Low-dielectric glass fiber material as well as preparation method and application thereof

Abstract

The invention provides a low dielectric glass fiber material as well as a preparation method and application thereof, and the low dielectric glass fiber material comprises the following components in percentage by weight: 54 to 57 percent of SiO2, 12 to 15 percent of Al2O3, 16 to 24 percent of B2O3, 1 to 2.5 percent of CaO, 2 to 5 percent of MgO, 2 to 4 percent of ZnO, 0.4 to 2 percent of TiO2, 0.2 to 0.5 percent of ZrO2 and 1.2 to 3.4 percent of CeO2. The glass with low dielectric constant and low dielectric loss performance is obtained by introducing low-content cerium oxide into a glass fiber material, controlling the content of SiO2 in a high range, adjusting the content of B2O3 in a low range and reasonably controlling the content of several main components, and the problems that the chemical stability of the glass fiber is reduced after cerium oxide is added, and the glass has low dielectric loss performance are solved. The thermal expansion coefficient is increased, so that thermal stress mismatching and cracking are caused when the material is matched with other materials for use.

Description

Technical Field

[0001] The present invention relates to the technical field of glass fiber materials, and particularly to a low-dielectric glass fiber material, a preparation method thereof, and an application thereof. Background Art

[0002] With the rapid development of electronic information technology, the integration degree of very large scale integrated circuit devices is getting higher and higher, and the demand for low-dielectric constant materials is becoming increasingly urgent. As an important electronic material, low-dielectric glass fiber has a wide range of applications in fields such as high-frequency and high-speed printed circuit boards, communication equipment, and aerospace. At present, the commonly used low-dielectric glass fibers at home and abroad are mainly E glass fiber and D glass fiber. Among them, the composition of E glass fiber is: 52-56% of SiO2, 12-16% of Al2O3, 5-10% of B2O3, 16-25% of CaO, 0-5.0% of MgO, 3-5% of Na2O+K2O. E glass fiber has the advantages of good processability, good water resistance, and low price, but its dielectric constant is about 6.7, which is relatively high, and the dielectric loss is greater than 10 -3 relatively large, unable to meet the requirements of high density and high-speed information processing; the composition of D glass fiber is: 72-76% of SiO2, 0-5% of Al2O3, 20-25% of B2O3, 3-5% of Na2O+K2O, its dielectric constant is about 4.1, and the dielectric loss is 8×10 -4 or so, but D glass fiber has the following disadvantages:

[0003] First of all, the relatively high content of SiO2 in D glass fiber results in poor drilling performance of its reinforced laminate, which is not conducive to subsequent processing; secondly, D glass fiber has a high glass softening point and poor meltability, and is prone to produce veins and bubbles, increasing the difficulty of wire drawing operation, resulting in very poor productivity and workability, high production cost, and being not easy to mass-produce; at the same time, the high melting temperature and high wire drawing temperature of D glass fiber require very strict quality for the kiln, which will reduce the kiln life; finally, the water resistance of the glass fiber is relatively poor, which is likely to cause the peeling of the fiber and the resin.

[0004] The patent with the publication number CN118459104A discloses a glass fiber, a preparation method thereof, and an application thereof. Introducing cerium oxide significantly reduces the high-temperature viscosity of the glass fiber and is beneficial to the industrial production of glass. However, after introducing cerium oxide, it will also cause the chemical stability of the glass fiber to decrease and the thermal expansion coefficient to increase, resulting in problems such as thermal stress mismatch and cracking when used in combination with other materials.

[0005] Therefore, it is necessary to develop a new type of low-dielectric glass fiber material to overcome the defects of the existing technology. Summary of the Invention

[0006] In view of this, the present invention provides a low-dielectric glass fiber material, its preparation method and application, which solve the technical problems of high dielectric loss, thermal stress mismatch and cracking in the prior art.

[0007] The technical solution of the present invention is realized as follows:

[0008] On the one hand, the present invention provides a low-dielectric glass fiber material, which includes the following components by weight percentage:

[0009] SiO2 54 - 57%, Al2O3 12 - 15%, B2O3 16 - 24%, CaO 1 - 2.5%, MgO 2 - 5%, ZnO 2 - 4%, TiO2 0.4 - 2%, ZrO2 0.2 - 0.5% and CeO2 1.2 - 3.4%.

[0010] On the basis of this technical solution, further preferably, CeO2 is subjected to a modification treatment, and the specific modification method includes the following steps:

[0011] Add CeO2 to the sodium stearate solution, stir to obtain a suspension, perform ultrasonic treatment for 0.5 - 1 h, filter, dry at 60 - 70 °C, pulverize, and heat-treat at 450 - 500 °C under gas protection to obtain modified CeO2.

