CN114933418A - Low dielectric constant and low dielectric loss glass fiber composition, glass fiber and application thereof - Google Patents
Low dielectric constant and low dielectric loss glass fiber composition, glass fiber and application thereof Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910017976 MgO 4 Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000011521 glass Substances 0.000 description 67
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- -1 cation metal oxide Chemical class 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000005491 wire drawing Methods 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical group B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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
- C03C13/00—Fibre or filament compositions
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
Abstract
The invention relates to the field of glass fibers, and discloses a low-dielectric-constant and low-dielectric-loss glass fiber composition, a glass fiber and application thereof. The composition contains the following components which are stored in a mixing way or are respectively and independently stored: SiO 2 2 、Al 2 O 3 、B 2 O 3 、CaO、MgO、ZnO、R 2 O、Y 2 O 3 、TiO 2 . The glass fiber prepared by the glass fiber composition provided by the invention has good production performance on the premise of low dielectric constant and low dielectric loss.
Description
Technical Field
The invention relates to the field of glass fibers, in particular to a glass fiber composition with low dielectric constant and low dielectric loss, a glass fiber and application thereof.
Background
In the application of traditional electronic products, most of the application frequency is concentrated below 1GHz, and the electrical property of the common glass fiber can meet the requirement of a printed circuit board. However, in a high-frequency and high-speed environment, for example, in a frequency band of several GHz to several tens of GHz, radio waves are used for communication in a 5 th generation mobile communication system (5G), and attenuation and distortion of a high-frequency signal itself are serious. In order to solve the problems of poor penetration and high attenuation speed of high-frequency signals, the reinforced glass fiber of the printed circuit board is required to have low dielectric constant and low dielectric loss.
Common printed circuit board reinforced glass fibers comprise D glass fibers and E glass fibers.
The D glass fiber is a low dielectric glass fiber, and comprises the following components in percentage by weight: SiO 2 2 ：72-76％；Al 2 O 3 ：0-5％；B 2 O 3 ：20-25％；Na 2 O+K 2 O: 3 to 5 percent. The D glass fiber has excellent dielectric property, the dielectric constant of the D glass fiber under the condition of 1MHz is 4.1, and the dielectric loss is about 0.0009. But due to its SiO 2 The content is high, the high-temperature viscosity of the glass is very high, the homogenization and clarification time is long, and the quality of the melted glass cannot meet the requirements of a forming process. Meanwhile, the D glass fiber has high forming temperature, poor wire drawing operation stability and high production cost, and the D glass fiber and the fabric thereof also have the problems of low strength, poor water resistance and the like, so the application field of the D glass fiber can not be expanded for a long time except for some special purposes.
E glass fiber composition ranges by weight: SiO 2 2 ：54-56％；Al 2 O 3 ：14-16％；CaO：20-24％；MgO：0-2％；B 2 O 3 ：8-10％；Na 2 O+K 2 O: 0 to 1 percent. The manufacturing performance of the E glass fiber is obviously improved compared with that of the D glass fiber, but the dielectric constant of the E glass fiber under the condition of 1MHz is 6.6, the dielectric loss is 0.008, and the use requirements of high-frequency and high-speed environments cannot be met.
In view of the foregoing disadvantages of the D glass fiber and the E glass fiber, experts and scholars at home and abroad have conducted many relevant studies in the field of low dielectric glass fiber, but all of them have some disadvantages, such as:
CN113474310A discloses a low dielectric glass composition containing SiO in the range of 52.0 to 59.5 mass% 2 17.5 to 25.5 mass% of B 2 O 3 9.0 to 14.0 mass% of Al 2 O 3 SrO in the range of 0.5-6.0 mass%, MgO in the range of 1.0-5.0 mass%, CaO in the range of 1.0-5.0 mass%, and F in the range of 0.1-2.5 mass% in total 2 And Cl 2 However, it contains F, Cl elements which pollute the environment, and it contains easily polarizable SrO and CaO, and the dielectric constant reaches 4.8.
