CN104529174A - Glass with low dielectric constant - Google Patents
Glass with low dielectric constant Download PDFInfo
- Publication number
- CN104529174A CN104529174A CN201510009267.1A CN201510009267A CN104529174A CN 104529174 A CN104529174 A CN 104529174A CN 201510009267 A CN201510009267 A CN 201510009267A CN 104529174 A CN104529174 A CN 104529174A
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- glass
- glass material
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- temperature
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Classifications
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
- C03C13/00—Fibre or filament compositions
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides glass with the low dielectric constant. The glass can be made of continuous glass fibers. The glass must comprise the following properties that (1), the dielectric constant ranges from 4.5 to 5.0; (2), the Log3 viscosity temperature is lower than 1,300 DEG C; (3), the liquidus temperature is lower than 1,100 DEG C, and the difference between the Log3 viscosity temperature and the liquidus temperature is higher than 75 DEG C; (4), the glass can tolerate the humid environment.
Description
Technical field
The invention provides a kind of glass with low dielectric constant made that can be used for continuous glass fibre, it must comprise following character:
1) specific inductivity: 4.5 to 5.0;
2) Log3 viscosity temperature < 1300 DEG C;
3) liquefaction temperature (liquidus temperature) < 1100 DEG C, and itself and Log3 viscosity temperature difference more than 75 DEG C; And
4) wet environment can be tolerated.
Background technology
The main component of glass fibre is silicon-dioxide, aluminum oxide, calcium oxide, boron oxide, magnesium oxide, sodium oxide etc., according to the number of alkali content in glass, alkali free glass fibre (sodium oxide 0-2%), medium-alkali glass fibre (sodium oxide 8-12%) and high alkali glass fibre (sodium oxide more than 13%) can be divided into.The cross section of glass fibre is rounded, and diameter is between several microns to 20 microns, and density is approximately public gram/cc of 2.4-2.7.Glass fibre is very tough, and tensile strength is approximately five times of same thickness steel wire, and the load that it can bear can reach 70 tonnes every square centimeter.Glass fibre belongs to inorganic fibre, has the features such as better thermotolerance, wet fastness, uninflammability, chemical resistance, anti-mildew, anti-moth, heat insulation, sound insulation, electrical insulating property in the chemically more than organic fibre.Industrially, glass fibre is mainly as the material of filtration, protection against corrosion, protection against the tide, heat insulation, sound insulation, insulation, damping.Glass fibre is made for outside fabric use apart from continuous print macrofiber and the staple fibre being cut into certain length, for adapting to industrial needs, develops again the products such as hollow fiber, wavy staple, pitted skin fiber, top coat fiber in recent years.Special purpose can be used as and picked up yarn, zero-twist yarn, voluminous yarn, union yarn, dyed yarn, conductive yam, strand, sewing thread, cable, tire netting twine, felt and various textile article.Glass fibre also can be used as the toughener of material in addition, is used for manufacturing reinforced plastics, reinforcing rubber, strengthening gypsum and the goods such as reinforced cementitious.
Flourish due to global information and electronic industry, printed circuit board (PCB), copper clad laminate, glass-fiber-fabric etc. are significantly extended all successively, cause the demand of electronic-grade glass yarn with and increase severely.Particularly, the glass fibre yarn be made up of electronic-grade glass material uses as the base material of printed circuit board (PCB).Generally speaking, the output of glass fibre yarn is for will be produced into glass cream by kiln high temperature melt after the grating such as sharp sand, Wingdale, soda ash and kaolin, through reeling off raw silk from cocoons, batch, the process such as twist yarn makes glass fiber yarn, then via warping, sizing, weave cotton cloth, after the process such as destarch, make glass-fiber-fabric.For meeting the quality requirements to yarn in glass-fiber-fabric processing procedure, glass yarn is not only wanted superfine and is wanted successively, carefully the allotment viscosity of glass paste and the speed of extraction need be leaned on to be controlled, after being pumped into silk again through above-mentioned to batch, after the process such as twist yarn, just become electronic grade glass cloth can electronic grade glass yarn.