[0012] On the basis of this technical solution, further preferably, the mass concentration of the sodium stearate solution is 4.5 - 7%.

[0013] On the basis of this technical solution, further preferably, the molar ratio of CeO2 to the sodium stearate solution is 1:6 - 10.

[0014] On the basis of this technical solution, further preferably, the power of the ultrasonic wave is 180 - 200 W.

[0015] On the second aspect, the present invention also provides a preparation method of the low-dielectric glass fiber material described in the first aspect, including the following steps:

[0016] Mix SiO2, Al2O3, B2O3, CaO, MgO, ZnO, TiO2, ZrO2 and CeO2 in proportion to obtain a mixture;

[0017] Melt the mixture at a temperature of 1300 - 1500 °C for a melting time of 2 - 3.5 h to obtain a glass melt;

[0018] Draw the glass melt, and then add a coupling agent for surface treatment to obtain the low-dielectric glass fiber material.

[0019] On the basis of this technical solution, more preferably, the coupling agent is vinyltrimethoxysilane, vinyltrichlorosilane or vinyltriethoxysilane.

[0020] On the basis of this technical solution, more preferably, the mass of the coupling agent is 0.8-1.1% of the mass of the mixture.

[0021] On the basis of this technical solution, it is further preferred that the wire drawing speed is 2500-4000 m / min and the wire drawing time is 20-30 min.

[0022] In a third aspect, the present invention further provides the use of the low-dielectric glass fiber material described in the first aspect and the low-dielectric glass fiber material obtained by the preparation method of the low-dielectric glass fiber material described in the second aspect in circuit board printing.

[0023] The low-dielectric glass fiber material and its preparation method and application described in the present invention have the following beneficial effects compared with the prior art:

[0024] The present invention adds cerium oxide to a low-dielectric glass fiber material. The cerium oxide acts as a network modifier in the glass fiber material and breaks the network of the glass fiber material, so that the cerium oxide can be used as a fluxing component for the glass fiber. Furthermore, cerium ions can also accumulate the glass fiber network at low temperatures and improve the network structure of the glass fiber. Therefore, the addition of cerium oxide may improve the dielectric properties of the glass fiber material. At the same time, the addition of a certain amount of cerium oxide can reduce the viscosity of the glass fiber, increase the thermal expansion coefficient, and affect the chemical stability of the glass fiber material itself, resulting in thermal stress mismatch and cracking problems when used in combination with other materials. On this basis, the present invention chemically modifies the cerium oxide by adding sodium stearate to react with hydroxyl groups on the surface of the cerium oxide to form a stearic acid layer, thereby effectively improving the dispersion effect after the addition of cerium oxide and enhancing thermal stability and chemical stability. The resulting glass fiber material has good dielectric properties and excellent thermal stability.

[0025] The present invention optimizes the internal structure of low-dielectric glass fiber by precisely controlling the content range of multiple main components such as SiO2, Al2O3, B2O3 and CeO2, ensuring that the low-dielectric glass fiber has good mechanical properties, corrosion resistance and forming properties, thereby overcoming the difficulty of obtaining high-performance glass fiber with lower production difficulty. DETAILED DESCRIPTION

[0026] The following will describe the technical solutions in the embodiments of the present invention clearly and completely in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0027] The present invention provides a low-dielectric glass fiber material, its preparation method and application. By introducing a lower content of cerium oxide into the glass fiber material and controlling the SiO2 content within a higher range and adjusting the B2O3 content within a lower range, the contents of several main components are reasonably controlled to obtain a glass with low dielectric constant and low dielectric loss performance.

[0028] Example 1

[0029] This example provides a low-dielectric glass fiber material, including the following components in weight percentages: SiO2 54%, Al2O3 12%, B2O3 16%, CaO 1%, MgO 2.2%, ZnO 2%, TiO2 0.4%, ZrO2 0.2% and CeO2 1.2%.

[0030] In this embodiment, specifically, CeO2 is subjected to a modification treatment. The specific modification method includes the following steps:

[0031] Add CeO2 to the sodium stearate solution, stir to obtain a suspension, perform ultrasonic treatment for 0.5 h, filter, dry at 60 °C, pulverize, and heat-treat at 450 °C under nitrogen protection to obtain modified CeO2.

[0032] In this embodiment, specifically, the mass concentration of the sodium stearate solution is 4.5%.

[0033] In this embodiment, specifically, the molar ratio of CeO2 to the sodium stearate solution is 1:10.

[0034] In this embodiment, specifically, the power of the ultrasonic wave is 200 W.

