C/60min, namely obtain PTFE copper-clad plate.
Embodiment 3
PTFE toner, particle diameter about 15 μm, Daikin company produces.
Fluoro-resin dispersion emulsion proportion of composing: PTFE emulsion 100g, appropriate amount of deionized water, is adjusted to 50% by solid content.Emulsion is that Daikin company produces.
Mineral filler: silicon-dioxide, particle diameter about 10 μm, East Sea silicon powder factory.
Lubricant, PIB, commercially available.
Get above-mentioned PTFE powder 800g, add 1200g silicon powder, carry out being uniformly mixed about 1.5 hours in high-speed mixer, add the lubricant PIB of 300g again, jogging speed mixes 20 minutes, forcing machine is sent by mixture, be extruded into the bar that diameter is about 5mm, this bar repeatedly rolls again, finally obtain the sheet material of 300 × 300 × 1.0mm specification, thermal treatment in 250 DEG C/360 minutes is carried out to this sheet material, after cooling, to immerse in above-mentioned fluoro-resin mark emulsion 7 minutes, baking oven is put into dry successively after taking-up, bake and bank up with earth and sinter, dry, cure and be followed successively by with sintering condition: 160 DEG C/4min, 300 DEG C/4min, 400 DEG C/4min.The Copper Foil that the both sides of gained base material cover 1OZ thick carries out lamination, and apply pressure about 300 ~ 500PSI, top temperature and retention time are 380 DEG C/60min, namely obtain PTFE copper-clad plate.
Carry out performance test to PTFE copper-clad plate described in embodiment 2 and 3, result is as shown in table 2.
Table 2
Comparative example 1
PTFE toner, particle diameter about 38 μm, Daikin company produces.
Fluoro-resin dispersion emulsion proportion of composing: PTFE emulsion 100g, PFA emulsion 10g, FEP emulsion 10g, appropriate amount of deionized water, is adjusted to 50% by solid content.Emulsion is all Daikin company and produces.
Mineral filler: silicon powder, particle diameter about 2 ~ 10 μm, East Sea silicon powder factory.
Lubricant, DPG, commercially available.
Get above-mentioned PTFE toner 1000g, add 1000g silicon powder, carry out being uniformly mixed about 1 hour in high-speed mixer, add the lubricant DPG of 300g again, jogging speed mixes 20 minutes, forcing machine is sent by mixture, be extruded into the bar that diameter is about 5mm, this bar repeatedly rolls again, finally obtain the sheet material of 300 × 300 × 1.0mm specification, thermal treatment in 300 DEG C/120 minutes is carried out to this sheet material, after cooling, the Copper Foil that the both sides of gained base material cover 1OZ thick carries out lamination, apply pressure about 300 ~ 500PSI, top temperature and retention time are 380 DEG C/60min, namely PTFE copper-clad plate is obtained.
Carry out performance test to copper-clad plate described in comparative example 1, can learn that comparative example 1 copper-clad plate base material water-intake rate is greater than 2%, stripping strength is lower than 0.8N/mm.
It should be noted that and understand, when not departing from the spirit and scope of the present invention required by accompanying claim, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (86)
1. a preparation method for high filler content PTFE base material, is characterized in that, described method comprises the steps:
(1) fluororesin powder is mixed with mineral filler, obtain the mixture of fluororesin powder and mineral filler, then add lubricant, continue to stir, obtain dough; Described fluororesin powder is PTFE toner;
(2) extruded by the dough that step (1) obtains, calendering, obtains sheet material;
(3) sheet material that step (2) obtains is heat-treated, to remove lubricant;
(4) sheet material after thermal treatment is infiltrated fluoro-resin dispersion emulsion, after leaving standstill, dry, cure, sintering, obtains high filler content PTFE base material, and described fluoro-resin dispersion emulsion is selected from the mixture of any one or at least two kinds in PTFE emulsion, PFA emulsion or FEP emulsion.
