CN104909578B - A kind of glass fibre - Google Patents

Abstract

The invention provides a kind of glass fiber, which comprises the following components, the components are calculated by mass percentage: 50-60% SiO ₂ ; 10-20% Al ₂ O ₃ ; 20.2-28% B ₂ O ₃ ; 0-4 %CaO; 4-10% MgO; 0-0.4% Na ₂ O and K ₂ O; 0.1-0.4% Li ₂ O; 0-2% F ₂ ; 0-0.2% Fe ₂ O ₃ ; 0-0.5% TiO ₂ . The present invention increases the proportion of B ₂ O ₃ components, and greatly reduces the content of Na ₂ O and K ₂ O components, so that various components interact, not only reduces the dielectric constant and dielectric loss, but also enables The glass fiber has better water resistance, lower molding temperature and crystallization upper limit temperature.

Description

a glass fiber

technical field

The invention relates to the field of inorganic non-metallic materials, in particular to a glass fiber.

Background technique

Glass fiber is a high-performance inorganic material with excellent mechanical properties, corrosion resistance, high temperature resistance and good insulation. With the rapid development of the electronic information industry, glass fiber needs to have lower dielectric constant and dielectric loss, so that the circuit board can propagate faster and have smaller propagation loss.

At present, the glass fibers commonly used in circuit boards at home and abroad are mainly E glass fibers and D glass fibers. Among them, the composition of E glass fibers is: 52-56% SiO ₂ , 12-16% Al ₂ O ₃ , 5-5% 10% B ₂ O ₃ , 16-25% CaO, 0-5.0% MgO, 3-5% Na ₂ O+K ₂ O, E glass fiber has good processability, good water resistance and low price and other advantages, but its dielectric constant is relatively high, about 6.7, and its dielectric loss is relatively large, greater than 10 ^-3 , which cannot meet the requirements of high density and high-speed information processing. The composition of glass fiber D is: 72-76% SiO ₂ , 0-5% Al ₂ O ₃ , 20-25% B ₂ O ₃ , 3-5% Na ₂ O+K ₂ O, and its dielectric The constant is about 4.1, and the dielectric loss is about 8×10 ^-4 , but D glass fiber has the following disadvantages: (1) Compared with E glass fiber, D glass fiber has a higher content of SiO ₂ , resulting in D glass fiber The drilling performance of the reinforced laminate is poor, which is not conducive to subsequent processing; (2) D glass fiber has a high glass softening point and poor melting property, and it is easy to produce veins and air bubbles, resulting in difficulties in drawing operations. There are many problems such as broken wires, so the productivity and workability are very poor, the production cost is high, and it is not easy to produce on a large scale; (3) D glass fiber has a high melting temperature and drawing temperature, generally above 1400 ° C, which is harmful to the kiln. The quality requirements of the furnace are very strict, which will reduce the life of the furnace; (4) D glass fiber has poor water resistance, and it is easy to cause the fiber and resin to peel off. In order to obtain glass fibers with better comprehensive properties, the dielectric properties should be comparable to those of D glass fibers, such as dielectric constant less than 4.5, dielectric loss less than 10 ^-3 ; processability and operability are excellent, such as drawing temperature not greater than 1350°C, The difference between the wire drawing temperature and the devitrification upper limit temperature is greater than 50°C; the glass fiber for printed circuit boards, which has water resistance and E glass fiber, has become one of the research focuses.

