CN107652628A - Quartz glass filler, resin combination and copper-clad plate - Google Patents
Quartz glass filler, resin combination and copper-clad plate Download PDFInfo
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- CN107652628A CN107652628A CN201710864647.2A CN201710864647A CN107652628A CN 107652628 A CN107652628 A CN 107652628A CN 201710864647 A CN201710864647 A CN 201710864647A CN 107652628 A CN107652628 A CN 107652628A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/28—Titanium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention relates to a kind of quartz glass filler, it is characterised in that：Mass content >=99.5% of silica in described quartz glass filler, mass content≤0.2% of alundum (Al2O3), mass content≤0.0005% of water, the mass content ＜ 0.01% of sodium oxide molybdena, the mass content ＜ 0.01% of potassium oxide, the mass content ＜ 0.01% of lithia, the mass content ＜ 0.01% of calcium oxide, the mass content ＜ 0.01% of magnesia, the mass content ＜ 0.01% of barium monoxide, the mass content ＜ 0.01% of strontium oxide strontia, the mass content ＜ 0.01% of di-iron trioxide, the mass content ＜ 0.01% of titanium dioxide, the dielectric constant of described quartz glass filler is 3.5 ~ 3.8, dielectric loss is 0.0001 ~ 0.001, hydrophobicity >=24 hour.
Description
Technical field
The invention belongs to copper-clad plate field, and in particular to a kind of quartz glass filler, resin combination and copper-clad plate.
Background technology
Copper-clad plate is that one or both sides are coated with copper with resin using insulating paper, glass fabric or the leaching of other fibrous materials
Paper tinsel, a kind of board-like material formed through hot pressing, it is PCB stock.
Currently used quartz glass (the oxidation of mass content 98.5%~99.7%, three two of silica in copper-clad plate
The mass content 0.1%~0.3% of aluminium, the mass content of water 0.1%~0.3%, the mass content of sodium oxide molybdena 0.05%~
0.1%th, the mass content 0.05%~0.1% of potassium oxide, the mass content 0.05%~0.1% of lithia, the matter of calcium oxide
Measure content 0.05%~0.1%, the mass content of magnesia 0.05%~0.1%, the mass content 0.05% of barium monoxide~
0.1%, the mass content 0.05%~0.1% of strontium oxide strontia, the mass content 0.05%~0.2% of di-iron trioxide, titanium dioxide
The mass content 0.05%~0.1% of titanium), its dielectric constant>3.8, dielectric loss>0.001, it is current easily acquisition filler
In, dielectric constant and the minimum material of dielectric loss, used in copper-clad plate, copper-clad plate dielectric properties are influenceed it is minimum, simultaneously
And can substitutes the low-k of high cost and the resin of low-dielectric loss, so covering in low-k and low-dielectric loss
Fused silica powder largely is used as filler in copper coin.As raising of the copper-clad plate to dielectric constant and dielectric loss requirement (is situated between
Electric constant：＜ 3.8, dielectric loss：＜ 0.001), current quartz glass can not meet the needs of copper-clad plate.Cause current
Fused silica powder can not meet that copper-clad plate has to the main reason for dielectric constant and dielectric loss requirements at the higher level：1st, quartz glass knot
There is scission of link in link between element in structure, so as to many small gap structures occur, while scission of link cause originally be silica silicon structure
Become silica structure, and silica structure in itself easily (deposit absorption atmosphere moisture formation hydroxyl by one kind that hydroxyl falls within moisture
In mode, moisture is lower, and hydroxy radical content is lower), and gap structure easily adsorbs the water in air due to capillarity
Point, cause this quartz glass hydroxy radical content higher；The 2nd, if quartz glass contains lithium, sodium, potassium element or calcium, magnesium, barium, strontium element
Or iron, titanium elements, these elements are to exist in the form of an ion in quartz glass, it easily causes ion hydration, and these are adsorbed
Water be also in the form of hydroxyl exist, so it is the another original for causing quartz glass hydroxy radical content high that these constituent contents are higher
Cause, while these elements easily polarize, and cause dielectric constant and the dielectric loss increase of material.And due to hydroxyl in fused silica powder
Base content is higher, therefore its hydrophily is strong, scattered in macromolecule resin so as to cause fused silica powder to be unfavorable for, and easily goes out
Now reunite；Other hydroxyl is polar group, and easily polarization causes the dielectric constant of material and dielectric loss higher for it.3rd, quartzy glass
Glass, when it is not transparent, it does not form complete glassy state, now in material often with quartz other crystal formations or have
Impurity is present, rather than the quartz glass dielectric constant and dielectric loss of glassy state are all higher；Simultaneously impurity therein also tend to be
Some metal ions, dielectric constant and the dielectric loss increase of material can be caused.4th, the water absorption rate height of material can cause material to exist
(dielectric constant ≈ 80) hygroscopic during storage, so as to cause the dielectric constant of material to become big, the degradation of copper-clad plate.
CN102503115B discloses a kind of production method of low-hydroxy quartz glass fibers, the invention using diameter 15~
40mm quartz glass bar is sent into vacuum deshydroxy stove, and the vacuum degree control of vacuum deshydroxy stove then heats within 10Mpa
1000~1100 DEG C, keep constant temperature 0.5~2 hour.Because quartz glass is a kind of full-bodied subcooled liquid, the temperature range
Hydroxyl between quartz glass lattice can not be discharged, while 0.5~2 hour, the time is short, it is impossible to discharges hydroxyl well, therefore
The hydroxyl for finding using the above method not reaching described in the invention through actual verification can control the effect in 5ppm or so, and
Quartz glass bar is that a solidification is overall, and eliminating hydroxide is difficult, and intracell hydroxyl also is difficult to deviate from, and because hydroxyl-removal is
A kind of reversible process, if by the material storage of hydroxyl-removal in atmosphere, the moisture in its meeting absorption air, regenerating hydroxyl
Base, so after making hydroxyl-removal in this way, hydroxyl can be also generated, and the hydroxyl inside this quartz glass bar can not remove
Go, being only broken into little particle could remove.
