CN107298531A - Glass fiber with low dielectric constant and preparation method thereof - Google Patents
Glass fiber with low dielectric constant and preparation method thereof Download PDFInfo
- Publication number
- CN107298531A CN107298531A CN201710554246.7A CN201710554246A CN107298531A CN 107298531 A CN107298531 A CN 107298531A CN 201710554246 A CN201710554246 A CN 201710554246A CN 107298531 A CN107298531 A CN 107298531A
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- Prior art keywords
- glass fibre
- glass
- dielectric constant
- wire
- tio
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Classifications
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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
- C03C13/00—Fibre or filament compositions
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a kind of glass fibre of low-k and preparation method thereof, it is made up of the following components of percentage by weight：SiO262%~65%, Al2O311%~13%, B2O313%~15%, CaO 5~8%, TiO20.5~2%, Li2O 0.5~2%, La2O30.5~2%, TiO2With La2O3Weight sum be not more than 3%.Using the glass fibre of this proportioning, with excellent processing performance and dielectric properties, its wire-drawing temperature is less than 1350 DEG C, and at room temperature, dielectric constant is 4.7~4.9 when frequency is 1MHz, and dielectric loss is 7~9 × 10‑4.It is suitable as the reinforcing material of printed circuit board (PCB).
Description
Technical field
The present invention relates to a kind of glass fibre of low-k, for the reinforcing material of printed circuit board (PCB), the present invention is also
It is related to the preparation method of this kind of glass fibre.
Background technology
In recent ten years, developing by leaps and bounds due to electronics and information industry, printed circuit board (PCB) is to high density and multilayer, super multilayer
Direction is developed, it is desirable to which copper-clad plate acts not only as substrate, also to develop signal transmssion line function, characteristic impedance accuracy control function,
And built-in passive element function etc. is served as in multi-layer sheet.This requires material to have low dielectric constant and dielectric loss.This
It is that then signal velocity is faster because the dielectric constant of material is smaller；Under certain frequencies of propagation, the dielectric loss of material
Smaller, then propagation loss is smaller.Printed circuit board (PCB) is generally made up of resin and glass fibre.Tree conventionally used for printed circuit board (PCB)
The dielectric properties of fat are gratifying, thus the key of the restriction above-mentioned characteristic of printed circuit board (PCB), are high-quality, high-quality
Glass fiber material.The dielectric constant of E glass fibres of printed circuit board (PCB) is conventionally used to 7 or so, it is impossible to meet circuit board and get over
Carry out the requirement of faster processing speed, therefore exploitation turns into mainly compared with the glass fibre that E glass has lower dielectric constant
R＆D direction.
For such case, many researchs have been done both at home and abroad, develop the glass fibre of some low-ks.Such as typical case
The composition of D glass fibre be：SiO272-76%, Al2O30-5%, B2O320-25%, Na2O+K2O3- 5%.Its dielectric constant
For 4.1 or so, dielectric loss is 8 × 10-4Left and right.But the SiO of D glass2Content is high, causes wire-drawing temperature to be up to 1410 DEG C of left sides
The right side, the drilling poor performance of glass fibre reinforced laminate, is unfavorable for following process, and water resistance is also very poor, easily cause fiber with
The stripping of resin.Japanese Nitto Boseki Co. Ltd's patent document 96194439.0 describes a kind of glass fiber with low dielectric constant
Composition, SiO250-60%, Al2O310-20%, B2O320-30%, Na2O+K2O+Li2O 0.5%, CaO 0-5%, MgO 0-
4%, Ti2O 0.5-4%., dielectric constant is in 4.2-4.5 or so, and wire-drawing temperature is more than 1280 DEG C.AGY Holding Corp. of the U.S.
