CN116670091A - Glass composition for glass fibers, glass fiber fabric, and glass fiber reinforced resin composition - Google Patents

Glass composition for glass fibers, glass fiber fabric, and glass fiber reinforced resin composition Download PDF

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Publication number
CN116670091A
CN116670091A CN202280008408.6A CN202280008408A CN116670091A CN 116670091 A CN116670091 A CN 116670091A CN 202280008408 A CN202280008408 A CN 202280008408A CN 116670091 A CN116670091 A CN 116670091A
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China
Prior art keywords
glass
mass
range
glass fibers
composition
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CN202280008408.6A
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Chinese (zh)
Inventor
细川贵庸
栗田忠史
野中贵史
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Nitto Boseki Co Ltd
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Nitto Boseki Co Ltd
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Priority claimed from PCT/JP2022/005136 external-priority patent/WO2022181340A1/en
Publication of CN116670091A publication Critical patent/CN116670091A/en
Pending legal-status Critical Current

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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
    • 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
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • 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
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • 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
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/40—Organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/242—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
    • D03D15/267—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B29B11/16—Making preforms characterised by structure or composition comprising fillers or reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
    • B29K2309/08—Glass
    • 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
    • C03C2213/00—Glass fibres or filaments
    • 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
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/1095—Coating to obtain coated fabrics
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Textile Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)
  • Reinforced Plastic Materials (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Woven Fabrics (AREA)

Abstract

The invention provides a glass composition for glass fibers, which has a reduced 1000 poise temperature. The glass composition for glass fibers can provide glass fibers having excellent water resistance and excellent dielectric characteristics in a high-frequency range. The glass composition for glass fibers contains SiO in an amount ranging from 50.00 to 61.00 mass% relative to the total amount of the glass composition for glass fibers 2 B in a range of 16.00 to 27.00 mass% 2 O 3 Al in a range of 7.00 to 14.00 mass% 2 O 3 P in the range of 0.20 to 4.00 mass% 2 O 5 TiO in the range of 0.50 to 5.00 mass percent 2 CaO in a range of 0.10 to 5.00 mass%, mgO in a range of 0 to 4.00 mass%, and the total amount of the CaO and MgO in the range of 0 to 2.00 mass%F of (2) 2 And Cl 2 ，SiO 2 Content ratio S, al of (2) 2 O 3 Content ratio A, P of (2) 2 O 5 Content ratio P, tiO of (2) 2 The content C of T, caO and the content M of MgO satisfy the following formula (1): 3.65 less than or equal to (S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤8.25…(1)。

Description

Glass composition for glass fibers, glass fiber fabric, and glass fiber reinforced resin composition
Technical Field
The present invention relates to a glass composition for glass fibers, glass fiber fabrics, and glass fiber reinforced resin compositions.
Background
The glass fiber is manufactured by the following processes: a glass raw material of a glass composition for glass fibers having a desired composition is prepared by melting in a glass melting furnace to obtain molten glass (a melt of the glass composition for glass fibers), the molten glass is ejected from a container (a sleeve) having a nozzle plate formed with several to several thousands of nozzle heads (nozzle chips), and the molten glass is cooled and solidified while being drawn by high-speed winding to become fibrous (hereinafter, this operation may be referred to as "spinning"). The sleeve is formed of a noble metal such as platinum.
Conventionally, glass fibers have been widely used in various applications because of their ability to increase the strength of resin molded articles used for housings or accessories of electronic devices such as servers, smart phones, and notebook computers.
In general, glass absorbs energy as heat with respect to alternating current, and therefore, when the resin molded product is used for a case or a fitting of the electronic device, there is a problem in that the resin molded product generates heat.
Here, the dielectric loss energy absorbed by the glass is proportional to the dielectric constant and dielectric loss tangent determined by the composition and structure of the glass, and can be represented by the following formula (a).
W＝kfv 2 ×ε 1/2 ×tanδ…(A)
Where W represents dielectric loss energy, k represents a constant, f represents frequency, v 2 Represents the potential gradient, ε represents the dielectric constant, and tan δ represents the dielectric loss tangent. As is clear from the formula (a), the higher the dielectric constant and the dielectric loss tangent, the higher the frequency, and thus the higher the heat generation of the resin molded product.
In recent years, glass fibers used for housings or parts of electronic devices are required to have a lower dielectric constant and a lower dielectric loss tangent in order to reduce dielectric loss due to the effect that the frequency of alternating current (f of the formula (a)) used for the electronic devices becomes high. In particular, since the dielectric loss tangent has a larger influence on the above formula (a) than the dielectric constant to the power of 1/2, it is required to have a low dielectric loss tangent.