CN106430912A discloses the preparation method and quartz glass of low-hydroxy-group squartz glass, and it is by silicon-containing material through changing
Learn vapour deposition and the first silica loosening body is made, wherein, there is stomata and hydroxyl in the first silica loosening body；
Dehydroxylation air-flow is passed through to the first silica loosening body, and at a temperature of dehydroxylation, makes the dehydroxylation air-flow to
After one silica loosening body dehydroxylation, the second silica loosening body is obtained；The second silica loosening body is being burnt
It is sintered under junction temperature, after cooling, obtains quartz glass finished product.This invention the inside passes through dehydroxylation air-flow and quartz glass
Hydroxyl reaction in surface, this method can not remove the hydroxyl of intracell.The dehydroxylation air-flow is limited in the invention
Including dehydroxylation gas, the dehydroxylation gas includes chlorine Cl2, dichloride oxygen sulphur SOCl2At least one of.And by making
With this dehydroxylation gas, Quartz glass surfaces chloride ion-containing can be caused, while both gases are all toxic gases, to environment
It is very harmful, and chlorion can increase the dielectric constant and dielectric loss of material, Jie of quartz glass of the surface with chlorion
Electric constant and dielectric loss are bigger than the quartz glass of the hydroxyl with same amount.The silicon-containing material is limited in the invention includes four
Silicon chloride, monosilane, disilane, hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, 12
The siloxanes of methyl ring six, tetradecamethylcycloheptasiloxane, the siloxanes of ten pregnancy basic ring eight, the siloxanes of ten prestox ring nine or 20
The siloxanes of methyl ring ten.And pure quartz glass is prepared using these materials, first, cost is very high, yield is extremely low, second, raw
The accessory substance of production either pollutes environment or causes carbon emission to increase.Limited in the invention combustion flame with hydrogen, methane,
At least one of acetylene is fuel gas, and oxygen or air are that combustion-supporting gas mutually burns to be formed.Actually these fuel gas
Body can generate hydroxyl, so obtaining in material or containing substantial amounts of during burning with the silica structure of quartz glass
Hydroxyl.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of hydroxy radical content is low and dielectric constant low (3.5~3.8), are situated between
Quartz glass filler, its preparation method and the application in copper-clad plate of electrical loss low (0.0001~0.001).
To solve above technical problem, the present invention adopts the following technical scheme that：
It is an object of the present invention to provide a kind of quartz glass filler, silica in described quartz glass filler
Mass content >=99.5%, mass content≤0.2% of alundum (Al2O3), mass content≤0.0005% of water, sodium oxide molybdena
Mass content ＜ 0.01%, potassium oxide mass content ＜ 0.01%, the mass content ＜ 0.01% of lithia, the matter of calcium oxide
Measure content ＜ 0.01%, the mass content ＜ 0.01% of magnesia, the mass content ＜ 0.01% of barium monoxide, the quality of strontium oxide strontia
Content ＜ 0.01%, the mass content ＜ 0.01% of di-iron trioxide, the mass content ＜ 0.01% of titanium dioxide, described stone
The dielectric constant of English glass filler is 3.5~3.8, dielectric loss is 0.0001~0.001, hydrophobicity >=24 hour.
Preferably, the dielectric constant of described quartz glass filler be 3.5~3.7, dielectric loss be 0.0001~
0.0008。
Preferably, the water absorption rate ＜ 5% of described quartz glass filler, more preferably ＜ 4.5%.
According to an embodiment, the quartz glass filler by raw material of quartz glass by being processed into primary quartz first
Glass dust, then carries out vacuum heating treatment to the primary fused silica powder, finally carries out surface modification treatment and obtains；It is described
Mass content >=99.5% of silica, mass content≤0.2% of alundum (Al2O3), the matter of water in primary fused silica powder
Content≤2%, the mass content ＜ 0.01% of sodium oxide molybdena, the mass content ＜ 0.01% of potassium oxide are measured, the quality of lithia contains
Measure ＜ 0.01%, the mass content ＜ 0.01% of calcium oxide, the mass content ＜ 0.01% of magnesia, the mass content of barium monoxide
＜ 0.01%, the mass content ＜ 0.01% of strontium oxide strontia, the mass content ＜ 0.01% of di-iron trioxide, the quality of titanium dioxide
Content ＜ 0.01%, maximum particle size≤15 micron of described primary fused silica powder.
Preferably, mass content >=99.7% of silica, the matter of alundum (Al2O3) in described raw material of quartz glass
Measure content≤0.2%, H2O mass content≤0.2%, the mass content ＜ 0.01% of sodium oxide molybdena, the mass content of potassium oxide
＜ 0.01%, the mass content ＜ 0.01% of lithia, the mass content ＜ 0.01% of calcium oxide, the mass content ＜ of magnesia
0.01%, the mass content ＜ 0.01% of barium monoxide, the mass content ＜ 0.01% of strontium oxide strontia, the mass content of di-iron trioxide
＜ 0.01%, the mass content ＜ 0.01% of titanium dioxide.