Patent document 200780048402.7 to describe a kind of composition of glass fiber with low dielectric constant as follows：SiO252-60%,
Al2O311-16%, B2O320-30%, CaO4-8%.Corresponding dielectric constant 4.5-5, dielectric loss≤5 × 10-4, wire drawing temperature
Degree is at 1350 DEG C or so.The patent document 200610166224.5 of Taishan Fibreglass Co., Ltd provides a kind of low Jie
Dielectric-constant glass fiber, consisting of：SiO250-60%, Al2O36-9.5%, B2O330.5-35%, CaO0-5%, ZnO0-
5%, TiO20.5-5%, wherein ZnO replace part CaO, MgO effect to reduce dielectric constant.Corresponding dielectric constant
3.9-4.4, dielectric loss (4-8.5) × 10-4, wire-drawing temperature is at 1350 DEG C or so.Sichuan Glass Fiber Co., Ltd. it is special
Sharp document 200910216020.1 describes a kind of glass fiber with low dielectric constant composition：SiO250-60%, Al2O312-
18%, B2O321-27%, CaO 0-1.8%, MgO0.5-3.2%, ZnO0.5-3.2%, TiO20.4-4%, CaF20.5%-
3%, CeO0.2%-0.6%.The glass fibre dielectric constant of the composition is 4.2-4.6.B in the composition of above-mentioned glass fibre2O3
Content it is higher, typically all more than 20%.Although use requirement can be met in terms of dielectric properties, high B2O3Content
Make boron volatilization serious, glass fibre composition fluctuation is larger, causes wire-drawing operation difficult, while harsh is required to kiln temperature, meeting
The tank furnace life-span is reduced, therefore manufacturing cost is higher, it is difficult to mass produce.In addition, high B2O3Content also causes glass fibre
Water resistance is reduced.The patent document 200780046066.2 of PPG companies of the U.S. describes a kind of B2O3Content is so-called for 7-11%'s
Glass fiber with low dielectric constant composition, but dielectric constant is more than 5.2.The dielectric constant of general dielectric glass fibre will
Ask below 5.Therefore the glass fibre has been not belonging to the category of dielectric glass fibre.Therefore go out from actual production and application
Hair is, it is necessary to a kind of SiO2Content is suitable, B2O3The relatively low glass fiber with low dielectric constant of content.
The content of the invention
In order to solve the above-mentioned technical problem, the first object of the present invention is to provide a kind of glass fibers of low-k
Dimension, B2O3Content it is low, glass spinning temperature differs greatly with devitrification ceiling temperature, good manufacturability.The second object of the present invention is
The preparation method of this kind of glass fibre is provided.
In order to realize above-mentioned first purpose, technical scheme is as follows：A kind of glass fibre of low-k, its
It is characterised by：It is made up of the following components of percentage by weight：SiO262%~65%, Al2O311%~13%, B2O313%
~15%, CaO 5~8%, TiO20.5~2%, Li2O 0.5~2%, La2O30.5~2%, TiO2With La2O3Weight
Sum is not more than 3%.
In this scenario, due to B2O3The reduction of content, in order to ensure dielectric constant below 5, it is necessary to corresponding reduction
CaO content, but this can cause the drastically rise of wire-drawing temperature, cause the decline of manufacturability and operability.In order to solve this
Contradiction, the present invention is by introducing the TiO acted on reduction glass viscosity2、Li2O and La2O3To reduce wire-drawing temperature.Pass through simultaneously
Cross many experiments, it is determined that the proper fit between different oxide compositions, reduced by the synergy between each composition
TiO2、Li2O and La2O3Introducing caused by glass fibre devitrification problem, realize physical and chemical performance and processing performance
Proper fit.In the glass fibre：
SiO2It is to form one of framework oxide of glass and glass fibre, SiO is worked as in the present invention2During less than 62wt%,
Dielectric constant becomes big.Work as SiO2During more than 65wt%, the high temperature viscosity of glass fibre becomes big, and wire-drawing temperature is uprised.
B2O3It is also to form one of framework oxide of glass, B is worked as in the present invention2O3During less than 13wt%, glass fibre
High temperature viscosity become big, wire-drawing temperature is high, and dielectric constant is high, easy devitrification during production.Work as B2O3During more than 15wt%, glass fibers
B during dimension production2O3Volatilization is serious, and fracture of wire is serious during wire-drawing operation, it is not easy to continuous production.