Move towards compact, multi-functional for adapting to electronic product, at a high speed and the development trend of high frequency, the improvement of electronic-grade glass material is obviously imperative, wherein especially important by the mode of ameliorating based on chemistry of photolithography techniques (optical lithography) or advanced low-k materials (low dielectric constantmaterials).Such as, due to Communication Equipment, satellite transmission instrument, mobil phone ... etc. there is digitized trend and its signal process also has demand faster, its printed circuit board (PCB) used must use the composition material of low dissipation loss (lowdielectric loss).Therefore, glass fiber material is widely used in printed circuit board (PCB), wherein conventional with E-glass (E-glass).
In theory, when an electric current flows through glass material, this glass material can absorb the energy of this electric current in the mode of heat absorption usually.This absorbed dielectric loss energy (dielectricloss energy, hereinafter referred to as W) with specific inductivity (the dielectric constant of this glass material, hereinafter referred to as ε or DK) and its dielectric tangent (dielectric tangent, hereinafter referred to as tan δ) be directly proportional, it can represent by following formula:
W=kfv2×εtanδ
Wherein W is dielectric loss energy, and k is a constant, and f is a frequency, and v2 is potential gradient, and ε represents specific inductivity, and tan δ is dielectric tangent.
For the E-glass of printed circuit board (PCB), for example, have under room temperature and 1MHz frequency specific inductivity be 7.0 with dielectric tangent be the characteristic of 12 × 10-4.Because circuit card has the requirement of higher density, high-insulativity and high processing rate etc., therefore, dielectric loss energy should be reduced, but the property value of E-glass is not sufficient to meet this demand as far as possible.Therefore, developing a kind of glass material having more a low-k and lower dielectric tangent compared with E-glass is become a main R&D direction.
For adapting to the demand, developing a kind of glass material is D-glass (D-glass).For example, D-glass can be a kind of have 75.3% SiO
2, 20.5% B
2o
3, 0.6% CaO, the MgO of 0.4%, the LiO of 0.6%
2, 1.1% NaO
2with 1.5% K
2the glass component of O.Separately, for example, D-glass have under room temperature and 1MHz frequency specific inductivity be 4.3 with dielectric tangent be 10 × 10
-4characteristic.But, one of shortcoming of D-glass is that its melting is poor, and easily cause striped and foam to make glass fibre at spinning process Fracture, thus obviously unfavorable with processing to the manufacture of product: in addition, another main drawback of D-glass is that the tack of the water tolerance of D-glass and itself and resin is poor, and thus this glass material is easily peeled off from printed circuit board (PCB).Therefore, the exploitation of glass material of new generation has its needs with improvement is real.
WO02/094728 discloses a kind of glass component of low-dielectric, and it comprises the SiO of 50-60%
2, 10-19% Al
2o
3, 16-25% B
2o
3, 0.5-4% P
2o
5the Na of ,≤1.5%
2the O ,≤K of 1.5%
2the O ,≤R of 2%
2the RO of F and 4-15% of the O ,≤CaO of 10% ,≤MgO, 0-2% of 10%, wherein R
2o=Na
2o+K
2o+Li
2o and RO=CaO
+mgO.
Another U.S. patent application case publication number 20030054936 also reveal that a kind of glass fibre with low-k, and it comprises the SiO of 50-60%
2, 10-18% Al
2o
3, 14-< 20% B
2o
3, 1-< 6% the Li of TiO2,0-0.3% of CaO, 0.5-5% of MgO, 2-5%
2the Na of O, 0-0.3%
2the K of O, 0-0.5%
2the F of O and 0-2%
2, wherein the content of Li2O+Na2O+K2O is 0-0.6%.
But, the glass material disclosed by prior art, its specific inductivity can be down to about 5.0, but through the result that may produce crystallization of reeling off raw silk from cocoons, and its moisture resistance is unsatisfactory.Therefore, say with regard to the manufacture of glass fiber material and its application in fields such as printed circuit board (PCB)s, really need to do further to improve for above-mentioned various characteristic.
Summary of the invention
The present invention is open a kind of glass with low dielectric constant made that can be used for continuous glass fibre, and it comprises following character:
1) specific inductivity: 4.5 to 5.0;
2) Log3 viscosity temperature < 1300 DEG C;
3) liquefaction temperature < 1100 DEG C, and itself and Log3 viscosity temperature difference more than 75 DEG C; And
4) wet environment can be tolerated.