[0035] More specifically, the preparation method of the low-dielectric glass fiber material includes the following steps: Mix SiO2, Al2O3, B2O3, CaO, MgO, ZnO, TiO2, ZrO2 and CeO2 in proportion to obtain a mixture; melt the mixture at a temperature of 1300 °C for 3.5 h to obtain a glass melt; draw the glass melt, and then add a coupling agent for surface treatment to obtain the low-dielectric glass fiber material.

[0036] More specifically, the coupling agent is vinyltrimethoxysilane.

[0037] More specifically, the mass of the coupling agent is 0.8% of the mass of the mixture.

[0038] More specifically, the wire drawing speed is 2500 m / min and the wire drawing time is 30 min.

[0039] Example 2

[0040] This example provides a low dielectric glass fiber material, comprising the following components in weight percentages:

[0041] SiO2 57%, Al2O3 15%, B2O3 24%, CaO 2.5%, MgO 5%, ZnO 4%, TiO2 2%, ZrO2 0.5% and CeO2 3.4%.

[0042] In this embodiment, specifically, CeO2 is subjected to a modification treatment. The specific modification method includes the following steps:

[0043] Add CeO2 to the sodium stearate solution, stir to obtain a suspension, and perform ultrasonic treatment for 1 h.

[0044] Filter, dry at 70 °C, pulverize, and heat-treat at 500 °C under nitrogen protection to obtain modified CeO2.

[0045] In this embodiment, specifically, the mass concentration of the sodium stearate solution is 7%.

[0046] In this embodiment, specifically, the molar ratio of CeO2 to the sodium stearate solution is 1:6.

[0047] In this embodiment, specifically, the power of the ultrasonic wave is 180 W.

[0048] More specifically, the preparation method of the low dielectric glass fiber material includes the following steps:

[0049] Mix SiO2, Al2O3, B2O3, CaO, MgO, ZnO, TiO2, ZrO2 and CeO2 in proportion.

[0050] Obtain a mixture.

[0051] Melt the mixture at a temperature of 1500 °C for 2 h to obtain a glass melt.

[0052] Draw the glass melt, and then add a coupling agent for surface treatment to obtain the low dielectric glass fiber material.

[0053] More specifically, the coupling agent is vinyltrimethoxysilane, vinyltrichlorosilane or vinyltriethoxysilane.

[0054] More specifically, the mass of the coupling agent is 1.1% of the mass of the mixture.

[0055] More specifically, the drawing speed is 4000 m / min and the drawing time is 20 min.

[0056] Example 3

[0057] This example provides a low-dielectric glass fiber material, comprising the following components in weight percentages: 55% of SiO2, 14% of Al2O3, 20% of B2O3, 1.5% of CaO, 2.5% of MgO, 3% of ZnO, 1.2% of TiO2, 0.4% of ZrO2, and 2.8% of CeO2.

[0058] In this embodiment, specifically, CeO2 is subjected to a modification treatment. The specific modification method comprises the following steps:

[0059] CeO2 is added to a sodium stearate solution, stirred to obtain a suspension, ultrasonically treated for 0.6 h, filtered, dried at 65 °C, pulverized, and heat-treated at 480 °C under nitrogen protection to obtain modified CeO2.

[0060] In this embodiment, specifically, the mass concentration of the sodium stearate solution is 6%.

[0061] In this embodiment, specifically, the molar ratio of CeO2 to the sodium stearate solution is 1:8.

[0062] In this embodiment, specifically, the power of the ultrasonic wave is 190 W.

[0063] More specifically, the preparation method of the low-dielectric glass fiber material comprises the following steps:

[0064] SiO2, Al2O3, B2O3, CaO, MgO, ZnO, TiO2, ZrO2, and CeO2 are mixed evenly in proportion to obtain a mixture;

[0065] The mixture is melted at a temperature of 1400 °C for 3 h to obtain a glass melt;

[0066] The glass melt is drawn, and after drawing, a coupling agent is added for surface treatment to obtain the low-dielectric glass fiber material.

[0067] More specifically, the coupling agent is vinyltrimethoxysilane, vinyltrichlorosilane, or vinyltriethoxysilane.

[0068] More specifically, the mass of the coupling agent is 0.9% of the mass of the mixture. More specifically, the drawing speed is 3500 m / min and the drawing time is 26 min.

[0069] Comparative Example 1

[0070] A glass fiber material, different from Example 1 in that cerium oxide is not introduced.

[0071] Comparative Example 2

[0072] A glass fiber material, different from Example 2 in that the cerium oxide is not modified.