SiO in simultaneously of the invention2And B2O3Weight sum preferably must be held between 75%~80%.If beyond this
Scope, the then easy devitrification of glass fibre, namely devitrification ceiling temperature can rise significantly.
Al2O3It is also to form one of framework oxide of glass, works as Al in the present invention2O3During less than 11wt%, hold during production
Easy devitrification, glass fibre dielectric poor water resistance.Work as Al2O3During more than 13wt%, the high temperature viscosity of glass fibre is big, wire-drawing temperature
It is high.
CaO plays a part of glass network adjusting body in the present invention, when CaO is less than 5wt%, the high temperature of glass fibre
Viscosity is big, and wire-drawing temperature is high, and water resistance is deteriorated.When CaO is more than 8wt%, the dielectric constant of glass fibre can increase, during production
Easily occurs devitrification.
Li2O plays a part of glass network adjusting body in the present invention, works as Li2When O is less than 0.5wt%, glass fibre
High temperature viscosity is big, and wire-drawing temperature is high.Work as Li2When O is more than 2wt%, the dielectric loss of glass fibre can increase.
TiO2The effect of glass network adjusting body is also functioned in the present invention, works as TiO2During less than 0.5wt%, glass fibre
High temperature viscosity it is big, wire-drawing temperature is high, and water resistance is deteriorated.Work as TiO2During more than 2wt%, the dielectric constant of glass fibre can increase
Greatly, easily occurs devitrification during production.
La2O3The effect of glass network adjusting body is also functioned in the present invention, works as La2O3During less than 0.5wt%, glass fibers
The high temperature viscosity of dimension is big, and wire-drawing temperature is high, and water resistance is deteriorated.Work as La2O3During more than 2wt%, the dielectric constant of glass fibre can increase
Greatly, easily occurs devitrification during production.
TiO in simultaneously of the invention2With La2O3Weight sum be not more than 3%.If it is out of this range, then glass fibre
Easy devitrification, namely devitrification ceiling temperature can rise significantly, and the difference of wire-drawing temperature and devitrification ceiling temperature can be strongly reduced, glass
The operability and manufacturability of fiber deteriorate.
The glass fibre prepared using present invention composition and weight percent, at room temperature, dielectric is normal when frequency is 1MHz
Number is 4.7~4.9, and dielectric loss is 7~9 × 10-4.Wire-drawing temperature between 1320~1350 DEG C, dielectric properties, water resistance,
Manufacturability and operating characteristics are excellent.
It is preferred that：It is made up of the following components of percentage by weight：SiO264.6%, Al2O311.2%, B2O314.8%, CaO
6.7%, TiO21.1%, Li2O 0.9%, La2O30.7%.Dielectric constant is low (4.7), wire-drawing temperature and devitrification ceiling temperature it
Difference reaches 190 DEG C, and processing performance is good.
It is preferred that：It is made up of the following components of percentage by weight：SiO264.5%, Al2O312%, B2O314.7%, CaO
5.4%, TiO21.0%, Li2O 1.8%, La2O30.6%.Dielectric constant is low (4.8), wire-drawing temperature and devitrification ceiling temperature it
Difference reaches 168 DEG C, and processing performance is good.
In order to realize above-mentioned second purpose, the technical scheme is that：A kind of system of the glass fibre of low-k
Preparation Method, it is characterised in that：It is put into kiln and is heated to after raw material any one of claim 1-3 is well mixed
1600 DEG C of -1650 DEG C of insulations, obtain after uniform, clarification glass metal, flow out and be made from the platinum bushing plate for being placed in kiln bottom
Glass fibre.Preparation technology is simple.