In view of the above, the present inventors have proposed a glass composition for glass fibers having a low dielectric constant and a low dielectric loss tangent, suppressing the occurrence of phase separation, and further reducing the viscosity at high temperatures, which contains SiO in an amount ranging from 52.0 to 59.5 mass% relative to the total amount of the glass composition for glass fibers 2 B in a range of 17.5 to 25.5 mass% 2 O 3 Al in a range of 9.0 to 14.0 mass% 2 O 3 0.5 to 6.0 mass% of SrO, 1.0 to 5.0 mass% of MgO, 1.0 to 5.0 mass% of CaO and 0.1 to 2.5 mass% of F in total 2 And Cl 2 (see patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent No. 6468409
Disclosure of Invention
Problems to be solved by the invention
On the other hand, a glass composition for glass fibers comprising glass fibers having a lower dielectric constant and dielectric loss tangent in a high frequency region of about 10GHz has been particularly demanded, in order to achieve the aboveThe problem is to reduce Al in the glass composition for glass fibers relative to the total amount of the glass composition for glass fibers 2 O 3 And alkaline earth metal oxides (CaO, mgO, and SrO), thereby correspondingly increasing SiO 2 And B 2 O 3 Is a ratio of the content of (3).
However, when SiO is contained in the glass composition for glass fibers 2 When the content of the glass composition for glass fibers is high, the 1000 poise temperature is high, and the viscosity of the glass is also high, which makes it difficult to mix, and thus there are problems that it is difficult to melt homogeneous glass and deterioration of the sleeve at the time of spinning becomes early.
In order to solve the above problems, the following technical solutions are considered: in the glass composition for glass fibers, P is used 2 O 5 Instead of SiO 2 The 1000 poise temperature can be reduced by maintaining excellent dielectric characteristics (low dielectric constant and low dielectric loss tangent) in a high frequency range by maintaining a part of the content ratio relative to the total glass composition for glass fibers.
However, in the above glass composition for glass fibers, if P is used 2 O 5 Instead of SiO 2 When the water resistance of the glass fiber obtained from the glass composition for glass fiber is lowered with respect to a part of the total content of the glass composition for glass fiber, there is a problem that the dielectric characteristics are deteriorated and the strength of the glass fiber is greatly lowered due to foreign matters deposited on the surface of the glass fiber by hydrolysis of glass.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a glass composition for glass fibers having a self-reduced 1000 poise temperature, with which excellent water resistance and excellent dielectric characteristics in a high frequency range can be obtained.
Means for solving the problems
In order to achieve the above object, the glass composition for glass fibers of the present invention is characterized by comprising: 50.00 to 61.00 mass% relative to the total glass composition for glass fiber % of SiO 2 B in a range of 16.00 to 27.00 mass% 2 O 3 Al in a range of 7.00 to 14.00 mass% 2 O 3 P in the range of 0.20 to 4.00 mass% 2 O 5 TiO in the range of 0.50 to 5.00 mass percent 2 CaO in a range of 0.10 to 5.00 mass%, mgO in a range of 0 to 4.00 mass%, and F in a total range of 0 to 2.00 mass% 2 And Cl 2 The SiO is 2 Content (mass%) S of the Al 2 O 3 Content (mass%) A of the above P 2 O 5 P, the content of TiO is as follows 2 The content (mass%) T of CaO, the content (mass%) C of CaO and the content (mass%) M of MgO satisfy the following formula (1),
3.65≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤8.25…(1)
the glass composition for glass fiber of the present invention contains SiO in the above-mentioned range 2 、B 2 O 3 、Al 2 O 3 、P 2 O 5 、TiO 2 CaO, mgO and F 2 And Cl 2 ，SiO 2 S, al (mass%) content 2 O 3 A, P (mass%) content 2 O 5 P, tiO (mass%) content 2 By satisfying the formula (1) with the content (mass%) C of T, caO and the content (mass%) M of MgO, the glass fiber composition can have a reduced 1000 poise temperature, and can provide a glass fiber having excellent water resistance and excellent dielectric characteristics such as low dielectric constant and low dielectric loss tangent in a high frequency region.
The glass fiber obtained by using the glass composition for glass fiber of the present invention has a low dielectric constant, which means that the dielectric constant is 4.1 or less at a measurement frequency of 10GHz, and a low dielectric loss tangent, which means that the dielectric loss tangent is 0.0011 or less at a measurement frequency of 10 GHz.
The glass fiber obtained using the glass composition for glass fiber of the present invention exhibits excellent water resistance, which means that the mass reduction rate is 2.0% or less when evaluated by the following water resistance evaluation method, and the glass fiber component is hardly eluted in water.