2. the method for claim 1, is characterized in that, the particle diameter of described fluororesin powder is within 50 μm.
3. method as claimed in claim 2, is characterized in that, within the particle diameter 45 μm of described fluororesin powder.
4. method as claimed in claim 3, is characterized in that, within the particle diameter 40 μm of described fluororesin powder.
5. the method for claim 1, it is characterized in that, described mineral filler is selected from the mixture of any one or at least two kinds in aluminium hydroxide, silicon-dioxide, titanium dioxide, barium titanate, talcum powder, mica, barium sulfate, zinc sulfide white, calcium carbonate, wollastonite, kaolin, brucite, diatomite, wilkinite, silicon powder or pumice sand.
6. method as claimed in claim 5, is characterized in that, described mineral filler is selected from the mixture of any one or at least two kinds in silicon-dioxide, titanium dioxide or barium titanate.
7. method as claimed in claim 6, it is characterized in that, described mineral filler is selected from silicon-dioxide or/and titanium dioxide.
8. the method for claim 1, is characterized in that, adopts coupling agent treatment inorganic filler surface.
9. the method for claim 1, is characterized in that, the particle diameter of described mineral filler is within 20 μm.
10. method as claimed in claim 9, it is characterized in that, the particle diameter of described mineral filler is within 17 μm.
11. methods as claimed in claim 10, is characterized in that, the particle diameter of described mineral filler is within 15 μm.
12. the method for claim 1, is characterized in that, described lubricant is selected from the mixture of any one or at least two kinds in fat hydrocarbon, metal soap, aliphatic amide type, aliphatics acids, aliphatic ester or aliphatics alcohols.
13. methods as claimed in claim 12, is characterized in that, described lubricant is selected from the mixture of any one or at least two kinds in fat hydrocarbon, aliphatics alcohols or aliphatic ester.
14. methods as claimed in claim 13, is characterized in that, described lubricant is selected from the mixture of any one or at least two kinds in dipropylene glycol, polyisobutene or dioctyl phthalate (DOP).
15. methods as claimed in claim 1 or 2, is characterized in that, the described heat treated temperature of step (3) is 250 ~ 350 DEG C.
16. methods as claimed in claim 15, is characterized in that, the described heat treated temperature of step (3) is 270 ~ 320 DEG C.
17. methods as claimed in claim 16, is characterized in that, the described heat treated temperature of step (3) is 300 DEG C.
18. methods as claimed in claim 1 or 2, it is characterized in that, the described heat treated time is 1 ~ 6 hour.
19. methods as claimed in claim 18, it is characterized in that, the described heat treated time is 1.5 ~ 5.5 hours.
20. methods as claimed in claim 19, it is characterized in that, the described heat treated time is 2 ~ 5 hours.
21. methods as claimed in claim 1 or 2, it is characterized in that, the time of repose described in step (4) is 2 ~ 7 minutes.
22. methods as claimed in claim 21, it is characterized in that, the time of repose described in step (4) is 3 ~ 6 minutes.
23. methods as claimed in claim 22, it is characterized in that, the time of repose described in step (4) is 3 ~ 5 minutes.
24. methods as claimed in claim 1 or 2, is characterized in that, the temperature of described drying is 80 ~ 150 DEG C.
25. methods as claimed in claim 24, is characterized in that, the temperature of described drying is 90 ~ 120 DEG C.
26. methods as claimed in claim 25, is characterized in that, the temperature of described drying is 95 ~ 110 DEG C.
27. methods as claimed in claim 1 or 2, is characterized in that, the time of described drying is 4 ~ 12 minutes.
28. want the method as described in 27 as right, and it is characterized in that, the time of described drying is 5 ~ 11 minutes.
29. methods as claimed in claim 28, is characterized in that, the time of described drying is 5 ~ 10 minutes.
30. methods as claimed in claim 1 or 2, is characterized in that, described in the temperature of curing be 200 ~ 300 DEG C.