WO2020/156374A1 discloses a low dielectric glass fiber having the following composition by weight: SiO 2 2 ：54-57％；Al 2 O 3 ：12-15％；B 2 O 3 ：16-25％；CaO：1-2.5％；MgO：2-5％；ZnO：2-4％；TiO 2 ：0.4-2％；ZrO 2 ：0-0.5％；Bi 2 O3: 0.1-1.5%, but Al thereof 2 O 3 The glass fiber has high content, insufficient free oxygen, more layered boron-oxygen triangles in the structure of the glass fiber, loose structure, high dielectric constant between 4.7 and 4.9 and high dielectric constant.
CN103351102A discloses a glass fiber composition, which comprises the following components in percentage by weight: SiO 2 2 ：50-58％；Al 2 O 3 ：10.5-16％；B 2 O 3 ：23.4-30％；CaO+MgO：＜7％；P 2 O 5 ：4.1-6％；Fe 2 O 3 : < 0.5%, but it contains a large amount of P 2 O 5 When the tank furnace method is adopted for production, the refractory material of the kiln can be corroded, so that the service life of the production line is shortened.
CN101012105A discloses a low dielectric constant fiber: SiO 2 2 ：50-60％；Al 2 O 3 ：6-9.5％；B 2 O 3 ：30.5-35％；CaO：0-5％；MgO：0-5％；ZnO：0.5-5％；TiO 2 ：0.5-3％；Na 2 O：0-1.5％；K 2 0：0-1.5％；Li 2 O: 0-1.5%, except that B 2 O 3 High content, serious volatilization in production process and fiberPoor component uniformity, more yarn breakage in the manufacturing process and poor water resistance.
CN102503153A discloses a low dielectric glass fiber material formula, which comprises the following components in percentage by mass: SiO 2 2 ：48％-58％；B 2 O 3 ：23％-25％；Al 2 O 3 ：13％-15％；Na 2 0：0.1％-1；CaO：3％-5％；MgO：0％-6％；Y 2 0 3 ：0.5-8％；CeO 2 ：0.5-0.6％；F：0-3wt％；TiO 2 : 0 to 0.45%, although the production characteristics are improved, it contains F element, which causes environmental pollution.
Disclosure of Invention
The invention aims to overcome the defects that the existing glass fiber has high dielectric constant and poor water resistance, is easy to have a wire breakage phenomenon in the manufacturing process and causes pollution to the environment.
In order to achieve the above object, a first aspect of the present invention provides a low dielectric constant and low dielectric loss glass fiber composition comprising two or more of the following components stored in admixture or independently:
SiO 2 、Al 2 O 3 、B 2 O 3 、CaO、MgO、ZnO、R 2 O、Y 2 O 3 、TiO 2 ；
the SiO is present in an amount based on the total weight of the composition 2 Is 51 to 56.5 wt%, the Al 2 O 3 In an amount of 7 to 11 wt%, said B 2 O 3 22-29 wt%, CaO 0-5 wt%, MgO 2-6 wt%, ZnO 0-9 wt%, and R 2 The content of O is 0.1 to 1 wt%, and the Y 2 O 3 Is 0-7 wt%, the TiO 2 The content of (B) is 0.01-2.5 wt%;
wherein, R is 2 O is selected from Na 2 O、K 2 At least one of O;
and said Al 2 O 3 Content M of 1 The B 2 O 3 Content M of 2 The above-mentionedContent M of CaO 3 The content M of MgO 4 The content M of ZnO 5 The R is 2 Content M of O 6 The Y mentioned 2 O 3 Content M of 7 The TiO described above 2 Content M of 8 Satisfies the requirement of formula (1), wherein the unit of content is wt%:
formula (1): -0.2<{0.98×M 6 +0.75×(M 3 +M 7 +M 8 )+0.45×(M 4 +M 5 )-M 1 }/M 2 <0.1；
At the same time, M 3 、M 5 、M 7 Not simultaneously 0.