The beneficial effects of the invention are as follows：Compared with prior art, the present invention has following features and beneficial effect：(1) originally
B in the composition of the glass fibre provided is provided2O3Content be not higher than 15%, be conducive to improve boron volatilization caused by glass fibers
Tie up composition fluctuation big, improve the continuity of glass fibre production, improve water resistance.(2) glass fibre that the present invention is provided
With low dielectric constant and dielectric loss, at room temperature, dielectric constant is 4.7~4.9 when frequency is 1MHz, and dielectric loss is 7
~9 × 10-4.(3) wire-drawing temperature of glass fibre and the difference of devitrification ceiling temperature that the present invention is provided are all higher than 100 DEG C, very
Be conducive to wire-drawing operation, it is easy to produce.(4) water resistance for the glass fibre that the present invention is provided is better than D glass fibre and other high
B2O3Glass fiber with low dielectric constant, with resin adhesive force it is good, be easy to following process, be particularly suitable for making the increasing of printed circuit board (PCB)
Strong material.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1
Embodiment 1-11 is prepared according to the formula in table 1 respectively, and preparation method is：
Batch is made according to recipe requirements in various raw materials, platinum crucible is loaded after being well mixed at 1600 DEG C to 1650
DEG C insulation 4 hours, obtains the glass metal of uniform clarification；The glass metal is poured on the stainless steel mould of preheating, Muffle is placed in
Sheet glass is made after furnace annealing, by the sheet glass it is cleaved, grinding, polishing after be made thickness about 1.5mm, be about 4mm, width about
3mm rectangular sheet, carries out the measurement of dielectric constant and dielectric loss after the rectangular sheet coats silver electrode.
Temperature when wire-drawing temperature refers to viscosity of glass metal for 1000 pool, the present invention is using high temperature viscosity instrument test glass metal
Viscosity at different temperatures, so that it is determined that wire-drawing temperature.
Devitrification ceiling temperature refers to that glass metal long-term heat preservation makes in the temperature of glass devitrification without occurring crystallization or split-phase
Limit, the present invention is using gradient oven process test devitrification ceiling temperature.
The glass dust that water resistance is ground to 360 microns~400 microns by determining is placed 24 hours in 80 DEG C of water
Weight loss is characterized.
The 1-11 of the embodiment of the present invention of table 1 component and result of the test
As shown in Table 1, the glass fibre that the present invention is provided has good manufacturability, operability, water resistance, relatively low Jie
Electric constant and relatively low dielectric loss；The wire-drawing temperature of glass fibre provided in an embodiment of the present invention is below 1350 DEG C, significantly
The wire-drawing temperature of the D glass fibre provided less than comparative example 1, is very beneficial for wire-drawing operation；Glass provided in an embodiment of the present invention
B in glass fiber2O3Content and comparative example 1 provide D glass fibre it is low by more than 7%；Glass fibre provided in an embodiment of the present invention
Water resistance be better than comparative example 1 provide D glass fibre.Therefore, the glass fibre that the present invention is provided goes for traditional D glass
The art of printed circuit boards that glass fiber is applied.
Silica and boron oxide serve as the effect of glass network former, it can also be seen that working as SiO from table 12And B2O3
Weight sum be less than 75%, dielectric constant increases to 5.4, and devitrification temperature increases to 1260 DEG C.Work as SiO2And B2O3Weight it
With higher than 80%, then wire-drawing temperature increases to 1380 DEG C.
Titanium oxide and lanthana serve as the effect of glass network adjusting body in the present invention, it can also be seen that working as from table 1
TiO2With La2O3Weight sum be more than 3% (comparative example 4), then the wire-drawing temperature of glass fibre although have decreased to 1312 DEG C,
But devitrification ceiling temperature has risen to 1280 DEG C, the difference of wire-drawing temperature and devitrification ceiling temperature has strongly reduced 32 DEG C, glass
The operability and manufacturability of glass fiber deteriorate.
The present invention is not limited to above-mentioned specific embodiment, it will be appreciated that one of ordinary skill in the art is without creative
Work just can make many modifications and variations according to the design of the present invention.In a word, all technical staff in the art are according to this
The design of invention passes through the available technical side of logical analysis, reasoning, or a limited experiment on the basis of existing technology
Case, all should be in the protection domain being defined in the patent claims.