In the method for evaluating water resistance, first, a glass raw material was mixed to a glass batch having a predetermined glass composition for glass fibers, and the glass batch was placed in a platinum crucible having a diameter of 80mm, heated at a temperature of 1550 ℃ for 4 hours, and then heated at a temperature of 1650 ℃ for 2 hours to melt the glass batch. Next, the homogenized glass cullet obtained from the crucible was put into a small cylindrical platinum sleeve having 1 round nozzle head at the bottom of the container, and heated to a predetermined temperature to melt the glass cullet. Then, the molten glass discharged from the nozzle head was wound around a stainless steel collet at a predetermined speed, and the molten glass was cooled and solidified while being drawn, whereby glass fibers having a fiber diameter of 13 μm and having a circular cross section in a perfect circle were obtained. Then, about 1g (glass fiber for test) of the glass fiber obtained above was collected from the collet, dried at 120℃for 1 hour, and the mass (mass before operation) was measured. Then, the test glass fiber was allowed to stand in 100ml of distilled water at 80℃for 24 hours, and then, the test glass fiber was obtained by using a metal mesh having openings of about 150 μm, washed with distilled water, and dried at 120℃for 1 hour, and the mass (mass after operation) was measured. Then, from the above-described pre-operation mass and post-operation mass, a mass reduction rate (100× (1- (post-operation mass/pre-operation mass)) was calculated.
The glass composition for glass fibers of the present invention has a reduced 1000 poise temperature, that is, a 1000 poise temperature of 1500 ℃ or less.
In the glass composition for glass fibers of the present invention, the above S, A, P, T, C and M preferably satisfy the following formula (2), more preferably satisfy the following formula (3), and even more preferably satisfy the following formula (4).
4.51≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.32…(2)
4.87≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.20…(3)
5.96≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.16…(4)
The present invention also provides a glass fiber comprising any one of the glass compositions for glass fiber. The present invention also provides a glass fiber fabric characterized by containing the glass fibers. Further, the present invention is also a glass fiber reinforced resin composition characterized by containing the glass fiber.
The glass fiber of the present invention can be obtained, for example, by: the glass composition for glass fibers of the present invention is melted, and the obtained melt is discharged from a sleeve having a nozzle plate with 1 to 8000 nozzle heads or holes, and is wound up at a high speed, whereby the melt is cooled and solidified while being stretched to be formed into a fiber shape. Accordingly, the glass fiber of the present invention has the same glass composition as the glass composition for glass fiber of the present invention.
Detailed Description
Next, embodiments of the present invention will be described in more detail.
The glass composition for glass fibers of the present embodiment contains: siO is present in an amount ranging from 50.00 to 61.00 mass% relative to the total amount of the glass composition for glass fibers 2 B in a range of 16.00 to 27.00 mass% 2 O 3 Al in a range of 7.00 to 14.00 mass% 2 O 3 P in the range of 0.20 to 4.00 mass% 2 O 5 TiO in the range of 0.50 to 5.00 mass percent 2 CaO in a range of 0.10 to 5.00 mass%, mgO in a range of 0 to 4.00 mass%, and F in a total range of 0 to 2.00 mass% 2 And Cl 2 The SiO is 2 Content (mass%) S of the Al 2 O 3 Content (mass%) A of the above P 2 O 5 P, the content of TiO is as follows 2 The content (mass%) T of CaO, the content (mass%) C of CaO and the content (mass%) M of MgO satisfy the following formula (1).
3.65≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤8.25…(1)
The implementation isThe glass composition for glass fibers of the embodiment contains SiO in the above range 2 、B 2 O 3 、Al 2 O 3 、P 2 O 5 、TiO 2 CaO, mgO and F 2 And Cl 2 ，SiO 2 S, al (mass%) content 2 O 3 A, P (mass%) content 2 O 5 P, tiO (mass%) content 2 By satisfying the formula (1) with the content (mass%) C of T, caO and the content (mass%) M of MgO, the glass fiber composition can be used to obtain a glass fiber having excellent water resistance, low dielectric constant of 4.1 or less and low dielectric loss tangent of 0.0011 or less in a high frequency region of 10GHz, and excellent dielectric characteristics, wherein the glass fiber itself has a reduced 1000 poise temperature of less than 1500 ℃.
Here, in the formula (1), "S/A" is SiO 2 Content of (2) and Al 2 O 3 The smaller the ratio of the content ratio of (C) means Al 2 O 3 In this case, the dielectric characteristics of the glass fiber tend to deteriorate as the content ratio of the glass fiber is relatively high. On the other hand, an increase in "S/A" means SiO 2 The higher the content ratio is, the better the dielectric characteristics of the glass fiber, but the 1000 poise temperature of the glass composition for glass fiber tends to be high.
"P X T" is P as an intermediate oxide 2 O 5 With TiO 2 The larger the value, the better the dielectric properties of the glass fiber, but the water resistance of the glass fiber tends to be poor. On the other hand, the smaller the "p×t", the higher the viscosity of the molten glass, and the higher the 1000 poise temperature of the glass composition for glass fibers tends to be.
"c+m" is the total content of CaO and MgO, which are alkaline earth oxides having a large influence on the dielectric characteristics of glass fibers, and tends to be worse as the value is larger. On the other hand, the smaller "C+M" is, the higher the 1000 poise temperature of the glass composition for glass fibers tends to be.