Preferably, the SiO is present in an amount based on the total weight of the composition 2 Is 51 to 56.5 wt%, the Al 2 O 3 In an amount of 7 to 11 wt%, said B 2 O 3 24-28 wt%, CaO 2-4 wt%, MgO 2-6 wt%, ZnO 0.5-5.5 wt%, and R 2 The content of O is 0.1 to 1 wt%, and the Y 2 O 3 In an amount of 0.5 to 4 wt%, said TiO 2 The content of (B) is 0.01-2.5 wt%.
A second aspect of the present invention provides a method of making glass fibers, the method comprising:
(1) mixing the components of the low dielectric constant and low dielectric loss glass fiber composition of the first aspect to obtain a mixture I;
(2) and sequentially carrying out heating treatment, forming and annealing treatment on the mixture I.
Preferably, in step (1), the mixing conditions at least satisfy: the stirring is carried out under the stirring condition, the rotating speed of the stirring is 10-16rpm, and the time is 5-20 min.
Preferably, in the step (2), the conditions of the heat treatment at least satisfy: the temperature is 1570-1610 ℃, and the time is 3-7 h.
Preferably, in the step (2), the annealing treatment is performed under conditions at least satisfying: the temperature is 500 ℃ and 600 ℃, and the time is 2-3 h.
A third aspect of the present invention provides a glass fiber produced by the method described in the second aspect.
Preferably, the glass fiber has a dielectric constant of less than 4.50 at 1MHz and a dielectric constant of less than 4.50 at 10 GHz.
Preferably, the glass fiber has a dielectric loss of less than 9X 10 under 1MHz conditions -4 Dielectric loss at 10GHz of 4.5X 10 -3 。
Preferably, the glass fibers have a forming temperature T3 below 1330 ℃ and a liquidus temperature TL below 1220 ℃ at a viscosity of 1000Pa s.
Preferably, the glass fiber has a breaking strength of more than 0.59N/tex and a thermal conductivity of 1.00-1.30W/(m.k).
A fourth aspect of the invention provides a use of the glass fiber described in the aforementioned third aspect in a circuit board.
The invention controls SiO 2 、Al 2 O 3 、B 2 O 3 Under the premise of content, the use amounts of MgO, ZnO and CaO are accurately adjusted to promote the transformation of oxides formed by the glass from boron-oxygen triangles with a layered network structure to boron-oxygen tetrahedrons with a frame network structure, so that the dielectric constant of the glass is reduced and the crystallization temperature of the glass is improved; meanwhile, the invention adopts a certain amount of Na 2 O、K 2 O is used as a fluxing agent to reduce the viscosity of the glass, thereby improving the production performance of the glass; in addition, the invention also adopts a certain amount of cation metal oxide Y with larger field intensity 2 O 3 、TiO 2 The glass network structure is adjusted and improved, so that the glass fiber with both service performance and manufacturing performance is obtained.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a low dielectric constant and low dielectric loss glass fiber composition containing two or more of the following components stored in admixture or independently:
SiO 2 、Al 2 O 3 、B 2 O 3 、CaO、MgO、ZnO、R 2 O、Y 2 O 3 、TiO 2 ；
based on the total weight of the composition, the SiO 2 Is 51 to 56.5 wt%, the Al 2 O 3 In an amount of 7 to 11 wt%, said B 2 O 3 22-29 wt%, CaO 0-5 wt%, MgO 2-6 wt%, ZnO 0-9 wt%, and R 2 The content of O is 0.1-1 wt%, and the Y is 2 O 3 Is 0-7 wt%, the TiO 2 The content of (B) is 0.01-2.5 wt%;
wherein, R is 2 O is selected from Na 2 O、K 2 At least one of O;
and said Al 2 O 3 Content M of 1 The B 2 O 3 Content M of 2 The content M of CaO 3 The content M of MgO 4 The content M of ZnO 5 The R is 2 Content M of O 6 The Y mentioned 2 O 3 Content M of 7 The TiO mentioned 2 Content M of 8 Satisfies the requirement of formula (1), wherein the unit of content is wt%:
formula (1): -0.2<{0.98×M 6 +0.75×(M 3 +M 7 +M 8 )+0.45×(M 4 +M 5 )-M 1 }/M 2 <0.1；
At the same time, M 3 、M 5 、M 7 Not simultaneously 0.