Specifically, the present invention is open a kind of glass material with low-k, and this glass material comprises following ingredients:
A.10-12 the Al of % by weight
2o
3;
B.5-10 the CaO of % by weight;
C.2-5 the MgO of % by weight;
D.16-20 the B of % by weight
2o
3;
E.0.05-0.15 the Fe of % by weight
2o
3;
F. the Na of < 0.2 % by weight
2o;
G. the SO of < 0.05 % by weight
3;
H. the K of < 0.2 % by weight
2o; And
I. remaining as SiO
2.
In another specific embodiment of the present invention, the above-mentioned glass material with low-k also comprises TiO
2, ZnO, SrO and F
2in at least one.
Compared to glass material composition of the prior art, glass material of the present invention can be free of the composition having fluorine and phosphorus, but can obtain more superior physical properties.
According to glass material of the present invention, it has following physical character: specific inductivity reduces to 4.5 to 5.0, Log3 viscosity temperature < 1300 DEG C, liquefaction temperature < 1100 DEG C and itself and aforementioned Log3 viscosity temperature difference more than 75 DEG C, and its moisture resistance greatly improves.This kind of glass material is lower due to specific inductivity, is therefore more suitable for the base material as printed circuit board (PCB) etc.; Because its liquefaction temperature is lower, the phenomenon of crystallization therefore can not be there is in time reeling off raw silk from cocoons; Due to its liquefaction temperature and Log3 viscosity temperature difference more than 75 DEG C, be therefore more conducive to the fabrication steps of carrying out reeling off raw silk from cocoons; In addition, because moisture resistance (represents with " alkali dissolution (alkalineleach) ", is less than 0.055 milligram of Na
2o/ gram of glass) also (be about 0.5 milligram of Na far beyond prior art
2o/ gram of glass) for good, the shortcoming that glass material is peeled off from printed circuit board (PCB) therefore significantly can be improved.
Embodiment
the design of the glass material of low-k
First stage:
1., according to the characteristic of each composition of glass material, such as this composition is to the possible influence degree of the various character such as the specific inductivity of glass material, allocates with various types of and various ratio.
2. measure the physical propertiess such as the Log3 viscosity of this glass material, liquefaction temperature, specific inductivity and dielectric tangent.
3. set up the significant test mode in order to Measuring Dielectric Constant of a tool and/or instrument.
4. set up the developing direction of the glass with low dielectric constant required for an allotment.
Subordinate phase:
1., based on required physical properties, the mode according to the first stage obtains required glass material.
2. measure the following character of this glass material:
-high-temperature viscosity curve
-softening temperature (softening point) temperature
-Xu Lengdian (annealing point) temperature
-strain point (strain point) temperature
The qualification of-liquefaction temperature, first and second phase
-specific refractory power
-thermal expansivity (from 0 DEG C to 300 DEG C)
-density
-under 100Hz, 1KHz, 10KHz, 1MHz and 1GHz and 23 DEG C, 100 DEG C with the specific inductivity under the conditional combination of 200 DEG C and dielectric tangent
-Yi JIS R3502 method of testing measures alkali stripping quantity (alkali elution)
embodiment
The glass material with low-k of the present invention can form by filling a prescription as follows:
Hold above-mentioned, the physical properties of this glass material is as follows:
the comparison of character
* R represents alkaline-earth metal
* R ' represents basic metal
In the present invention, glass composition as above, limits reason as follows:
SiO
2be the main oxides of glass ware forming, and have the effect of stablizing each composition, generally can wish SiO
2content is lower, can obtain preferably melting effect, but too low meeting causes ε specific inductivity bigger than normal, and glass water tolerance reduces.Content is high, Stability Analysis of Structures, and water resistance is good, if too high time, viscosity becomes large, and mold temperature significantly improves, and causes being not easy to reel off raw silk from cocoons, and increases energy cost, generally can with reference to SiO in E glass
2content, as a reference, optimal selection scope 52-56%.