Thus, the formula (1) combines these trends, and it can be inferred that the balance of dielectric properties of glass fibers, water resistance of glass fibers, and 1000 poise temperature of the glass composition for glass fibers is exhibited.
In the glass composition for glass fibers of the present embodiment, if SiO 2 When the content of the glass composition for glass fibers is less than 50.00 mass%, the mechanical strength of the glass fibers obtained from the glass composition for glass fibers is greatly reduced, and the glass fibers have impaired functions as reinforcing materials in the glass fiber-reinforced resin composition. In addition, the glass fiber is susceptible to deterioration when exposed to an acidic environment. On the other hand, if SiO 2 When the content of the glass composition for glass fibers exceeds 61.00 mass%, the viscosity at high temperature becomes high, and therefore the temperature at which the glass material is melted becomes high, which is not suitable for industrial glass fiber production from the viewpoint of production cost.
In the glass composition for glass fibers of the present embodiment, siO 2 The content of the glass composition for glass fibers is preferably in the range of 52.10 to 59.90 mass%, more preferably in the range of 54.10 to 59.70 mass%, even more preferably in the range of 56.10 to 59.60 mass%, particularly preferably in the range of 57.60 to 59.50 mass%, and most preferably in the range of 58.10 to 59.40 mass%.
In the glass composition for glass fibers of the present embodiment, if B 2 O 3 When the content of the glass composition for glass fibers is less than 16.00 mass%, the dielectric loss tangent of the glass fibers obtained from the glass composition for glass fibers cannot be sufficiently reduced. On the other hand, if B 2 O 3 When the content of the glass composition for glass fibers exceeds 27.00 mass%, the glass fibers obtained from the glass composition for glass fibers may be phase-separated, and the chemical durability of the glass fibers may be reduced.
In the glass composition for glass fibers of the present embodiment, B 2 O 3 The content ratio of the glass composition relative to the total glass composition for glass fibers is preferablyThe content of the binder is in the range of 19.60 to 24.90 mass%, more preferably 20.10 to 24.50 mass%, still more preferably 20.60 to 24.00 mass%, particularly preferably 21.10 to 23.50 mass%, and most preferably 21.50 to 23.00 mass%.
In the glass composition for glass fibers of the present embodiment, the glass composition is prepared by reacting B 2 O 3 The glass composition for glass fibers has a content of 19.60 mass% or more relative to the total amount of the glass composition for glass fibers, and the viscosity of molten glass obtained from the glass composition for glass fibers is kept low, so that the production cost is reduced, and the glass composition is suitable for industrial glass fiber production.
In the glass composition for glass fibers of the present embodiment, B 2 O 3 The content of (2) is 24.90 mass% or less relative to the total amount of the glass composition for glass fibers, and the volatile components in the production of glass fibers from the glass composition for glass fibers through molten glass can be reduced. In addition, the furnace body loss of the glass melting furnace for melting the glass composition for glass fibers can be reduced, and the furnace body lifetime is prolonged, so that the manufacturing cost can be reduced.
In the glass composition for glass fibers of the present embodiment, if Al 2 O 3 If the content of the glass composition for glass fibers is less than 7.00 mass%, the glass fibers obtained from the glass composition for glass fibers may be phase-separated, which may reduce the chemical durability of the glass fibers. On the other hand, if Al 2 O 3 When the content of the glass composition for glass fibers exceeds 14.00 mass%, the dielectric loss tangent of the glass fibers obtained from the glass composition for glass fibers cannot be sufficiently reduced.
In the glass composition for glass fibers of the present embodiment, al 2 O 3 The content of the glass composition for glass fibers is preferably in the range of 8.00 to 13.50 mass%, more preferably in the range of 9.00 to 13.00 mass%, even more preferably in the range of 9.60 to 12.80 mass%, particularly preferably in the range of 10.10 to 12.40 mass%, particularly preferably in the range of 10.30 to 11.90 mass%, and most preferably in the range of 10 mass%, based on the total amount of the glass composition for glass fibers The content is in the range of 50 to 11.50 mass%, and most preferably in the range of 10.60 to 10.90 mass%.
In the glass composition for glass fibers of the present embodiment, the glass composition is produced by mixing Al 2 O 3 The content of the glass composition for glass fibers is 13.00 mass% or less relative to the total amount of the glass composition for glass fibers, and the liquid phase temperature is greatly reduced, so that the working temperature range is widened, and stable spinning can be performed.
In the glass composition for glass fibers of the present embodiment, if P 2 O 5 When the content of the glass composition for glass fibers is less than 0.20 mass%, it is difficult to achieve both a reduction in the dielectric loss tangent of glass fibers obtained from the glass composition for glass fibers and a reduction in the 1000 poise temperature of the glass composition for glass fibers. On the other hand, if P 2 O 5 If the content of the glass composition for glass fibers exceeds 4.00 mass%, the occurrence of phase separation of glass fibers obtained from the glass composition for glass fibers cannot be suppressed, and the water resistance is deteriorated.