The inventor of the invention defines the content range of each component in the glass fiber composition provided by the invention based on the following thought:
SiO 2 the oxide is a glass former oxide, and the irregular continuous network is formed by silicon-oxygen tetrahedral structural units to form a framework of the glass. When SiO is present 2 When the content is too low, the integrity of a glass network is poor, the strength of the glass is reduced, the problem of wire breakage is easy to occur in the wire drawing process, and meanwhile, the chemical stability and the water resistance of the glass are reduced; when SiO is present 2 When the content is too high, the glass is difficult to melt, the viscosity is very high, clarification and homogenization are difficult, the fiber forming temperature is high, the stability of wire drawing operation is poor, and the production cost is high. Therefore, the inventors of the present invention have conducted extensive studies and then have found that SiO is a rare earth metal 2 The content is limited to 51-56.5 wt%.
B 2 O 3 Also glass former oxides, boron-oxygen tetrahedrons [ BO 4 ]The structure is a frame structure, the structure is compact, and the dielectric constant can be effectively reduced. If, however, B 2 O 3 The content is continuously increased, the glass does not have enough free oxygen, and boron-oxygen trigonal [ BO ] with a laminated structure 3 ]Boron-oxygen tetrahedron (BO) with increased content and frame structure 4 ]The content is reduced, thereby leading to the loose structure of the glass network and unstable chemical property. Too high B 2 O 3 The content also causes an increase in volatilization, and tends to cause unevenness in glass composition. Therefore, the inventors of the present invention have conducted extensive studies and found that B 2 O 3 The content is defined as 22-29 wt.%.
Al 2 O 3 As glass intermediate oxide, Al 2 O 3 Can reduce the crystallization tendency of the glass and improve the chemical stability of the glass, but has too low Al 2 O 3 The content is detrimental to the water resistance of the glass. Because the alundum structure is more stable than the boroxine structure, the aluminum ions in the structural glass unit preferentially acquire free oxygen to form alundum, and then the excess free oxygen and the boroxine [ BO ] triangle 3 ]Conversion to boron-oxygen tetrahedron [ BO 4 ]. In addition, Al is disadvantageous in reducing dielectric loss of glass due to the bulky alundum 2 O 3 The content should not be too high. Therefore, the inventors of the present invention studied Al after a lot of studies 2 O 3 The content is defined as 7-11 wt.%.
MgO and CaO are alkaline earth metal oxides, and the addition of one or both of MgO and CaO is beneficial to reducing the high-temperature viscosity of the glass, thereby improving the meltability and the formability of the glass, being beneficial to the spinning forming operation during the manufacture of glass fibers, and being beneficial to improving the water resistance and the chemical stability of the glass fibers. However, too much of either or both of them will cause the glass network to break, resulting in deterioration of dielectric properties. Accordingly, the inventors of the present invention limited the content of CaO to 0-5 wt% and the content of MgO to 2-6 wt% through extensive studies.
ZnO has 18 outer-layer electronic structures, zinc ions are easier to polarize relative to alkaline earth metals, the viscosity of the glass can be reduced at high temperature, and compared with the glass without ZnO in the same high-temperature state, the glass containing ZnO has lower viscosity and higher atomic movement speed, is difficult to form crystal nuclei, and therefore the crystallization upper limit temperature of the glass is reduced. In addition, the zinc ions and the magnesium ions have the same charge number and the ion radiuses are close, and when the zinc ions and the magnesium ions are used together, the similar mixed alkaline earth effect can be generated, and the optimal toughness, chemical resistance and dielectric property are obtained. However, when the content of ZnO is too high, the destruction and depolymerization of the network structure of glass by ZnO increases, which is not favorable for reducing the dielectric constant and dielectric loss of the glass fiber. Therefore, the inventors of the present invention have limited the content of ZnO to 0 to 9 wt% through extensive studies.