In the present invention, described raw material of quartz glass is obtained by the purchase of Lingshou County Zhong Shikeyuan Mineral Products Trades Co., Ltd
, after by I take charge of voluntarily found quartz glass and grinding fused silica powder.
According to a preferred embodiment, the method that described primary fused silica powder is processed into by described raw material of quartz glass
For：Described raw material of quartz glass is founded 8~16 hours at 1700 DEG C~1950 DEG C and forms quartz glass liquation, will be described
Through crushing, picking out transparency silica glass particle after the cooling of quartz glass liquation, described silica glass particle is ground to most
The powder of big granularity≤15 micron is described primary fused silica powder.
According to a further preferably mode, described glass melting temperature is 1800 DEG C~1900 DEG C, melting time 10
~14 hours.
According to a further preferably mode, maximum particle size≤8 micron of described primary fused silica powder.
According to a further preferably mode, pass through grinding described in a kind of progress in ball milling, airflow milling or vibromill
Mill processing.
According to a further preferably mode, after the cooling of described quartz glass liquation, the big of 4~5cm is first broken into
Granule materials, then hand picking go out the quartz glass block of water white transparency, bubble-free, free from admixture, then by described quartz glass
Block is broken into 1~2mm small particles material, and described silica glass particle is then picked out by high gradient magnetic separator.According to
One embodiment, the method for carrying out vacuum heating treatment to the primary fused silica powder are：Using with relatively independent
The reactor of first chamber and second chamber, described reactor has heating and vacuumizes function, first by described primary stone
English glass dust is 10 in vacuum in described first chamber-1~10-5Mpa, temperature are to be incubated 5 at 1400 DEG C~1600 DEG C
~10 hours, then move in described second chamber, be 10 in vacuum-1~10-5Mpa, when cooling to 25 DEG C~30 DEG C,
Transfer the material into the band inner membrance jumbo bag vacuumized.
Preferably, described reactor is roller kilns.
Preferably：Cooling extent is 3 DEG C/min~5 DEG C/min.
The present invention uses quartz glass powder so that substantial amounts of space exposes, and the hydroxyl under the condition of high temperature in lattice is easily
Abjection, and cool down and pack under vacuum conditions so that material will not absorb moisture generation hydroxyl.
According to a further preferably mode, described primary fused silica powder is loaded into saggar made of quartz glass
In, then described saggar is put into described first chamber and carries out insulation and second chamber is cooled.
According to a preferred embodiment, described surface modification treatment, described titanate esters are carried out using titanate coupling agent
The structural formula of coupling agent is as follows：
Wherein A is CH3CH2-, m 1, X areR is-CH2-CH2-
CH2-, Y isN is 3.
It is further preferred that the structural formula of described titanate coupling agent is as follows：
It is further preferred that the inventory of described titanate coupling agent is described primary fused silica powder quality
0.5%~4%.
It is further preferable that the inventory of described titanate coupling agent is the 1% of described primary fused silica powder quality
~3.5%.
Most preferably, the inventory of described titanate coupling agent for described primary fused silica powder quality 2%~
3%.
In the present invention, the synthetic route of described titanate coupling agent is：
1、
2、
3、
4、
5、
6、
The synthetic method of described titanate coupling agent comprises the following steps：
Step (1), TiCl is added in a kettle4And C2H5OH, react 3~8 hours and obtain at 60 DEG C~120 DEG C
C2H5OTiCl3。
Step (2), described C is added in a kettle2H5OTiCl3And C6H4OHCl, at 60 DEG C~120 DEG C, at 4~6
Reaction obtains C under atmospheric pressure2H5OTi(OC6H4Cl)3。
Step (3), ClCH is added in a kettle2CH2CH3And Mg, in the presence of ether, in 50 DEG C~60 DEG C reactions
Obtain ClMgCH2CH2CH3。
Step (4), described C is added in a kettle2H5OTi(OC6H4Cl)3With described ClMgCH2CH2CH3, in second
Reaction obtains C in the presence of ether2H5OTi(OC6H4CH2CH2CH3)3。
Step (5), described C is added in a kettle2H5OTi(OC6H4CH2CH2CH3)3, it is passed through Cl2, then pass through light
According to obtained C2H5OTi(OC6H4CH2CH2CH2Cl)3。
Step (6), described C is added in a kettle2H5OTi(OC6H4CH2CH2CH2Cl)3With60
DEG C~120 DEG C, under 2~4 atmospheric pressure, react 5~8 hours titanate coupling agents for being made described.
Preferably, described TiCl4With described C2H5OH molar ratio is 1~2：1.
Preferably, described C2H5OTiCl3With described C6H4OHCl molar ratio is 1：3~3.5.
Preferably, described ClCH2CH2CH3Molar ratio with described Mg is 1：1~1.5.
Preferably, described C2H5OTi(OC6H4CH2CH2CH3)3With described Cl2Molar ratio be 2~3：1.
Preferably, the intensity of illumination is 40~60cd.
Preferably, described C2H5OTi(OC6H4CH2CH2CH2Cl)3With it is describedMolar ratio
For 1：4~5.
It is a further object to provide a kind of preparation method of above-mentioned quartz glass filler, comprise the following steps：
Step (1), raw material of quartz glass is founded to 8~16 hours formation quartz glass liquations at 1700 DEG C~1950 DEG C,
Through crushing, picking out transparent silica glass particle after described quartz glass liquation is cooled down, by described quartz glass
Particulate abrasive to the powder of maximum particle size≤15 micron is described primary fused silica powder.