In the glass composition for glass fibers of the present embodiment, P 2 O 5 The content of the glass composition for glass fibers is preferably in the range of 0.30 to 3.50 mass%, more preferably in the range of 0.50 to 3.20 mass%, even more preferably in the range of 0.70 to 2.90 mass%, particularly preferably in the range of 0.90 to 2.70 mass%, and most preferably in the range of 1.00 to 2.50 mass% relative to the total amount of the glass composition.
In the glass composition for glass fibers of the present embodiment, tiO 2 When the content of the glass composition for glass fibers is less than 0.50 mass%, the viscosity at high temperature becomes high, and therefore the temperature at which the glass material is melted becomes high, which is not suitable for industrial glass fiber production from the viewpoint of production cost. On the other hand, tiO 2 When the content of the glass composition for glass fibers exceeds 5.00 mass%, the dielectric loss tangent of the glass fibers obtained from the glass composition for glass fibers cannot be sufficiently reduced, and the liquid phase temperature of the glass composition for glass fibers cannot be stabilized due to a large increase in the liquid phase temperatureAnd (3) manufacturing fixed glass fibers.
In the glass composition for glass fibers of the present embodiment, tiO 2 The content of the glass composition for glass fibers is preferably in the range of 0.60 to 4.90 mass%, more preferably in the range of 1.00 to 4.50 mass%, even more preferably in the range of 1.50 to 4.00 mass%, particularly preferably in the range of 1.60 to 3.50 mass%, particularly preferably in the range of 1.70 to 3.40 mass%, particularly preferably in the range of 1.80 to 3.30 mass%, and most preferably in the range of 2.10 to 3.20 mass%.
In the glass composition for glass fibers of the present embodiment, if the content of CaO relative to the total amount of the glass composition for glass fibers is less than 0.10 mass%, crystallization of glass is difficult to be suppressed, and the liquidus temperature of the glass composition for glass fibers increases greatly, so that the operating temperature range cannot be sufficiently ensured. On the other hand, if the content of CaO in the total glass composition for glass fibers exceeds 5.00 mass%, the dielectric loss tangent of the glass fibers obtained from the glass composition for glass fibers cannot be sufficiently reduced.
In the glass composition for glass fibers of the present embodiment, the content of CaO is preferably in the range of 0.50 to 4.50 mass%, more preferably in the range of 0.70 to 4.00 mass%, even more preferably in the range of 0.90 to 3.50 mass%, particularly preferably in the range of 1.10 to 3.00 mass%, most preferably in the range of 1.30 to 2.70 mass%, and most preferably in the range of 1.50 to 2.50 mass% relative to the total amount of the glass composition for glass fibers.
In the glass composition for glass fibers of the present embodiment, if the content of MgO exceeds 4.00 mass% relative to the total amount of the glass composition for glass fibers, striae may occur in the melt of the glass composition for glass fibers, and breakage of the glass fibers may easily occur during spinning.
In the glass composition for glass fibers of the present embodiment, the content of MgO is preferably in the range of less than 3.00 mass%, more preferably in the range of less than 2.00 mass%, even more preferably in the range of less than 1.50 mass%, particularly preferably in the range of less than 1.00 mass%, particularly preferably in the range of less than 0.95 mass%, and most preferably in the range of less than 0.50 mass% relative to the total amount of the glass composition for glass fibers.
In the glass composition for glass fibers of the present embodiment, if F 2 And Cl 2 When the total content of the glass compositions for glass fibers exceeds 2.00 mass%, the chemical durability of the glass fibers obtained from the glass compositions for glass fibers is reduced.
In the glass composition for glass fibers of the present embodiment, F 2 And Cl 2 The total content of the glass composition for glass fibers is preferably in the range of 0.10 to 1.80 mass%, more preferably in the range of 0.30 to 1.60 mass%, and even more preferably in the range of 0.50 to 1.50 mass%.
In the glass composition for glass fibers of the present embodiment, F 2 And Cl 2 The dielectric constant of the glass fiber obtained from the glass composition for glass fiber can be further reduced by setting the total content of the glass composition for glass fiber to 0.30 mass% or more.
In the glass composition for glass fibers of the present embodiment, F 2 And Cl 2 The total content of the glass composition for glass fibers is 1.60 mass% or less, and thus, when glass fibers are produced from the glass composition for glass fibers, F-originating source can be suppressed 2 And the generation of the volatile Cl2, and can prevent the deterioration of the environment around the furnace body of the glass melting furnace for melting the glass composition for glass fibers.
The glass composition for glass fibers of the present embodiment may contain SrO in an amount ranging from 0 to 6.00 mass% relative to the total amount of the glass composition for glass fibers. When the glass composition for glass fibers of the present embodiment contains SrO, if the content of SrO exceeds 6.00 mass%, the dielectric characteristics of the glass fibers obtained from the glass composition for glass fibers deteriorate, and the target dielectric characteristics cannot be satisfied.