Chinese patent document with application number 02810477.3 discloses a low dielectric constant glass fiber, its typical composition is: 53% SiO ₂ , 15.8% Al ₂ O ₃ , 19.6% B ₂ O ₃ , 0.5% Na ₂ O+K ₂ O, 5.3% CaO, 3.9% MgO and 1.2% P ₂ O ₅ , the dielectric constant of the glass fiber is 4.9, and P ₂ O ₅ which is easy to corrode the furnace is added, Higher requirements for kilns;

The application number is 96194439.0 Chinese patent literature disclosed in the low dielectric constant glass fiber to reduce the content of calcium oxide, its dielectric constant is about 4.2 ~ 4.5; in order to improve the melting performance, introduced 1% ~ 4 % TiO ₂ , too high content of TiO ₂ will seriously affect the color of glass fiber and limit its application;

The Chinese patent application number 200780048402.7 discloses a low dielectric constant glass fiber, the composition of which is as follows: 52-60% of SiO ₂ , 11-16% of Al ₂ O ₃ , 20-30% of B ₂ O ₃ , The dielectric loss of 4-8% CaO is ≤5×10 ^-4 , but due to the high content of CaO, the dielectric constant is still high, 4.5-5;

The Chinese patent document with the application number CN200610166224.5 discloses a low dielectric constant glass fiber, the composition of which is: 50-60% SiO ₂ , 6-9.5% Al ₂ O ₃ , 30.5-35% B ₂ O ₃ , 0-5% CaO, 0-5% ZnO, 0.5-5% TiO ₂ , wherein ZnO replaces part of CaO and MgO to reduce the dielectric constant, and its dielectric constant is 3.9-4.4, The dielectric loss is 4×10 ^-4 to 8.5×10 ^-4 , but the drawing temperature of the glass fiber is relatively high, generally greater than 1350°C, and its B ₂ O ₃ content is relatively high, which not only pollutes the environment, but also easily causes the composition Large fluctuations will increase the corrosion of the furnace. In addition, the water resistance of the glass fiber is also poor;

The Chinese patent document with application number 200910216020.1 discloses a low dielectric constant glass fiber, the composition of which is: 50-60% SiO ₂ , 12-18% Al ₂ O ₃ , 21-27% B ₂ O ₃ , 0-1.8% CaO, 0.5-3.2% MgO, 0.5-3.2% ZnO, 0.4-4% TiO ₂ , 0.5%-3% CaF ₂ , 0.2%-0.6% CeO, the glass fiber It has the advantages of good water resistance, good adhesion with resin, easy subsequent processing, and a dielectric constant of 4.2-4.6, but its dielectric loss is still high, ranging from 10×10 ^-4 to 12×10 ^-4 , and TiO ₂ High content is not good for glass color.

The Chinese patent document with application number 201410238080.4 discloses a low dielectric constant glass fiber, the composition of which is: 50-60% SiO ₂ , 10-20% Al ₂ O ₃ , 12-20% B ₂ O ₃ , 0~4% CaO, 4~10% MgO, 0.1~0.5% K ₂ O+Na ₂ O, 0~0.5% Li ₂ O, 0.2%~3% F ₂ , 0~0.2% Fe ₂ O ₃ , the glass fiber has good water resistance and tensile strength, excellent mechanical properties and good for post-processing, etc., but the B ₂ O ₃ content is low, and the dielectric constant still cannot reach the optimal state. The constant is about 4.7, and the glass fiber molding temperature is too high, which affects the production efficiency.

Generally speaking, there are some problems in the various low-dielectric glass fiber technical solutions disclosed at present. Some are too difficult to produce, some have unsatisfactory dielectric properties, and some have high raw material costs and poor economic efficiency.

Contents of the invention

The technical problem solved by the invention is to provide a glass fiber with good dielectric properties and low molding temperature.

The invention discloses a glass fiber, which comprises the following components, and the components are expressed in mass percentage:

Preferably, the following components are included, and the components are expressed in mass percent:

Preferably, the following components are included, and the components are expressed in mass percent:

Preferably, the following components are included, and the components are expressed in mass percent:

Preferably, include:

52% SiO ₂ , 12% Al ₂ O ₃ , 26.9% B ₂ O ₃ , 1.5% CaO, 6.4% MgO, 0.1% Na ₂ O and K ₂ O, 0.1% Li ₂ O, 0.8% F ₂ , 0.1% _Fe2O3 , 0.1 _{% TiO2} .