Alkali metal oxide Na 2 O and K 2 O is a good fluxing agent, can reduce the viscosity of the glass and improve the production performance of the glass. However, if the monovalent cation is increased, the glass network structure is easily loosened, the network gap is increased, and the dielectric constant and the dielectric loss are greatly influenced. Therefore, the inventors of the present invention conducted extensive studies and found that R is 2 The content of O is limited to 0.1 to 1 wt%.
Y 2 O 3 Yttrium ion and TiO in (III) 2 The titanium ion field intensity is larger, the broken bond of the network and the stable electron and charge can be strongly attracted, the addition of one or both of the titanium ion field intensity and the stable electron and charge can enter the network gap, the density of the network is increased, the electron displacement polarization and the ion displacement polarization are both reduced, and the cation doped in the glass network and the non-bridge directly adjacent to the cation areThe dipolar mechanism exists between oxygen ions to promote AlO 5 ]、[AlO 6 ]、[BO 3 ]Tetrahedron of equiangular polyhedron [ AlO 4 ]And [ BO ] 4 ]The transformation increases the degree of polymerization of the glass network and reduces the number of non-bridging oxygen ions in the glass, thereby reducing the dielectric constant and dielectric loss of the glass. However, if the amount is excessively added, the tendency of the glass to crystallize increases, and the formation range of the glass decreases. Therefore, the inventors of the present invention conducted extensive studies to find Y 2 O 3 Is limited to 0 to 7 wt%, and TiO is added 2 The content of (B) is limited to 0.01-2.5 wt%.
In addition, the inventors of the present invention have found through creative research that, when the content of each component in the glass fiber composition provided based on the present invention satisfies formula (1), the ability of providing free oxygen ions is advantageous for reducing the dielectric constant, dielectric loss and crystallization temperature of the glass.
Preferably, the SiO is present in an amount based on the total weight of the composition 2 Is 51 to 56.5 wt%, the Al 2 O 3 In an amount of 7 to 11 wt%, said B 2 O 3 24-28 wt%, CaO 2-4 wt%, MgO 2-6 wt%, ZnO 0.5-5.5 wt%, and R 2 The content of O is 0.1 to 1 wt%, and the Y 2 O 3 In an amount of 0.5 to 4 wt%, said TiO 2 The content of (B) is 0.01-2.5 wt%.
As previously mentioned, a second aspect of the invention provides a method of making glass fibers, the method comprising:
(1) mixing the components of the glass fiber composition with low dielectric constant and low dielectric loss described in the first aspect to obtain a mixture I;
(2) and sequentially carrying out heating treatment, forming and annealing treatment on the mixture I.
Preferably, in step (1), the mixing conditions at least satisfy: the stirring is carried out under the stirring condition, the rotating speed of the stirring is 10-16rpm, and the time is 5-20 min.
Preferably, in the step (2), the conditions of the heat treatment at least satisfy: the temperature is 1570-1610 ℃, and the time is 3-7 h.
Preferably, in the step (2), the annealing treatment is performed under conditions at least satisfying: the temperature is 500-600 ℃, and the time is 2-3 h.
As previously mentioned, a third aspect of the present invention provides a glass fiber made by the method described in the second aspect above.
Preferably, the glass fiber has a dielectric constant of less than 4.50 at 1MHz and a dielectric constant of less than 4.50 at 10 GHz.
Preferably, the glass fiber has a dielectric loss of less than 9X 10 under 1MHz conditions -4 Dielectric loss at 10GHz of 4.5X 10 -3 。
Preferably, the glass fibers have a forming temperature T3 below 1330 ℃ and a liquidus temperature TL below 1220 ℃ at a viscosity of 1000Pa s.
Preferably, the glass fiber has a breaking strength of more than 0.59N/tex and a thermal conductivity of 1.00-1.30W/(m.k).
As mentioned previously, a fourth aspect of the invention provides a use of the glass fibre described in the previous third aspect in a circuit board.