31. methods as claimed in claim 30, is characterized in that, described in the temperature of curing be 220 ~ 280 DEG C.
32. methods as claimed in claim 31, is characterized in that, described in the temperature of curing be 250 DEG C.
33. methods as claimed in claim 1 or 2, is characterized in that, described in time of curing be 4 ~ 12 minutes.
34. methods as claimed in claim 33, is characterized in that, described in time of curing be 5 ~ 11 minutes.
35. methods as claimed in claim 34, is characterized in that, described in time of curing be 5 ~ 10 minutes.
36. methods as claimed in claim 1 or 2, is characterized in that, the temperature of described sintering is 340 ~ 400 DEG C.
37. methods as claimed in claim 36, is characterized in that, the temperature of described sintering is 350 ~ 390 DEG C.
38. methods as claimed in claim 37, is characterized in that, the temperature of described sintering is 380 DEG C.
39. methods as claimed in claim 1 or 2, is characterized in that, the time of described sintering is 4 ~ 12 minutes.
40. methods as claimed in claim 39, is characterized in that, the time of described sintering is 5 ~ 11 minutes.
41. methods as claimed in claim 40, is characterized in that, the time of described sintering is 5 ~ 10 minutes.
42. 1 kinds of high filler content PTFE base materials, is characterized in that, described high filler content PTFE base material is prepared by the described method of one of claim 1-41.
43. 1 kinds of high filler content PTFE copper-clad plate, is characterized in that, described high filler content PTFE copper-clad plate comprises at least one high filler content PTFE base material as claimed in claim 42, and be overlying on superimposed after the side of PTFE base material or the Copper Foil of both sides.
The preparation method of 44. 1 kinds of high filler content PTFE copper-clad plate, is characterized in that, described method is: Copper Foil is covered, then lamination in the side of high filler content PTFE base material according to claim 42 or both sides, can obtain high filler content PTFE copper-clad plate.
45. methods as claimed in claim 44, it is characterized in that, described method comprises the steps:
(1) fluororesin powder is mixed with mineral filler, obtain the mixture of fluororesin powder and mineral filler, then add lubricant, continue to stir, obtain dough; Described fluororesin powder is PTFE toner;
(2) extruded by the dough that step (1) obtains, calendering, obtains sheet material;
(3) sheet material that step (2) obtains is heat-treated, to remove lubricant;
(4) sheet material after thermal treatment is infiltrated fluoro-resin dispersion emulsion, after leaving standstill, dry, cure, sintering, obtains high filler content PTFE base material;
(5) Copper Foil is covered, then lamination in side or the both sides of PTFE base material step (4) obtained, and can obtain high filler content PTFE copper-clad plate.
46. methods as claimed in claim 45, is characterized in that, the particle diameter of described fluororesin powder is within 50 μm.
47. methods as claimed in claim 46, is characterized in that, the particle diameter of described fluororesin powder is within 45 μm.
48. methods as claimed in claim 47, is characterized in that, the particle diameter of described fluororesin powder is within 40 μm.
49. methods as claimed in claim 45, it is characterized in that, described mineral filler is selected from the mixture of any one or at least two kinds in aluminium hydroxide, silicon-dioxide, titanium dioxide, barium titanate, talcum powder, mica, barium sulfate, zinc sulfide white, calcium carbonate, wollastonite, kaolin, brucite, diatomite, wilkinite or pumice sand.
50. methods as claimed in claim 49, is characterized in that, described mineral filler is selected from the mixture of any one or at least two kinds in silicon-dioxide, titanium dioxide or barium titanate.
51. methods as claimed in claim 50, it is characterized in that, described mineral filler is selected from silicon-dioxide or/and titanium dioxide.
52. methods as claimed in claim 45, is characterized in that, adopt coupling agent treatment inorganic filler surface.
53. methods as claimed in claim 45, is characterized in that, the particle diameter of described mineral filler is within 20 μm.