Step (2), had using the reactor with relatively independent first chamber and second chamber, described reactor
Function is heated and vacuumized, is 10 in vacuum first by described primary fused silica powder in described first chamber-1~
10-5Mpa, temperature are to be incubated 5~10 hours at 1400 DEG C~1600 DEG C, are then moved in described second chamber, in vacuum
For 10-1~10-5Mpa, when cooling to 25 DEG C~30 DEG C, transfer the material into the band inner membrance jumbo bag vacuumized.
Further preferably：Described reactor is roller kilns.
Further preferably：Cooling extent is 3 DEG C/min~5 DEG C/min.
Step (3), using coupling agent to through step (2) processing after primary fused silica powder carry out surface modification treatment obtain
To described quartz glass filler.
It is further preferred that the inventory of described coupling agent for described primary fused silica powder quality 0.5%~
4%.
It is further preferable that the inventory of described coupling agent for described primary fused silica powder quality 1%~
3.5%.
Most preferably, the inventory of described coupling agent is the 2%~3% of described primary fused silica powder quality.
It is further preferred that described coupling agent and the primary fused silica powder after step (2) processing are added
Enter into high-speed mixer, mixed 8~12 minutes at 2000~4000rpm, 110 DEG C~150 DEG C, be then turned on exhausting and cause
The vacuum of described high-speed mixer is 10-1~10-5Mpa, complete surface modification treatment.
According to a preferred embodiment, maximum particle size≤8 meter of described primary fused silica powder.
According to a preferred embodiment, pass through the milled processed described in a kind of progress in ball milling, airflow milling or vibromill.
According to a preferred embodiment, after the cooling of described quartz glass liquation, 4~5cm large granular materials are first broken into,
Then hand picking goes out the quartz glass block of water white transparency, bubble-free, free from admixture, then described quartz glass block is broken into 1
~2mm small particles material, described silica glass particle is then picked out by color selector and high gradient magnetic separator.
According to a preferred embodiment, described primary fused silica powder is fitted into saggar made of quartz glass, then
Described saggar is put into described first chamber and be incubated.
According to a preferred embodiment, described coupling agent is titanate coupling agent.
Third object of the present invention is to provide the purposes that a kind of described quartz glass filler is used to prepare copper-clad plate.
Fourth object of the present invention is to provide a kind of resin combination, and comprising filler, described filler is all or part of
For described quartz glass filler.
The 5th purpose of the present invention is to provide a kind of copper-clad plate, comprising resin combination, described resin combination bag
Containing filler, described filler is all or part of described quartz glass filler.
Due to the implementation of above technical scheme, the present invention has following advantage compared with prior art：
The present invention is using the primary fused silica powder ground so that substantial amounts of crystals space exposure, and in high temperature shape
Hydroxyl under state in lattice is easily deviate from, and the reduction of hydroxyl reduces dielectric constant and dielectric loss；The present invention further passes through
The coupled action of high hydrophobic, polymolecularity the titanate coupling agent independently synthesized, silica group is shielded, prevent its from
Moisture generation hydroxyl in absorption air again, and vacuum storage is carried out to the product of making so that material will not absorb water
Point, so as to contain that dielectric constant and dielectric loss improve.
Because the quartz glass filler hydroxy radical content of the present invention is low and uses at high hydrophobic, high dispersive titanate coupling agent
Reason, it is easily mixed with macromolecule resin, and its dielectric constant and dielectric loss decrease, relative to currently used stone
English glass dust has lower dielectric constant and dielectric loss as filler copper-clad plate, and the water absorption rate of such a material is lower,
Its obtained material will not cause poor dielectric performance because of moisture is absorbed.
Embodiment
The present invention is described in further details below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to say
The bright basic principles, principal features and advantages of the present invention, and the present invention is not limited by the following examples.Used in embodiment
Implementation condition can do further adjustment according to specific requirement, and unreceipted implementation condition is usually the condition in normal experiment.
Without indicating, " % " is mass percent.The commercially available acquisition of raw material in the present invention.
Method of testing：
Hydrophobicity：10g samples are taken, are placed in the beaker equipped with 500ml pure water, material sinking situation are observed, when material 24
Hour does not sink, then it is assumed that material hydrophobicity is good.
Dielectric constant and dielectric loss test：By packing quality content 25%, polyphenylene oxide resin (Asahi Chemical Industry, 500H) quality
Content 15%, bisphenol f type epoxy resin (Changchun chemical industry, BFE170) mass content 20%, (bis-phenol of cyanate ester mass content 20%
A type cyanates, Yangzhou Jiangdu, Jiangsu Province area Wuqiao resin processing plant), dicyandiamide (ISO, Zhengzhou Zhi Yuan chemical products Co., Ltd)
Mass content 10%, glass cloth mass content 10% (2116, Chongqing world composite) are fabricated to resin content 60%,
The prepreg of packing quality content 25%, then using Network Analyzer under 10GHZ, test the dielectric constant of prepreg
And dielectric loss.
Hydroxy radical content：Hydroxyl is a kind of existing way of moisture, by the high-temperature calcination to material, material weight before and after test
The situation of change of the change of amount, as hydroxyl.
Water absorption rate：Material is exposed to relative humidity 85%, 24h at 85 DEG C of temperature, material is dried to perseverance at 105 DEG C
Weight, ratio (exposure after/exposure before) * 100%=water absorption rates of moisture before and after contrast material exposure.