The present invention will be described in detail below by way of examples.
In the following examples, the raw materials used are all commercially available unless otherwise specified.
In the following examples, the total amount of the composition used is 100g unless otherwise specified.
In the present invention, the room temperature means 25. + -. 2 ℃ unless otherwise specified.
Example 1
(1) 53.60g of SiO 2 9.90g of Al 2 O 3 26.30g of B 2 O 3 2.40g of MgO, 1.70g of CaO, 3.30g of ZnO, 0.60g of R 2 O (containing 0.35g of Na therein) 2 O, 0.25g of K 2 O) and 2.20g of TiO 2 Stirring at the rotating speed of 15rpm for 15min to obtain a mixture I;
(2) adding the mixture I into a platinum crucible, heating and treating the mixture I for 4 hours at 1590 ℃ in a lifting furnace, stirring the mixture and exhausting the gas, adding the mixture into a mould to form block glass, then annealing the block glass for 2 hours at 550 ℃ in an annealing furnace, and annealing the block glass to room temperature to obtain glass X1.
Examples 2 to 9
Examples 2 to 9 were carried out in a similar manner to example 1, except that the starting materials were used in different amounts, to give glass X2, glass X3, glass X4, glass X5, glass X6, glass X7, glass X8 and glass X9, respectively, as specified in Table 1.
Comparative example 1:
this comparative example was conducted in a similar manner to example 1 except that the starting materials were used in different amounts and the other conditions were the same as in example 1 to obtain glass DX1, as specified in Table 1.
Comparative example 2:
this comparative example was carried out in a similar manner to example 1, except that the amounts of the starting materials were different and the other conditions were the same as in example 1, to obtain glass DX2, see in particular Table 1.
Comparative example 3:
this comparative example was carried out in a similar manner to example 1, except that: glass DX3 was obtained by using no MgO and the same conditions as in example 1, see Table 1 for details.
Comparative example 4:
this comparative example was carried out in a similar manner to example 1, except that the amounts of the starting materials were different and the other conditions were the same as in example 1, to obtain glass DX4, see in particular Table 1.
Comparative example 5
This comparative example was carried out in a similar manner to example 1, except that: glass DX5 was obtained in the same manner as in example 1 except that CaO and ZnO were not used, specifically referring to Table 1.
Test example
The glasses prepared in the examples and the comparative examples were subjected to the following tests, the specific test methods are as follows, and the specific results are shown in table 2:
(1) dielectric constant and dielectric loss: the glass was subjected to slicing, grinding and polishing, and then tested for dielectric constant and dielectric loss, according to the test method in ASTM-D150.
(2) Molding temperature T3 at a viscosity of 1000Pa · s: the high temperature viscosity temperature of the glass is determined with reference to the test method in astm c-965.
(3) Liquidus temperature TL: the liquidus temperature of the glass fiber was measured by the gradient temperature furnace method in ASTMC-829.
(4) Breaking strength: and (3) according to the test method in GB/T7690-2013, remelting and drawing glass to measure the breaking strength.
(5) Water resistance: the glass was processed into a powder having a particle size of 400. + -. 50 μm, placed in a constant-temperature water bath at 80 ℃ for 24 hours and then dried at 110 ℃ for 4 hours, and the percentage of weight reduction was measured.
(6) Coefficient of thermal conductivity: the thermal conductivity of the glass was tested according to the test method of GB/T7962.13-1987.
TABLE 1
TABLE 2
Note: in the table,. DELTA.T.T 3-TL.
TABLE 2
As can be seen from the results in Table 2, the glass fiber prepared by using the glass fiber composition provided by the invention has good production performance on the premise of having both low dielectric constant and low dielectric loss. Specifically, the following are:
the glass fiber prepared from the glass fiber composition provided by the invention has the T3 temperature (glass drawing temperature) lower than 1330 ℃, the TL temperature (upper crystallization limit temperature) lower than 1220 ℃ and the Delta T temperature higher than 80 ℃;
the breaking strength of the glass fiber prepared by the glass fiber composition provided by the invention is more than or equal to 0.6N/tex, and the weight loss percentage is less than 0.4 wt%.