Preferred include: 54% SiO ₂ , 15% Al ₂ O ₃ , 22.4% B ₂ O ₃ , 2.5% CaO, 5% MgO, 0.1% Na ₂ O and K ₂ O, 0.1% Li ₂ O, 0.8% F ₂ , 0.1% Fe ₂ O ₃ .

Preferred include: 51% SiO ₂ , 15.6% Al ₂ O ₃ , 24.8% B ₂ O ₃ , 2.5% CaO, 5.0% MgO, 0.1% Na ₂ O and K ₂ O, 0.1% Li ₂ O, 0.8% F ₂ , 0.1% Fe ₂ O ₃ .

Preferred include: 54.8% SiO ₂ , 15.5% Al ₂ O ₃ , 21.5% B ₂ O ₃ , 3% CaO, 4.4% MgO, 0.05% Na ₂ O and K ₂ O, 0.05% Li ₂ O, 0.8% F ₂ , 0.1% Fe ₂ O ₃ .

Preferred include: 56% SiO ₂ , 15% Al ₂ O ₃ , 21.2% B ₂ O ₃ , 2.5% CaO, 4.2% MgO, 0.1% Na ₂ O and K ₂ O, 0.1% Li ₂ O, 0.8% F ₂ , 0.1% Fe ₂ O ₃ .

Preferred include: 58% SiO ₂ , 13.5% Al ₂ O ₃ , 20.8% B ₂ O ₃ , 2% CaO, 4.6% MgO, 0.1% Na ₂ O and K ₂ O, 0.1% Li ₂ O, 0.8% F ₂ , 0.1% Fe ₂ O ₃ .

Compared with the prior art, the glass fiber of the present invention includes the following components, which are expressed in mass percent: 50-60% SiO ₂ ; 10-20% Al ₂ O ₃ ; 20.2-28% B ₂ O ₃ ; 0-4% CaO; 4-10% MgO; 0-0.4% Na ₂ O and K ₂ O; 0.1-0.4% Li ₂ O; 0-2% F ₂ ; 0-0.2% Fe ₂ O ₃ ; 0-0.5% TiO ₂ . The present invention increases the proportion of B ₂ O ₃ components, and greatly reduces the content of Na ₂ O and K ₂ O components, so that various components interact, not only reduces the dielectric constant and dielectric loss, but also enables The glass fiber has better water resistance, lower molding temperature and crystallization upper limit temperature. Experimental results show that the dielectric constant of the glass fiber of the present invention does not exceed 4.4, the dielectric loss tangent value does not exceed 10 ^-3 , the molding temperature does not exceed 1325°C, and the upper limit temperature of crystallization is lower than 1200°C, so it can meet the requirements of the tank kiln. At the same time, the present invention does not need to add expensive rare earths or other rare materials, and does not contain BaO, _P2O5 , etc. that may affect other properties of glass _fibers .

detailed description

In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with examples, but it should be understood that these descriptions are only to further illustrate the features and advantages of the present invention, rather than limiting the claims of the present invention.

The embodiment of the present invention discloses a glass fiber, which includes the following components, and the components are expressed in mass percentage:

The present invention has no special limitation on the sources of all raw materials, and commercially available products can be used.

In the present invention, _SiO2 is one of the main oxides forming the glass network, which mainly plays a role in improving the mechanical strength, chemical stability and thermal stability of the glass. At a frequency of 1MHz, the dielectric constant of suitable glass is 3.8, and the dielectric loss tangent is 0.0003, so a higher _SiO2 content can reduce the dielectric properties of glass fibers. The mass percent content of _SiO2 described in the present invention is 50～60%, is 52～58% in some embodiments, is 54～56% in some other embodiments, and is 54.5～54.5% in some embodiments 55.5%.