When the glass composition for glass fibers of the present embodiment contains SrO, the content of SrO relative to the total amount of the glass composition for glass fibers is preferably in the range of 4.00 mass% or less, more preferably in the range of 3.00 mass% or less, even more preferably in the range of 2.00 mass% or less, particularly preferably in the range of less than 1.00 mass%, most preferably in the range of less than 0.50 mass%, and most preferably in the range of less than 0.45 mass%.
The glass composition for glass fibers of the present embodiment may contain Na in a range of less than 1.00 mass% relative to the total content of the glass composition for glass fibers 2 O、K 2 O and Li 2 O. The glass composition for glass fibers of the present embodiment contains Na 2 O、K 2 O and Li 2 In the case of O, if the total content exceeds 1.00 mass%, the dielectric characteristics of the glass fiber obtained from the glass composition for glass fiber are significantly deteriorated, and the target dielectric characteristics cannot be achieved.
The glass composition for glass fibers of the present embodiment contains Na 2 O、K 2 O and Li 2 In the case of O, na 2 O、K 2 O and Li 2 The total content of O relative to the total glass composition for glass fibers is preferably in the range of less than 0.80 mass%, more preferably in the range of less than 0.50 mass%, even more preferably in the range of less than 0.20 mass%, particularly preferably in the range of less than 0.10 mass%, and most preferably in the range of less than 0.05 mass%.
The glass composition for glass fibers of the present embodiment may contain ZnO in a content of 0 to 3.00 mass% relative to the total amount of the glass composition for glass fibers. When the glass composition for glass fibers of the present embodiment contains ZnO, if the ZnO content exceeds 3.00 mass%, the glass fibers obtained from the glass composition for glass fibers are likely to generate devitrification during spinning, and stable glass fiber production is not possible, and the dielectric characteristics of the glass fibers are deteriorated.
When the glass composition for glass fibers of the present embodiment contains ZnO, the content of ZnO is preferably in the range of 2.50 mass% or less, more preferably in the range of 1.50 mass% or less, and even more preferably in the range of 0.50 mass% or less, relative to the total amount of the glass composition for glass fibers.
The glass composition for glass fibers of the present embodiment may contain MnO in an amount ranging from 0 to 3.00 mass% relative to the total amount of the glass composition for glass fibers 2 . The glass composition for glass fibers of the present embodiment contains MnO 2 In the case of MnO 2 If the content exceeds 3.00 mass%, the dielectric characteristics of the glass fiber obtained from the glass composition for glass fiber deteriorate, and the desired dielectric characteristics cannot be obtained.
The glass composition for glass fibers of the present embodiment contains MnO 2 In the case of (2), mnO 2 The content of the glass composition for glass fibers is preferably in the range of 2.50 mass% or less, more preferably in the range of 1.50 mass% or less, and even more preferably in the range of 0.50 mass% or less, relative to the total amount of the glass composition for glass fibers.
The glass composition for glass fibers of the present embodiment may contain Fe in a content of 0 mass% or more and 1.00 mass% or less relative to the total amount of the glass composition for glass fibers 2 O 3 . The glass composition for glass fibers of the present embodiment contains Fe 2 O 3 In the case of (2), from the viewpoint of suppressing bubbles contained in the glass fiber, fe is effective 2 O 3 The content of (2) is in the range of 0.10 mass% or more and 0.60 mass% or less.
The glass composition for glass fibers of the present embodiment may contain SnO in a content of 0 mass% or more and 1.00 mass% or less relative to the total amount of the glass composition for glass fibers 2 . The glass composition for glass fibers of the present embodiment contains SnO 2 In the case of (2), from the viewpoint of suppressing bubbles contained in glass fibers, snO is effective 2 The content of (2) is in the range of 0.10 mass% or more and 0.60 mass% or less.
In addition, as long as ZrO 2 The content of the glass composition for glass fibers was as followsIn the range of less than 0.50 mass%, the glass composition for glass fibers of the present embodiment may contain ZrO 2 . The glass composition for glass fibers of the present embodiment contains ZrO 2 In the case of ZrO 2 The glass fiber obtained from the glass composition for glass fiber has a content of 0.50 mass% or more relative to the total amount of the glass composition for glass fiber, and devitrification is likely to occur during spinning, and stable glass fiber production cannot be performed.
The glass composition for glass fibers of the present embodiment contains ZrO 2 In the case of ZrO 2 The content of the glass composition for glass fibers is preferably in a range of less than 0.45 mass%, more preferably in a range of less than 0.40 mass%, even more preferably in a range of less than 0.20 mass%, particularly preferably in a range of less than 0.10 mass%, and most preferably in a range of less than 0.05 mass%.