The glass fiber prepared by the glass fiber composition provided by the invention has the thermal conductivity coefficient of 1.00-1.30W/(m.k), is beneficial to heat dissipation of a printed circuit board, and ensures the service performance of the circuit board.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A glass fiber composition with low dielectric constant and low dielectric loss is characterized by comprising the following components which are stored in a mixed manner or independently:
SiO 2 、Al 2 O 3 、B 2 O 3 、CaO、MgO、ZnO、R 2 O、Y 2 O 3 、TiO 2 ；
based on the total weight of the composition, the SiO 2 Is 51 to 56.5 wt%, the Al 2 O 3 In an amount of 7 to 11 wt%, said B 2 O 3 22-29 wt%, CaO 0-5 wt%, MgO 2-6 wt%, ZnO 0-9 wt%, and R 2 The content of O is 0.1-1 wt%, and the Y is 2 O 3 Is 0-7 wt%, the TiO 2 The content of (B) is 0.01-2.5 wt%;
wherein, R is 2 O is selected from Na 2 O、K 2 At least one of O;
and said Al 2 O 3 Content M of 1 Said B 2 O 3 Content M of 2 The content M of CaO 3 The content M of MgO 4 The content M of ZnO 5 R said 2 Content M of O 6 The Y mentioned 2 O 3 Content M of 7 The TiO described above 2 Content M of 8 Satisfies the requirement of formula (1), wherein the unit of content is wt%:
formula (1): -0.2<{0.98×M 6 +0.75×(M 3 +M 7 +M 8 )+0.45×(M 4 +M 5 )-M 1 }/M 2 <0.1；
At the same time, M 3 、M 5 、M 7 Not simultaneously 0.
2. The composition of claim 1, wherein the SiO is present in an amount based on the total weight of the composition 2 Is 51 to 56.5 wt%, the Al 2 O 3 In an amount of 7 to 11 wt%, said B 2 O 3 24-28 wt%, CaO 2-4 wt%, MgO 2-6 wt%, ZnO 0.5-5.5 wt%, and R 2 The content of O is 0.1-1 wt%, and the Y is 2 O 3 In an amount of 0.5 to 4 wt%, said TiO 2 The content of (B) is 0.01-2.5 wt%.
3. A method of making glass fibers, comprising:
(1) mixing the components of the low dielectric constant and low dielectric loss glass fiber composition of claim 1 or 2 to obtain a mixture I;
(2) and sequentially carrying out heating treatment, forming and annealing treatment on the mixture I.
4. The method according to claim 3, wherein in step (1), the mixing conditions at least satisfy: the stirring is carried out under the stirring condition, the rotating speed of the stirring is 10-16rpm, and the time is 5-20 min.
5. The method according to claim 3 or 4, wherein in step (2), the conditions of the heat treatment at least satisfy: the temperature is 1570-1610 ℃, and the time is 3-7 h.
6. The method according to any one of claims 3 to 5, wherein in the step (2), the condition of the annealing treatment at least satisfies: the temperature is 500-600 ℃, and the time is 2-3 h.
7. Glass fibers produced by the process of any one of claims 3 to 6.
8. The glass fiber according to claim 7, wherein the glass fiber has a dielectric constant of less than 4.50 at 1MHz and a dielectric constant of less than 4.50 at 10 GHz;
preferably, the glass fiber has a dielectric loss of less than 9X 10 under 1MHz conditions -4 Dielectric loss at 10GHz of 4.5X 10 -3 。
9. The glass fiber according to claim 7 or 8, wherein the glass fiber has a forming temperature T3 below 1330 ℃ at a viscosity of 1000 Pa-s, a liquidus temperature TL below 1220 ℃;
preferably, the glass fiber has a breaking strength of more than 0.59N/tex and a thermal conductivity of 1.00-1.30W/(m.k).
10. Use of a glass fiber according to any of claims 7 to 9 in a circuit board.
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