Al
2o
3also be one of important oxide compound of glass ware forming, play an important role in water tolerance, generally with Al
2o
3replace some SiO
2, lower glass ware forming temperature can be had; Al
2o
3time too low, water tolerance and chemical durability can be deteriorated, and too high meeting causes glass viscosity to increase, and improve devitrification risk, easily cause difficulty of reeling off raw silk from cocoons, optimal selection scope 10-12%.
B
2o
3there is effect of fluxing preferably, the temperature of glass ware forming can be reduced, add in right amount and preferably mechanical property can be provided; B
2o
3content is too low, ε specific inductivity, and tan δ dielectric tangent can become large, and glass viscosity uprises, and time too high, chemical durability is deteriorated, B
2o
3volatilization uprises, and is difficult to produce uniform glass, and wire drawing is easily broken, and Bushing consumes quickening, optimal selection scope 16-20%.
The adjustable glass viscosity of MgO and CaO, improves chemical stability, physical strength, used in combinationly improves fiberizing efficiency, too high ε specific inductivity and the tan δ dielectric tangent of all making becomes large, optimal selection scope MgO:2-5%, CaO:5-10%, RO:6-10%.
TiO
2for reduction viscosity and tan δ dielectric tangent be effective, can produce non-melting phenomenon time too low, dielectric tangent increases, otherwise the too high chemical resistant properties that easily causes is deteriorated, optimal selection scope 2-4%.
Li
2o, Na
2o and K
2o alkali metal group oxide compound all can reduce glass viscosity, is good fusing assistant, but has great negative impact to the dielectric properties of glass, therefore usage quantity must strictly control, and tan δ dielectric tangent can be caused time excessive to become large; ε specific inductivity is pressed Li-Na-K order and is increased, but when using Na
+, K
+replace Li
+after, the ε specific inductivity of glass decreases.
Na
2o and K
2o optimal selection range L EssT.LTssT.LT 0.2%, R '
2o < 0.4%.
From above-mentioned data, according to glass material of the present invention, as better in WO02/094728 and US20030054936 in the E-glass that its specific inductivity and dielectric tangent value are all comparatively conventional and prior art.Secondly, according to glass material of the present invention, its operating temperature range (i.e. the gap of liquefaction temperature and Log3 viscosity temperature) reaches more than 75 DEG C, it is the fabrication steps being more conducive to carrying out reeling off raw silk from cocoons, and due to its liquefaction temperature lower, therefore can not there is the phenomenon of crystallization in time reeling off raw silk from cocoons.Moreover according to glass material of the present invention, its moisture resistance is expressed as with alkali dissolution and is less than 0.055 milligram of Na
2o/ gram of glass, therefore significantly can improve the shortcoming that glass material is peeled off from printed circuit board (PCB).In sum, the present invention is more suitable for as electronic-grade glass material relative to glass material of the prior art.
Claims (11)
1. have a glass material for low-k, this glass material comprises following ingredients:
A.10-12 the Al of % by weight
2o
3;
B.5-10 the C of % by weight
ao;
C.2-5 the MgO of % by weight;
D.16-20 the B of % by weight
2o
3;
E.0.05-0.15 the Fe of % by weight
2o
3;
F. the Na of < 0.2 % by weight
2o;
G. the SO of < 0.05 % by weight
3;
H. the K of < 0.2 % by weight
2o; And
I. remaining as SiO
2.
2. glass material according to claim 1, it also comprises TiO
2, ZnO, SrO and F
2in at least one.
3. glass material according to claim 1 and 2, wherein the specific inductivity of this glass material is 4.5 to 5.0.
4. glass material according to claim 1 and 2, wherein the dielectric tangent of this glass material is less than 10 × 10
-4.
5. the glass material according to application claim 1 or 2, wherein the Log3 viscosity temperature of this glass material is not more than 1300 DEG C.
6. glass material according to claim 1 and 2, wherein the liquefaction temperature of this glass material is less than 1100 DEG C.
7. glass material according to claim 1 and 2, the wherein liquefaction temperature of this glass material and Log3 viscosity temperature difference more than 75 DEG C.
8. glass material according to claim 1 and 2, wherein the moisture resistance of this glass material represents with alkali dissolution, is less than 0.055 milligram of Na
2o/ gram of glass.
9. glass material according to claim 1 and 2, wherein this glass material system is as electronic-grade glass material.