54. methods as claimed in claim 53, is characterized in that, the particle diameter of described mineral filler is within 17 μm.
55. methods as claimed in claim 54, is characterized in that, the particle diameter of described mineral filler is within 15 μm.
56. methods as claimed in claim 45, is characterized in that, described lubricant is selected from the mixture of any one or at least two kinds in fat hydrocarbon, metal soap, aliphatic amide type, aliphatics acids, aliphatic ester or aliphatics alcohols.
57. methods as claimed in claim 56, is characterized in that, described lubricant is selected from the mixture of any one or at least two kinds in fat hydrocarbon, aliphatics alcohols or aliphatic ester.
58. methods as claimed in claim 57, is characterized in that, described lubricant is selected from the mixture of any one or at least two kinds in dipropylene glycol, polyisobutene or dioctyl phthalate (DOP).
59. methods as claimed in claim 45, is characterized in that, the described heat treated temperature of step (3) is 250 ~ 350 DEG C.
60. methods as claimed in claim 59, is characterized in that, the described heat treated temperature of step (3) is 270 ~ 320 DEG C.
61. methods as claimed in claim 60, is characterized in that, the described heat treated temperature of step (3) is 300 DEG C.
62. methods as claimed in claim 45, it is characterized in that, the described heat treated time is 1 ~ 6 hour.
63. methods as claimed in claim 62, it is characterized in that, the described heat treated time is 1.5 ~ 5.5 hours.
64. methods as described in claim 63, it is characterized in that, the described heat treated time is 2 ~ 5 hours.
65. methods as claimed in claim 45, it is characterized in that, the time of repose described in step (4) is 2 ~ 7 minutes.
66. methods as described in claim 65, it is characterized in that, the time of repose described in step (4) is 3 ~ 6 minutes.
67. methods as described in claim 66, it is characterized in that, the time of repose described in step (4) is 3 ~ 5 minutes.
68. methods as claimed in claim 45, is characterized in that, the temperature of described drying is 80 ~ 150 DEG C.
69. methods as recited in claim 68, it is characterized in that, the temperature of described drying is 90 ~ 120 DEG C.
70. methods as described in claim 69, it is characterized in that, the temperature of described drying is 95 ~ 110 DEG C.
71. methods as claimed in claim 45, is characterized in that, the time of described drying is 4 ~ 12 minutes.
72. methods as described in claim 71, it is characterized in that, the time of described drying is 5 ~ 11 minutes.
73. methods as described in claim 72, it is characterized in that, the time of described drying is 5 ~ 10 minutes.
74. methods as claimed in claim 45, is characterized in that, described in the temperature of curing be 200 ~ 300 DEG C.
75. methods as described in claim 74, is characterized in that, described in the temperature of curing be 220 ~ 280 DEG C.
76. methods as described in claim 75, is characterized in that, described in the temperature of curing be 250 DEG C.
77. methods as claimed in claim 45, is characterized in that, described in time of curing be 4 ~ 12 minutes.
78. methods as described in claim 77, is characterized in that, described in time of curing be 5 ~ 11 minutes.
79. methods as described in claim 78, is characterized in that, described in time of curing be 5 ~ 10 minutes.
80. methods as claimed in claim 45, is characterized in that, the temperature of described sintering is 340 ~ 400 DEG C.
81. methods as described in claim 80, it is characterized in that, the temperature of described sintering is 350 ~ 390 DEG C.
82. methods as described in claim 81, it is characterized in that, the temperature of described sintering is 380 DEG C.
83. methods as claimed in claim 45, is characterized in that, the time of described sintering is 4 ~ 12 minutes.
84. methods as described in claim 83, it is characterized in that, the time of described sintering is 5 ~ 11 minutes.
85. methods as described in claim 84, it is characterized in that, the time of described sintering is 5 ~ 10 minutes.
86. 1 kinds of printed circuit boards, is characterized in that, described printed circuit board is prepared by least one high filler content PTFE copper-clad plate as claimed in claim 43.
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