In addition, as long as Cr 2 O 3 The glass composition for glass fibers of the present embodiment may contain Cr in a content of less than 0.05 mass% relative to the total amount of the glass composition for glass fibers 2 O 3 . The glass composition for glass fibers of the present embodiment contains Cr 2 O 3 In the case of (C), cr 2 O 3 The glass fiber obtained from the glass composition for glass fiber has a content of 0.05 mass% or more relative to the total amount of the glass composition for glass fiber, and devitrification is likely to occur during spinning, and stable glass fiber production cannot be performed.
In the glass composition for glass fibers of the present embodiment, as impurities derived from the raw material, ba, co, ni, cu, mo, W, ce, Y, la, bi, gd, pr, sc or an oxide of Yb may be contained in a range of less than 1.00 mass% relative to the total content of the glass composition for glass fibers. In particular, the glass composition for glass fibers of the present embodiment contains BaO, ceO 2 、Y 2 O 3 、La 2 O 3 、Bi 2 O 3 、Gd 2 O 3 、Pr 2 O 3 、Sc 2 O 3 Or Yb 2 O 3 In the case of impurities, the content is preferably in the range of less than 0.40 mass%, more preferably in the range of less than 0.20 mass%, even more preferably in the range of less than 0.10 mass%, particularly preferably in the range of less than 0.05 mass%, and most preferably in the range of less than 0.01 mass%, each independently.
In the glass composition for glass fibers of the present embodiment, the above S, A, P, T, C and M preferably satisfy the following formula (1-1), more preferably satisfy the following formula (1-2), still more preferably satisfy the following formula (1-3), particularly preferably satisfy the following formula (2), most preferably satisfy the following formula (3), and most preferably satisfy the following formula (4).
3.86≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.32…(1-1)
4.00≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.32…(1-2)
4.25≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.32…(1-3)
4.51≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.32…(2)
4.87≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.20…(3)
5.96≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.16…(4)
By satisfying the formula (2), the glass composition for glass fibers according to the present embodiment can have a self-reduced 1000 poise temperature of less than 1500 ℃, and glass fibers having excellent water resistance and extremely excellent dielectric characteristics such as a low dielectric constant of 4.0 or less and a low dielectric loss tangent of 0.0010 or less in a high frequency region of a measurement frequency of 10GHz can be obtained using the glass composition for glass fibers.
Further, by satisfying the formula (3) in the glass composition for glass fibers according to the present embodiment, it is possible to obtain glass fibers having excellent glass fiber manufacturability at 1000 poise temperature lower than 1500 ℃ and operating temperature range of 150 ℃ or higher, and also having excellent water resistance and extremely excellent dielectric characteristics such as low dielectric constant of 4.0 or less and low dielectric loss tangent of 0.0010 or less in a high frequency region of 10GHz measured by using the glass composition for glass fibers.
Further, by satisfying the formula (4) in the glass composition for glass fibers of the present embodiment, it is possible to obtain glass fibers having extremely excellent dielectric characteristics such as excellent water resistance, a low dielectric constant of 4.0 or less and a low dielectric loss tangent of 0.0010 or less in a high frequency region of a measurement frequency of 10GHz, while having extremely excellent glass fiber manufacturability in which the glass composition for glass fibers has a self-reduced 1000 poise temperature of less than 1500 ℃ and an operating temperature range of 200 ℃ or more.
In the glass composition for glass fibers of the present embodiment, the content of each component may be measured using an ICP emission spectroscopic analyzer for Li as a light element, and the other element may be measured using a wavelength dispersive fluorescent X-ray analyzer.
The measurement method is as follows: first, a glass batch prepared by mixing glass raw materials was placed in a platinum crucible, held at a temperature of 1550 ℃ for 4 hours in an electric furnace, and then held at a temperature of 1650 ℃ for 2 hours, and melted while stirring, to thereby obtain a homogeneous molten glass. Alternatively, glass fibers were placed in a platinum crucible, and kept at a temperature of 1550 ℃ for 6 hours in an electric furnace, and melted while stirring, thereby obtaining a homogeneous molten glass.
When the organic substance is adhered to the surface of the glass fiber, or when the glass fiber is mainly contained as a reinforcing material in the organic substance (resin), the glass fiber is heated in a muffle furnace at a temperature of 300 to 650 ℃ for about 0.5 to 24 hours, for example, and the organic substance is removed and then used.
Next, the obtained molten glass was flowed out onto a carbon plate to prepare glass cullet, which was then pulverized and powdered. After the glass powder obtained above was thermally decomposed with an acid, li as a light element was quantitatively analyzed using an ICP emission spectrometry device. After the glass powder was molded into a disk shape by a press, other elements were quantitatively analyzed by a wavelength dispersive fluorescent X-ray analyzer. Specifically, the quantitative analysis using the wavelength dispersive fluorescent X-ray analyzer is performed by creating a standard curve sample based on the result of measurement by the basic parameter method and analyzing the sample by the standard curve method. The content of each component in the standard curve sample can be quantitatively analyzed by an ICP emission spectrometry device. The content and total amount of each component can be calculated by oxide conversion on the quantitative analysis results, and the content of each component can be obtained from these values.