10. glass material according to claim 9, wherein this electronic-grade glass material system is as the base material of printed circuit board (PCB).
11. a glass fibre, it is made up of glass material according to claim 1.
Priority Applications (1)
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CN201510009267.1A CN104529174A (en) | 2015-01-08 | 2015-01-08 | Glass with low dielectric constant |
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---|---|---|---|
CN201510009267.1A CN104529174A (en) | 2015-01-08 | 2015-01-08 | Glass with low dielectric constant |
Publications (1)
Publication Number | Publication Date |
---|---|
CN104529174A true CN104529174A (en) | 2015-04-22 |
Family
ID=52844865
Family Applications (1)
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CN201510009267.1A Pending CN104529174A (en) | 2015-01-08 | 2015-01-08 | Glass with low dielectric constant |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108383378A (en) * | 2018-06-04 | 2018-08-10 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of glass with low dielectric constant |
CN109626843A (en) * | 2018-12-31 | 2019-04-16 | 郑州翎羽新材料有限公司 | A kind of glass fibre of roughing in surface |
CN110028249A (en) * | 2019-01-30 | 2019-07-19 | 河南光远新材料股份有限公司 | A kind of dielectric glass fibre component and its manufacturing method |
CN111032760A (en) * | 2017-08-02 | 2020-04-17 | 索尔维特殊聚合物美国有限责任公司 | Reinforced thermoplastic polymer compositions comprising low dielectric flat glass fibers and corresponding articles |
WO2020166518A1 (en) * | 2019-02-12 | 2020-08-20 | 日東紡績株式会社 | Glass fiber-reinforced resin molded article |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004107112A (en) * | 2002-09-17 | 2004-04-08 | Nippon Electric Glass Co Ltd | Low dielectric constant low dielectric dissipation factor glass fiber |
CN1752040A (en) * | 2004-09-22 | 2006-03-29 | 台湾玻璃工业股份有限公司 | Glass having low dielectric constant |
CN101558019A (en) * | 2006-12-14 | 2009-10-14 | Ppg工业俄亥俄公司 | Low dielectric glass and fiber glass for electronic applications |
-
2015
- 2015-01-08 CN CN201510009267.1A patent/CN104529174A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004107112A (en) * | 2002-09-17 | 2004-04-08 | Nippon Electric Glass Co Ltd | Low dielectric constant low dielectric dissipation factor glass fiber |
CN1752040A (en) * | 2004-09-22 | 2006-03-29 | 台湾玻璃工业股份有限公司 | Glass having low dielectric constant |
CN101558019A (en) * | 2006-12-14 | 2009-10-14 | Ppg工业俄亥俄公司 | Low dielectric glass and fiber glass for electronic applications |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111032760A (en) * | 2017-08-02 | 2020-04-17 | 索尔维特殊聚合物美国有限责任公司 | Reinforced thermoplastic polymer compositions comprising low dielectric flat glass fibers and corresponding articles |
CN108383378A (en) * | 2018-06-04 | 2018-08-10 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of glass with low dielectric constant |
CN109626843A (en) * | 2018-12-31 | 2019-04-16 | 郑州翎羽新材料有限公司 | A kind of glass fibre of roughing in surface |
CN110028249A (en) * | 2019-01-30 | 2019-07-19 | 河南光远新材料股份有限公司 | A kind of dielectric glass fibre component and its manufacturing method |
CN110028249B (en) * | 2019-01-30 | 2020-09-18 | 河南光远新材料股份有限公司 | Low dielectric glass fiber component and manufacturing method thereof |
WO2020166518A1 (en) * | 2019-02-12 | 2020-08-20 | 日東紡績株式会社 | Glass fiber-reinforced resin molded article |
JPWO2020166518A1 (en) * | 2019-02-12 | 2021-12-16 | 日東紡績株式会社 | Glass fiber reinforced resin molded product |
JP7410411B2 (en) | 2019-02-12 | 2024-01-10 | 日東紡績株式会社 | Glass fiber reinforced resin molded products |
US12098254B2 (en) | 2019-02-12 | 2024-09-24 | Nitto Boseki Co., Ltd. | Glass fiber-reinforced resin molded article |
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Application publication date: 20150422 |