Claims (4)
1. a kind of glass fibre of low-k, it is characterised in that：It is made up of the following components of percentage by weight：SiO262%
~65%, Al2O311%~13%, B2O313%~15%, CaO 5~8%, TiO20.5~2%, Li2O 0.5~2%,
La2O30.5~2%, TiO2With La2O3Weight sum be not more than 3%.
2. the glass fibre of low-k according to claim 1, it is characterised in that：By the following components of percentage by weight
Composition：SiO264.6%, Al2O311.2%, B2O314.8%, CaO 6.7%, TiO21.1%, Li2O 0.9%, La2O3
0.7%.
3. the glass fibre of low-k according to claim 1, it is characterised in that：By the following components of percentage by weight
Composition：SiO264.5%, Al2O312%, B2O314.7%, CaO 5.4%, TiO21.0%, Li2O 1.8%, La2O3
0.6%.
4. a kind of preparation method of the glass fibre of low-k, it is characterised in that：By any one of claim 1-3
Raw material it is well mixed after be put into kiln and be heated to 1600 DEG C of -1650 DEG C of insulations, obtain after uniform, clarification glass metal, from
Glass fibre is made in the platinum bushing plate outflow for being placed in kiln bottom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710554246.7A CN107298531A (en) | 2017-07-07 | 2017-07-07 | Glass fiber with low dielectric constant and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710554246.7A CN107298531A (en) | 2017-07-07 | 2017-07-07 | Glass fiber with low dielectric constant and preparation method thereof |
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| CN107298531A true CN107298531A (en) | 2017-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710554246.7A Pending CN107298531A (en) | 2017-07-07 | 2017-07-07 | Glass fiber with low dielectric constant and preparation method thereof |
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Cited By (3)
| 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 |
| CN110451811A (en) * | 2019-09-03 | 2019-11-15 | 济南大学 | A kind of doping Yb2O3The low dielectric glass of free-floride and preparation method thereof |
| CN115321824A (en) * | 2022-09-09 | 2022-11-11 | 清远忠信世纪电子材料有限公司 | Low-dielectric glass fiber capable of being formed at low temperature |
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| US4824806A (en) * | 1986-03-27 | 1989-04-25 | Nippon Sheet Glass Co., Ltd. | Glass fibers having low dielectric constant |
| JPH0710598A (en) * | 1993-06-22 | 1995-01-13 | Nippon Electric Glass Co Ltd | Low dielectric constant glass fiber |
| JP2003137590A (en) * | 2001-05-09 | 2003-05-14 | Nippon Electric Glass Co Ltd | Low dielectric constant low dielectric dissipation factor glass, and glass fiber and glass fiber fabric using the glass |
| CN101269915A (en) * | 2008-05-07 | 2008-09-24 | 济南大学 | Glass fibre with low dielectric constant |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4824806A (en) * | 1986-03-27 | 1989-04-25 | Nippon Sheet Glass Co., Ltd. | Glass fibers having low dielectric constant |
| JPH0710598A (en) * | 1993-06-22 | 1995-01-13 | Nippon Electric Glass Co Ltd | Low dielectric constant glass fiber |
| JP2003137590A (en) * | 2001-05-09 | 2003-05-14 | Nippon Electric Glass Co Ltd | Low dielectric constant low dielectric dissipation factor glass, and glass fiber and glass fiber fabric using the glass |
| CN101269915A (en) * | 2008-05-07 | 2008-09-24 | 济南大学 | Glass fibre with low dielectric constant |
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| 朱晓燕: "低介电玻璃纤维组合物技术简介", 《科技视界》 * |
Cited By (4)
| 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 |
| CN110451811A (en) * | 2019-09-03 | 2019-11-15 | 济南大学 | A kind of doping Yb2O3The low dielectric glass of free-floride and preparation method thereof |
| CN115321824A (en) * | 2022-09-09 | 2022-11-11 | 清远忠信世纪电子材料有限公司 | Low-dielectric glass fiber capable of being formed at low temperature |
| CN115321824B (en) * | 2022-09-09 | 2023-11-17 | 清远忠信世纪电子材料有限公司 | Low-dielectric glass fiber capable of being molded at low temperature |
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Application publication date: 20171027 |