The preparation of embodiment 1, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0004%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
This is preference：Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.68%,
Al2O3：0.15%, H2O：0.00036%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：
0.0004%, MgO：0.0002%, BaO：0.0002%, SrO：0.0003%, Fe2O3：0.0007%, TiO2：0.0006%,
Hydrophobicity：It is good, dielectric constant：3.52 dielectric loss：0.0003, water absorption rate:4.2%, it was preference to be somebody's turn to do, its alkali metal, alkaline earth
Metal, the oxide of transition metal is few, and is handled by optimal coupling agent treatment amount processing and optimal processing technology, its
Hydroxy radical content is few, and water absorption rate is low, and the dielectric constant and dielectric loss of material are low.
The preparation of comparative example 1, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0169%, K2O：
0.0004%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.70%, Al2O3：0.16%,
H2O：0.00045%, Na2O：0.0153%, K2O：0.0003%, Li2O：0.0005%, CaO：0.0003%, MgO：
0.0004%, BaO：0.0002%, SrO：0.0006%, Fe2O3：0.0003%, TiO2：0.0004%, hydrophobicity：It is good, dielectric
Constant：3.86 dielectric loss：0.0025, water absorption rate：9.25%, Na2The increase of O content, the hydroxy radical content increase of material, material
The water absorption rate increase of material, dielectric constant and dielectric loss become big.
The preparation of comparative example 2, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0005%, K2O：
0.0172%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.70%, Al2O3：0.16%,
H2O：0.00045%, Na2O：0.0004%, K2O：0.0163%, Li2O：0.0003%, CaO：0.0004%, MgO：
0.0001%, BaO：0.0002%, SrO：0.0005%, Fe2O3：0.0006%, TiO2：0.0004%, hydrophobicity：It is good, dielectric
Constant：3.84 dielectric loss：0.0022, water absorption rate：9.05%, K2The increase of O content, the hydroxy radical content increase of material, material
Water absorption rate increase, dielectric constant and dielectric loss become big.
The preparation of comparative example 3, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0005%, Li2O：0.0193%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.70%, Al2O3：0.16%,
H2O：0.00043%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0178%, CaO：0.0004%, MgO：
0.0001%, BaO：0.0002%, SrO：0.0005%, Fe2O3：0.0005%, TiO2：0.0004%, hydrophobicity：It is good, dielectric
Constant：3.82 dielectric loss：0.0020, water absorption rate：8.95%, Li2The increase of O content, the hydroxy radical content increase of material, material
The water absorption rate increase of material, dielectric constant and dielectric loss become big.
The preparation of comparative example 4, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0005%, Li2O：0.0003%, CaO：0.0156%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.70%, Al2O3：0.16%,
H2O：0.00042%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0154%, MgO：
0.0001%, BaO：0.0002%, SrO：0.0005%, Fe2O3：0.0005%, TiO2：0.0004%, hydrophobicity：It is good, dielectric
Constant：3.82 dielectric loss：0.0020, water absorption rate：8.70%, the increase of CaO content, the hydroxy radical content increase of material, material
Water absorption rate increase, dielectric constant and dielectric loss become big.
The preparation of comparative example 5, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0005%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0193%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized；
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.70%, Al2O3：0.16%,
H2O：0.00042%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0006%, MgO：
0.0181%, BaO：0.0002%, SrO：0.0005%, Fe2O3：0.0005%, TiO2：0.0004%, hydrophobicity：It is good, dielectric
Constant：3.80 dielectric loss：0.0018, water absorption rate：8.62%, the increase of content of MgO, the hydroxy radical content increase of material, material
Water absorption rate increase, dielectric constant and dielectric loss become big.
The preparation of comparative example 6, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0005%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0143%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.70%, Al2O3：0.16%,
H2O：0.00042%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0006%, MgO：
0.0001%, BaO：0.0142%, SrO：0.0005%, Fe2O3：0.0005%, TiO2：0.0004%, hydrophobicity：It is good, dielectric
Constant：3.88 dielectric loss：0.0029, water absorption rate：The increase of 8.52%, BaO content, the hydroxy radical content increase of material, material
Water absorption rate increase, dielectric constant and dielectric loss become big.
The preparation of comparative example 7, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0005%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0175%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.70%, Al2O3：0.16%,
H2O：0.00042%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0006%, MgO：
0.0001%, BaO：0.0002%, SrO：0.0168%, Fe2O3：0.0005%, TiO2：0.0004%, hydrophobicity：It is good, dielectric
Constant：3.86 dielectric loss：0.0025, water absorption rate：The increase of 8.60%, SrO content, the hydroxy radical content increase of material, material
Water absorption rate increase, dielectric constant and dielectric loss become big.
The preparation of comparative example 8, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0005%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0162%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized；
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.70%, Al2O3：0.16%,
H2O：0.00042%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0006%, MgO：
0.0001%, BaO：0.0002%, SrO：0.0006%, Fe2O3：0.0160%, TiO2：0.0004%, hydrophobicity：It is good, dielectric
Constant：3.83 dielectric loss：0.0016, water absorption rate：7.50%, Fe2O3The increase of content, the hydroxy radical content increase of material, material
The water absorption rate increase of material, dielectric constant and dielectric loss become big.