[0073] Comparative Example 3

[0074] A glass fiber material, different from Example 3 in that in the weight percentage of the material, SiO2 is 48%, Al2O3 is 20%, and B2O3 is 29%.

[0075] Comparative Example 4

[0076] A glass fiber material, different from Example 1 in that the mass concentration of the sodium stearate solution is 2.5%.

[0077] Comparative Example 5

[0078] A glass fiber material, different from Example 1 in that the coupling agent is not added.

[0079] The low-dielectric glass fiber material prepared by the method of the present invention is applied in circuit board printing, has excellent dielectric properties, and has simple production conditions.

[0080] The properties of the glass fiber materials obtained in each example and comparative example were tested, and the results are shown in Table 1.

[0081] Table 1 Performance test of glass fiber materials in examples and comparative examples

[0082]

[0083]

[0084] As can be seen from Table 1, in Comparative Examples 1-5, without introducing cerium oxide, without modifying cerium oxide, with different ratios of main components or different ratios of modified components and without adding a coupling agent, their dielectric constants and dielectric losses are significantly higher than those of Examples 1-3. At the same time, the thermal expansion coefficients of the former also remain at a relatively high level, but the tensile strength is lower than that of Examples 1-3. The reason for the analysis may be that after chemically modifying the existing cerium oxide, sodium stearate is added in a reasonable ratio to react with the hydroxyl groups on the surface of cerium oxide to form a stearic acid layer, which better improves the dispersion effect after adding cerium oxide, enhances the thermal stability and chemical stability, and at the same time, the reasonable ratio of the main components keeps the dielectric constant and dielectric loss of the glass fiber material at a relatively low level.

[0085] In summary, the present invention provides a low-dielectric glass fiber material, its preparation method and application. Adding cerium oxide can improve the dielectric properties of the glass fiber material. Chemically modifying cerium oxide and adding sodium stearate to react with the hydroxyl groups on the surface of cerium oxide to form a stearic acid layer, which better improves the dispersion effect after adding cerium oxide, solves the technical problems that the chemical stability of the glass fiber decreases and the thermal expansion coefficient increases after adding cerium oxide, resulting in thermal stress mismatch and cracking when used in combination with other materials.

[0086] The above is only the preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A low dielectric glass fiber material, characterized in that, By weight percentage, it includes the following components: 54 - 57% of SiO2, 12 - 15% of Al2O3, 16 - 24% of B2O3, 1 - 2.5% of CaO, 2 - 5% of MgO, 2 - 4% of ZnO, 0.4 - 2% of TiO2, 0.2 - 0.5% of ZrO2, and 1.2 - 3.4% of CeO2.

2. The low-dielectric glass fiber material according to claim 1, characterized in that CeO2 is subjected to a modification treatment. The specific modification method includes the following steps: Add CeO2 to the sodium stearate solution, stir to obtain a suspension, perform ultrasonic treatment for 0.5 - 1 h, filter, dry at 60 - 70 °C, pulverize, and heat-treat at 450 - 500 °C under gas protection to obtain the modified CeO2.

3. The low-dielectric glass fiber material according to claim 2, characterized in that The mass concentration of the sodium stearate solution is 4.5 - 7%.

4. The low-dielectric glass fiber material according to claim 3, wherein The molar ratio of CeO2 to the sodium stearate solution is 1:6 - 10.

5. The low-dielectric glass fiber material according to claim 4, wherein The power of the ultrasonic wave is 180 - 200 W.

6. The preparation method of the low-dielectric glass fiber material according to any one of claims 1-5, characterized in that, It includes the following steps: Mix SiO2, Al2O3, B2O3, CaO, MgO, ZnO, TiO2, ZrO2, and CeO2 in proportion to obtain a mixture; Melt the mixture at a temperature of 1300 - 1500 °C for 2 - 3.5 h to obtain a glass melt; Draw the glass melt, and then add a coupling agent for surface treatment to obtain the low-dielectric glass fiber material.

7. The preparation method of the low-dielectric glass fiber material according to claim 6, characterized in that, The coupling agent is vinyltrimethoxysilane, vinyltrichlorosilane, or vinyltriethoxysilane.

8. The preparation method of the low-dielectric glass fiber material according to claim 7, characterized in that, The mass of the coupling agent is 0.8 - 1.1% of the mass of the mixture.

9. The preparation method of the low-dielectric glass fiber material according to claim 6, wherein, The drawing speed is 2500 - 4000 m / min, and the drawing time is 20 - 30 min.

10. The application of the low-dielectric glass fiber material as described in claims 1 - 5 and the low-dielectric glass fiber material obtained by the preparation method of the low-dielectric glass fiber material as described in claims 6 - 9 in circuit board printing.

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