In the present invention, B ₂ O ₃ not only serves as a filler for the glass network structure, but also serves as a co-solvent to reduce the viscosity of the glass. Although its content exceeds ₂₀ %, the water resistance of the glass fiber will be deteriorated, but the present invention increases the proportion _of B2O3, and it is found that after it cooperates with other components, it not only makes the glass fiber have a lower The dielectric constant and dielectric loss, and the water resistance of glass fiber has not deteriorated sharply. In the present invention, the mass percentage of B ₂ O ₃ is 20.2-28%, in some embodiments it is 20.3-24%, in some other embodiments it is 20.4-23%, and in some embodiments it is 20.5% ~21.5%.

The present invention greatly reduces the content of K ₂ O and Na ₂ O components, so that the water resistance of the glass fiber is better and the processing efficiency is higher, thereby meeting the requirements of the market; more reasonable molding difficulty is obtained, and the molding temperature does not exceed 1325°C, and the crystallization upper limit temperature is lower than 1200°C, so it can meet the needs of large-scale production of the tank kiln method.

In the present invention, MgO with a mass percentage of not less than 4% is added, because the alkali metal content will affect the dielectric properties of glass, but MgO can significantly improve the mechanical properties of glass fibers, and the dielectric constant of glass obtained with MgO at 4% to 10% There is basically no obvious increase, and its tensile strength is 5% to 15% higher than other similar products, which reduces the amount of wool yarn in the weaving process, greatly improves the rate of high-quality products and yield, and the mechanical properties of the obtained products are also improved. more excellent. In addition, MgO is easy to form a magnesium silicate film on the surface of the glass, which protects the glass and enhances the water resistance and corrosion resistance of the glass. In the present invention, the mass percentage of MgO is 4-10%, in some embodiments, it is 4.1-6%, in some other embodiments, it is 4.2-5%, and in some embodiments, it is 4.3-4.5%.

The invention adds Li _{2 O with a mass percentage of not more than 0.4%. Li 2 O} is a strong auxiliary solvent, which can enhance the clarification quality of glass liquid and reduce the melting temperature of glass. Li+ has a small radius, a strong field, and a strong ability to combine with oxygen ions. It has a strong polymerization effect, can improve the stability and surface tension of the glass, and reduce the tendency of crystallization. In the present invention, the mass percentage of Li ₂ O is 0.1-0.4%, in some embodiments it is 0.01-2%, in some other embodiments it is 0.02-0.2%, and in some embodiments it is 0.05-0.05%. 0.15%.

In the present invention, F ₂ is introduced by CaF ₂ . CaF ₂ as a co-solvent can help the gas to be discharged quickly during the glass melting process, reduce the surface tension of the glass liquid, enhance the clarification effect of the glass liquid, greatly reduce the number of bubbles in the glass, and strengthen the glass. Electrical insulating properties of fibers. In the present invention, the mass percentage of F2 is _0-2 %, in some embodiments it is 0.01-1.5%, in some other embodiments it is 0.05-1.3%, in some embodiments it is 0.5-1.2% %.

In the present invention, the mass percentage of Al ₂ O ₃ is 10-20%, 13-18% in some embodiments, 15-17% in other embodiments, and 15.5-17% in some other embodiments. 16.5%.

The mass percentage of CaO in the present invention is 0-4%, in some embodiments, it is 2-4%, in some other embodiments, it is 2.5-4%, and in some embodiments, it is 3-4%.

The mass percentage of Fe ₂ O ₃ in the present invention is 0-0.2%, in some embodiments it is 0.01-0.15%, in some other embodiments it is 0.02-0.15%, and in some embodiments it is 0.03-0.03%. 0.12%.

In the present invention, although the inclusion of TiO ₂ will affect the color of the glass fiber, the present invention finds that TiO ₂ is used in conjunction with other components and by adjusting the mass percentage of each component, the glass fiber can be maintained at a lower level. The dielectric constant and reduce the forming temperature of glass fiber. The mass percentage of TiO ₂ is 0.1-0.4%, in some embodiments, it is 0.01-2%, in some other embodiments, it is 0.02-0.2%, and in some embodiments, it is 0.05-0.15%.