The preparation of comparative example 9, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0005%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0185% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 2.5% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.70%, Al2O3：0.16%,
H2O：0.00042%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0006%, MgO：
0.0001%, BaO：0.0002%, SrO：0.0006%, Fe2O3：0.0007%, TiO2：0.0179%, hydrophobicity：It is good, dielectric
Constant：3.87 dielectric loss：0.0030, water absorption rate：7.20%, TiO2The increase of content, the hydroxy radical content increase of material, material
The water absorption rate increase of material, dielectric constant and dielectric loss become big.
The preparation of comparative example 10, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0004%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.68%, Al2O3：0.15%,
H2O：0.00038%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0004%, MgO：
0.0002%, BaO：0.0002%, SrO：0.0003%, Fe2O3：0.0007%, TiO2：0.0006%, hydrophobicity：Difference (is put into
Sink in water), dielectric constant：3.76 dielectric loss：0.0008, water absorption rate 15.2%, not using coupling agent treatment, material
The water absorption rate of material is high.
The preparation of comparative example 11, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0004%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 0.3% of the primary fused silica powder weight after step (5) processing,
Then mixed 10 minutes at 3000rpm, 115 DEG C, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
To fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.68%, Al2O3：0.15%,
H2O：0.00038%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0004%, MgO：
0.0002%, BaO：0.0002%, SrO：0.0003%, Fe2O3：0.0007%, TiO2：0.0006%, hydrophobicity：Difference (is put into
In water, all sink after 20 minutes), dielectric constant：3.76 dielectric loss：0.0008, water absorption rate 13.8%, coupling agent treatment
Amount is few, and the water absorption rate of material is high.
The preparation of comparative example 12, quartz glass filler：
Step (1), using with SiO2：99.75%, Al2O3：0.12%, H2O：0.10%, Na2O：0.0006%, K2O：
0.0004%, Li2O：0.0003%, CaO：0.0005%, MgO：0.0002%, BaO：0.0003%, SrO：0.0005%,
Fe2O3：0.0006%, TiO2：0.0005% pure quartz glass raw material, in electric arc furnaces, 12h shapes are founded by 1850 DEG C
Into uniform quartz glass liquation.
Step (2), after quartz glass liquation cooling after, pour out melted ingot, be broken into 4cm large granular materials, hand picking
Water white transparency, bubble-free, the quartz glass block of free from admixture.
Step (3), by the quartz glass block small particles material in small, broken bits into 1mm, by high gradient magnetic separator, select transparent
Silica glass particle.
Step (4), it will be 7.5 microns through the material after step (3) processing by ball milling to material maximum particle size and obtain
To primary fused silica powder.
Step (5), ground primary fused silica powder is fitted into saggar made of quartz glass, described first
It is 10 in vacuum in chamber-3Mpa, temperature are to be incubated 7 hours at 1450 DEG C, are then moved in described second chamber, true
Reciprocal of duty cycle is 10-3Mpa, cooled using 3 DEG C/min~5 DEG C/min as cooling extent, when temperature is cooled to 28 DEG C, material is turned
Move in the band inner membrance jumbo bag vacuumized.
Step (6), by through step (5) processing after primary fused silica powder be transported in high-speed mixer, then add
Titanate coupling agent, the dosage of titanate coupling agent are 5% of the primary fused silica powder weight after step (5) processing, so
Mixed 10 minutes at 3000rpm, 115 DEG C afterwards, be then turned on exhausting and make it that the vacuum of high-speed mixer is 10-3Mpa, obtain
Fused silica powder filler.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.68%, Al2O3：0.15%,
H2O：0.00038%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0004%, MgO：
0.0002%, BaO：0.0002%, SrO：0.0003%, Fe2O3：0.0007%, TiO2：0.0006%, hydrophobicity：Difference (is put into
In water, all sink after 20 minutes), dielectric constant：3.76 dielectric loss：0.008, water absorption rate 4.0%, coupling agent treatment amount
More, the water absorption rate of material is low, but dielectric loss increase, caused by the dipole moment polarization mainly in coupling agent is slow.
The preparation of comparative example 13, quartz glass filler：
Step (1), according to embodiment 1, but found 12h by 1680 DEG C when founding.
Conclusion：Glass melting temperature is relatively low, and material can not melt, it is impossible to form quartz glass.
The preparation of comparative example 14, quartz glass filler：
Step (1), according to embodiment 1, but found 7h by 1850 DEG C when founding.
Conclusion：Melting time is short, and material can melt, it is impossible to forms transparent quartz glass, hydrophobicity：It is good, dielectric constant：
3.92 dielectric loss：0.0020, water absorption rate：4.6%, it is not transparent quartz glass, the dielectric constant of material is high, dielectric damage
Consumption is high.
The preparation of comparative example 15, quartz glass filler：
Step (1), according to embodiment 1, but pass through when founding and found 8h by 2000 DEG C.
Conclusion：Glass melting temperature is too high, and melting time is short, and material can melt, but forms substantial amounts of quartzy steam, the row of blocking
Feed channel.
The preparation of comparative example 16, quartz glass filler：
Step (1) is 1mpa in vacuum, dropped using 3 DEG C/min~5 DEG C/min as cooling extent according to embodiment 1
Temperature, when temperature is cooled to 28 DEG C, transfer the material into the band inner membrance jumbo bag vacuumized.
Pass through quartz glass filler made from the above method, its chemical composition SiO2：99.68%, Al2O3：0.15%,
H2O：0.00106%, Na2O：0.0005%, K2O：0.0003%, Li2O：0.0002%, CaO：0.0004%, MgO：
0.0002%, BaO：0.0002%, SrO：0.0003%, Fe2O3：0.0007%, TiO2：0.0006%, hydrophobicity：It is good, dielectric
Constant：3.76 dielectric loss：0.0009, water absorption rate:5.3%, vacuum is inadequate, and the hydroxyl of material removes not enough, dielectric constant
Height, dielectric loss are high.
Comparative example 17, commercially available fused silica powder (525ari, silicon is than section mining industry)：
Step (1), its chemical composition are：SiO2：98.68%, Al2O3：0.13%, H2O：0.11%, Na2O：0.058%,
K2O：0.067%, Li2O：0.062%, CaO：0.059%, MgO：0.071%, BaO：0.058%, SrO：0.053%,
Fe2O3：0.052%, TiO2：0.073%.
Hydrophobicity：Difference (is put into water, all sink after 5 minutes), dielectric constant：3.92 dielectric loss：0.0032, inhale
Water rate 15.6%, the water absorption rate of material is high, and dielectric constant is high, and dielectric loss is big.
The preparation of embodiment 2, coupling agent：
1st, 80mol TiCl is added in a clean reactor4(titanium tetrachloride, Jinan Yin Ju Chemical Co., Ltd.s) and
50mol C2H5OH (DY-01233, Jiangsu Dong Yi Chemical Co., Ltd.s), reacts 5 hours under 115 DEG C, an atmospheric pressure, so
50mol C is obtained by rectifying afterwards2H5OTiCl3。
2nd, by the C of 50mol made from above-mentioned 1 in a clean reactor2H5OTiCl3With 150mol C6H4OHCl(BT/
5218-557 Shouguang City Lu Ke chemical industry Co., Ltd) 50mol C is made under 105 DEG C, 5 atmospheric pressure2H5OTi
(OC6H4Cl)3。
3. by 50mol ClCH in a clean reactor2CH2CH3(FM1, Shandong Fu Wang chemical industry are limited with 60mol Mg
Company) in 200mol Et2In O (ether, Suzhou Hua Yuan chemical industry) solvent, in 55 DEG C of temperature, 1 atmospheric pressure is made 50mol's
ClMgCH2CH2CH3。
4th, the C of 50mol made from above-mentioned 2 is added in above-mentioned 3 reactor2H5OTi(OC6H4Cl)3It is made by rectifying
50mol C2H5OTi(OC6H4CH2CH2CH3)3。
5th, by 50molC made from above-mentioned 42H5OTi(OC6H4CH2CH2CH3)3, it is put into a clean reactor, is passed through
20mol Cl2(6061AL, Hengshui City Taocheng District Xin Hai chemical industry Instrument Ltd.), then by illumination (light intensity 50cd) and
20molC is made in rectifying2H5OTi(OC6H4CH2CH2CH2Cl)3。
6th, by 20molC made from above-mentioned 52H5OTi(OC6H4CH2CH2CH2Cl)3+80mol(styrene,
The limited public company of the strong foreign trade of Zhengzhou space) it is put into a clean reactor, under 112 DEG C, 3 atmospheric pressure, reaction 6 is small
When, 20mol is made by rectifying
Claims (10)
- A kind of 1. quartz glass filler, it is characterised in that：The mass content of silica in described quartz glass filler >= 99.5%th, the mass content ＜ of mass content≤0.2% of alundum (Al2O3), mass content≤0.0005% of water, sodium oxide molybdena 0.01%th, the mass content ＜ 0.01% of potassium oxide, the mass content ＜ 0.01% of lithia, the mass content ＜ of calcium oxide 0.01%th, the mass content ＜ 0.01% of magnesia, the mass content ＜ 0.01% of barium monoxide, the mass content ＜ of strontium oxide strontia 0.01%, the mass content ＜ 0.01% of di-iron trioxide, the mass content ＜ 0.01% of titanium dioxide, described quartz glass are filled out The dielectric constant of material is that 3.5 ~ 3.8, dielectric loss is 0.0001 ~ 0.001, hydrophobicity >=24 hour.
- 2. quartz glass filler according to claim 1, it is characterised in that：The quartz glass filler passes through first by stone English frit is processed into primary fused silica powder, then carries out vacuum heating treatment to the primary fused silica powder, finally Surface modification treatment is carried out to obtain；Mass content >=99.5% of silica, three oxidations two in described primary fused silica powder Mass content≤0.2% of aluminium, mass content≤0.2% of water, the mass content ＜ 0.01% of sodium oxide molybdena, the quality of potassium oxide contain Measure ＜ 0.01%, the mass content ＜ 0.01% of lithia, the mass content ＜ 0.01% of calcium oxide, the mass content ＜ of magnesia 0.01%, the mass content ＜ 0.01% of barium monoxide, the mass content ＜ 0.01% of strontium oxide strontia, the mass content ＜ of di-iron trioxide 0.01%, the mass content ＜ 0.01% of titanium dioxide, maximum particle size≤15 micron of described primary fused silica powder.
- 3. quartz glass filler according to claim 2, it is characterised in that：Titanium dioxide in described raw material of quartz glass Mass content >=99.7% of silicon, mass content≤0.2% of alundum (Al2O3), H2O mass content≤0.2%, sodium oxide molybdena Mass content ＜ 0.01%, potassium oxide mass content ＜ 0.01%, the mass content ＜ 0.01% of lithia, the quality of calcium oxide Content ＜ 0.01%, magnesia mass content ＜ 0.01%, the mass content ＜ 0.01% of barium monoxide, the mass content of strontium oxide strontia ＜ 0.01%, the mass content ＜ 0.01% of di-iron trioxide, the mass content ＜ 0.01% of titanium dioxide；It is coupled using titanate esters Agent carries out described surface modification treatment, and the inventory of described titanate coupling agent is described primary fused silica powder quality 1% ~ 4%.