The present invention finds the best balance point among low-dielectric glass fiber performance, production difficulty and cost by adjusting each component and its proportioning ratio. The action and effect of the present invention belong to the comprehensive action of various components, not the unique action of individual components. Glass fibers prepared according to the composition of the present invention are molded at temperatures below 1330°C.

The preparation method of the glass fiber is not particularly limited in the present invention, and it can be prepared according to the tank kiln method well known to those skilled in the art.

According to the actual formula of the glass, calculate the required raw material addition ratio; according to the ratio, the various raw materials are quantitatively transported to the mixing bin, fully mixed evenly, and qualified batch materials are obtained; the batch materials are transported to the kiln head bin of the pool kiln, and The feeder is delivered to the tank kiln at a uniform speed; the batch material is heated, melted, clarified and homogenized in the tank kiln to form qualified molten glass; the molten glass is cooled to the molding temperature through the working channel, and then flows out through the platinum drain plate to form Glass filament: under the high-speed traction of the wire drawing machine, the glass filament is quickly drawn into a glass fiber with a set diameter, and after being sprayed and cooled, coated with a sizing agent, and bundled, it is wound into a silk cake by the wire drawing machine; in the programmed automatic drying furnace In the process, the silk cake is dried to obtain dry glass fiber strands, that is, untwisted direct yarn.

In order to further understand the present invention, the glass fiber provided by the present invention will be described in detail below in conjunction with examples, and the protection scope of the present invention is not limited by the following examples.

Embodiment 1～6

The glass fiber is prepared by the pool kiln method.

Quantitatively transport various raw materials to the mixing bin according to the proportion, fully mix and evenly, and obtain qualified batch materials;

Convey the batch material to the kiln head silo of the tank kiln, and deliver it to the tank kiln at a uniform speed by the feeder;

The batch materials are heated, melted, clarified and homogenized in the tank kiln at a temperature not exceeding 1330°C to form qualified molten glass; the molten glass is cooled to the forming temperature through the working channel, and then flows out through the platinum drain plate to form glass filaments;

The glass filaments are quickly drawn into glass fibers with a set diameter under the high-speed traction of the wire drawing machine. After being sprayed and cooled, coated with a sizing agent and bundled, they are wound into a silk cake by the wire drawing machine; in the programmed automatic drying furnace, The silk cake is dried to obtain dry glass fiber strands, namely untwisted direct yarn.

Table 1 shows the chemical components of the glass compositions of each embodiment and comparative example, and the unit is mass percent.

The high-temperature viscosity of glass fiber is detected by BROOKFIELD high-temperature viscometer produced by ORTON; the glass liquidus temperature is detected by Orton Model gradient furnace; the glass softening point is measured by Orton Model SP-1100 softening point detector.

When the total content of ingredients in Table 1 is slightly less than or greater than 100%, it can be understood that the remaining amount is equivalent to impurities or a small amount of unanalyzed ingredients, or is caused by acceptable errors in the analysis method adopted.

T _logη=3 represents the temperature at which the glass viscosity is 10 ³ poise, which is equivalent to the temperature of the glass liquid during glass fiber molding, also known as the glass fiber molding temperature. It is detected by high temperature viscometer.

T _L in the table represents the glass liquidus temperature, which is equivalent to the temperature when the glass crystallization rate is 0, and also corresponds to the upper limit of the glass crystallization temperature. A glass crystallization gradient furnace was used for detection.

ΔT in the table represents the difference of T _logη=3 -T _L , which is equivalent to the range of glass fiber molding.

The dielectric properties in the table are tested according to the following method: prepare the batch materials according to the glass components listed in the table, mix them evenly, put them into a platinum crucible, place them in a high-temperature resistance furnace, keep them warm at 1450-1500°C, and after they are fully melted and clarified, quickly import In the mold, a round glass piece is made. Then both sides of the glass sheet are polished to obtain a test sample. At room temperature, the dielectric constant and dielectric loss of the sample were detected at a frequency of 1 MHz.