- 4. the quartz glass filler according to Claims 2 or 3, it is characterised in that：Processed by described raw material of quartz glass Method into described primary fused silica powder is：It is small that described raw material of quartz glass at 1700 DEG C ~ 1950 DEG C is founded 8 ~ 16 When form quartz glass liquation, by after described quartz glass liquation cooling through crushing, picking out transparent silica glass particle, By described silica glass particle, the powder for being ground to maximum particle size≤15 micron is described primary fused silica powder.
- 5. quartz glass filler according to claim 4, it is characterised in that：After described quartz glass liquation cooling, first 4 ~ 5cm large granular materials are broken into, then hand picking goes out the quartz glass block of water white transparency, then by described quartz glass Block is broken into 1 ~ 2mm small particles material, and described silica glass particle is then picked out by high gradient magnetic separator.
- 6. the quartz glass filler according to Claims 2 or 3, it is characterised in that：The primary fused silica powder is carried out The method of vacuum heating treatment is：Using the reactor with relatively independent first chamber and second chamber, described reaction Utensil has heating and vacuumizes function, is in vacuum in described first chamber by described primary fused silica powder first 10-1~10-5Mpa, temperature are to be incubated 5 ~ 10 hours at 1400 DEG C ~ 1600 DEG C, are then moved in described second chamber, true Reciprocal of duty cycle is 10-1~10-5Mpa, when cooling to 25 DEG C~30 DEG C, transfer the material into the band inner membrance jumbo bag vacuumized.
- 7. the quartz glass filler according to Claims 2 or 3, it is characterised in that：Described in being carried out using titanate coupling agent Surface modification treatment, the structural formula of described titanate coupling agent is as follows：, wherein A is CH3CH2-, m 1, X are, R is-CH2-CH2-CH2-, Y is, n 3.
- A kind of 8. preparation method of quartz glass filler as any one of claim 1 to 7, it is characterised in that：Including Following steps：Step（1）, raw material of quartz glass founded at 1700 DEG C ~ 1950 DEG C 8 ~ 16 hours form quartz glass liquation, will described in The cooling of quartz glass liquation after through crushing, picking out transparent silica glass particle, described silica glass particle is ground Powder to maximum particle size≤15 micron is described primary fused silica powder；Step（2）, using the reactor with relatively independent first chamber and second chamber, described reactor has heating With vacuumize function, first by described primary fused silica powder in described first chamber, vacuum be 10-1~10-5 Mpa, temperature are to be incubated 5 ~ 10 hours at 1400 DEG C ~ 1600 DEG C, are then moved in described second chamber, are 10 in vacuum-1 ~10-5Mpa, when cooling to 25 DEG C~30 DEG C, transfer the material into the band inner membrance jumbo bag vacuumized；Step（3）, using coupling agent to through step（2）Primary fused silica powder after processing carries out surface modification treatment and obtains institute The quartz glass filler stated.
- 9. a kind of resin combination, includes filler, it is characterised in that：Described filler is all or part of in claim 1 to 7 Quartz glass filler described in any one.
- A kind of 10. copper-clad plate, it is characterised in that：It includes the quartz glass filler any one of claim 1 to 7.
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Citations (4)
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|---|---|---|---|---|
| CN101215074A (en) * | 2008-01-17 | 2008-07-09 | 徐传龙 | Production technique for drawing crystal powder used for low-hydroxyl quartz glass soft pipe and pipe drawing method |
| CN102120583A (en) * | 2011-03-29 | 2011-07-13 | 段其九 | Crucible for electronic industry and method for purifying high-purity quartz sand as lining material |
| CN103360793A (en) * | 2012-03-27 | 2013-10-23 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Low-dielectric constant filler and preparation technology thereof |
| CN105131527A (en) * | 2015-09-17 | 2015-12-09 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Copper clad laminate with low dielectric constant and manufacturing method of copper clad laminate |
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| US8658719B2 (en) * | 2009-06-11 | 2014-02-25 | Arlon | Low loss pre-pregs and laminates and compositions useful for the preparation thereof |
| CN102206399B (en) * | 2011-04-15 | 2013-01-02 | 广东生益科技股份有限公司 | Composition for copper-clad laminate with low dielectric constant and copper-clad laminate manufactured by using same |
| CN105802186B (en) * | 2016-03-18 | 2018-12-14 | 苏州海旭新材料科技有限公司 | A kind of copper-clad plate filler, resin combination and its application in copper-clad plate |
| CN106633648B (en) * | 2016-12-08 | 2018-12-25 | 重庆市锦艺硅材料开发有限公司苏州分公司 | A kind of resistance to Ion transfer filler and copper-clad plate |
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|---|---|---|---|---|
| CN101215074A (en) * | 2008-01-17 | 2008-07-09 | 徐传龙 | Production technique for drawing crystal powder used for low-hydroxyl quartz glass soft pipe and pipe drawing method |
| CN102120583A (en) * | 2011-03-29 | 2011-07-13 | 段其九 | Crucible for electronic industry and method for purifying high-purity quartz sand as lining material |
| CN103360793A (en) * | 2012-03-27 | 2013-10-23 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Low-dielectric constant filler and preparation technology thereof |
| CN105131527A (en) * | 2015-09-17 | 2015-12-09 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Copper clad laminate with low dielectric constant and manufacturing method of copper clad laminate |
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