Yarn tensile strength detection method: refer to the national standard GB/T 7690.3-2013 "Measurement of Glass Fiber Breaking Strength and Breaking Elongation", the experimental samples involved in the present invention are all 20.4tex±1tex untwisted spun yarns, and the fiber diameter is 7um± 1um.

Acid resistance test method: Grind the glass sample to 200-300 mesh, weigh 10-15g of powder and place it in 0.5mol.L ^-1 H ₂ SO ₄ solution, soak it at a constant temperature of 80°C for 24 hours, pass through the balance Weigh the difference before and after the weight, and calculate the weight loss rate.

Alkali resistance test method: Grind the glass sample to 200-300 mesh, weigh 10-15g powder and place it in 0.1mol.L ^-1 NaOH solution, soak it for 24 hours at a constant temperature of 80°C, and weigh it with a balance The weight loss rate is calculated based on the poor quality of the front and back.

Water resistance test method: Grind the glass sample to 200-300 mesh, weigh 10-15g of powder and place it in pure water, soak it under boiling conditions for 72 hours, compare the quality difference before and after with a balance, and calculate the weight loss rate.

Bubble determination method:

Comparative example 1

Using the same tank kiln method as in Examples 1-6, E glass fiber and D glass fiber were prepared. For specific ingredients, see pages 53-54 of "The Complete Book of Glass Fiber and Mineral Wool".

The chemical composition and performance parameter of the glass fiber of each embodiment and comparative example of table 1

Clearly, these embodiments of the present invention have an excellent balance of glass fiber dielectric properties and manufacturing difficulty. Their dielectric constants do not exceed 4.4, and their dielectric loss is equivalent to that of D glass fiber; and their molding temperature does not exceed 1330°C, and their molding range ΔT is greater than 50°C. Therefore, compared with D glass fiber, the glass fiber prepared by the present invention is more cost-effective, and it is easier to realize the large-scale production of tank kiln method; compared with E glass fiber, its dielectric property has significant advantages.

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. A glass fiber, comprising the following components, said components in mass percent: 2. glass fiber according to claim 1, is characterized in that, comprises following component, and described component is by mass percentage: 3. The glass fiber according to any one of claims 1 to 2, characterized in that it comprises the following components, which are expressed in mass percent: 4. The glass fiber according to claim 1, characterized in that it comprises: 54% SiO ₂ , 15% Al ₂ O ₃ , 22.4% B ₂ O ₃ , 2.5% CaO, 5% MgO, 0.1% Na ₂ O and K2O, 0.1 _{% Li2O} , 0.8 _% F2, 0.1 _{% Fe2O3} . 5. The glass fiber according to claim 1, characterized by comprising: 54.8% SiO ₂ , 15.5% Al ₂ O ₃ , 21.5% B ₂ O ₃ , 3% CaO, 4.4% MgO, 0.05% Na ₂ O and K2O, 0.05 _{% Li2O} , 0.6 _% F2, 0.1 _{% Fe2O3} . 6. The glass fiber according to claim 2, characterized by comprising: 56% SiO ₂ , 15% Al ₂ O ₃ , 21.2% B ₂ O ₃ , 2.5% CaO, 4.2% MgO, 0.1% Na ₂ O and K2O, 0.1 _{% Li2O} , 0.8 _% F2, 0.1 _{% Fe2O3} . 7. The glass fiber according to claim 1, characterized by comprising: 58% SiO ₂ , 13.5% Al ₂ O ₃ , 20.8% B ₂ O ₃ , 2% CaO, 4.6% MgO, 0.1% Na ₂ O and K2O, 0.1 _{% Li2O} , 0.8 _% F2, 0.1 _{% Fe2O3} .