The glass composition for glass fibers of the present embodiment can be obtained by: the glass raw material (glass batch) prepared so as to have the above composition after melting and solidification is melted, cooled and solidified.
In forming the glass fiber of the present embodiment using the glass composition for glass fiber of the present embodiment, first, the glass raw material prepared in the above manner is supplied to a glass melting furnace, and the glass raw material is melted at a temperature in the above 1000 poise temperature or higher, specifically, at a temperature in the range of 1400 to 1700 ℃. Then, molten glass melted to a predetermined temperature is discharged from 1 to 8000 nozzle heads or holes controlled to the predetermined temperature, and is drawn by high-speed winding, cooled, and solidified to form glass fibers.
Here, the glass filaments (glass filaments) ejected from 1 nozzle head or orifice and cooled and solidified generally have a right circular cross-sectional shape and have a diameter in the range of 3.0 to 35.0 μm. In the application requiring low dielectric characteristics, the glass filaments preferably have a diameter in the range of 3.0 to 6.0. Mu.m, more preferably 3.0 to 4.5. Mu.m.
On the other hand, when the nozzle head has a non-circular shape and has a protrusion or a notch for quenching the molten glass, a glass filament having a non-circular (for example, elliptical or oblong) cross-sectional shape can be obtained by controlling the temperature conditions. When the glass filament has an elliptical or oblong cross-sectional shape, the ratio of the long diameter to the short diameter (long diameter/short diameter) of the cross-sectional shape is, for example, in the range of 2.0 to 10.0, and the fiber diameter (converted fiber diameter) when the cross-sectional area is converted into a normal circle is in the range of 3.0 to 35.0 μm.
The glass fiber of the present embodiment is generally in the form of a glass fiber bundle (glass strands) in which 10 to 8000 glass filaments are bundled, and has a weight in the range of 1 to 10000tex (g/km). The glass filaments discharged from the plurality of nozzle heads or holes may be bundled into 1 glass fiber bundle, or may be bundled into a plurality of glass fiber bundles.
The glass fiber of the present embodiment may take various forms as follows: yarns, fabrics, knits, nonwoven fabrics (including chopped strand mats and multiaxial nonwoven fabrics), chopped strands, rovings, powders, and the like obtained by further subjecting the glass strands to various processes.
The surface of the glass fiber of the present embodiment may be coated with an organic substance for the purpose of improving bundling properties of glass filaments, improving adhesion properties of the glass fiber to a resin, improving uniform dispersion properties of the glass fiber in a mixture of the glass fiber and the resin or an inorganic material, and the like. Examples of such organic substances include: starch, polyurethane resins, epoxy resins, vinyl acetate resins, acrylic resins, modified polypropylene (in particular, carboxylic acid modified polypropylene), copolymers of (poly) carboxylic acid (in particular, maleic acid) and unsaturated monomers, and the like.
The glass fiber of the present embodiment may be coated with a resin composition containing a silane coupling agent, a lubricant, a surfactant, and the like, in addition to these resins. The glass fiber of the present embodiment may be coated with a treatment agent composition containing a silane coupling agent, a surfactant, or the like, instead of the resin. Such a resin composition or treating agent composition coats the glass fiber in a proportion ranging from 0.03 to 2.0 mass% based on the mass of the glass fiber of the present embodiment in a state of not being coated with the resin composition or treating agent composition.
The coating of glass fibers with organic substances can be performed, for example, by: in the glass fiber manufacturing process, a known method such as a roll coater is used to apply a resin solution or a resin composition solution to glass fibers, and then the glass fibers to which the resin solution or the resin composition solution has been applied are dried. In addition, the coating of the glass fiber by the organic matters can be carried out by the following modes: the glass fiber of the present embodiment in the form of a fabric is immersed in the treating agent composition solution, and then the glass fiber to which the treating agent composition is applied is dried.
Here, as the silane coupling agent, there may be mentioned: aminosilanes, chlorosilanes, mercaptosilanes, vinylsilanes, (meth) acrylic silanes, and the like.
Examples of aminosilanes include γ -aminopropyl triethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, N- β - (aminoethyl) -N' - β - (aminoethyl) - γ -aminopropyl trimethoxysilane, and γ -anilinopropyl trimethoxysilane.
Examples of chlorosilanes include gamma-chloropropyltrimethoxysilane.
Examples of the epoxysilane include (β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and γ -epoxypropoxypropyltrimethoxysilane.
Examples of mercaptosilanes include gamma-mercaptotrimethoxysilane.
Examples of the vinylsilane include vinyltrimethoxysilane and N- β - (N-vinylbenzylaminoethyl) - γ -aminopropyl trimethoxysilane.
Examples of the (meth) acrylic silane include gamma-methacryloxypropyl trimethoxysilane.
In this embodiment, the silane coupling agent may be used alone, or two or more of the silane coupling agents may be used in combination.
Examples of the lubricant include: modified silicone oils, animal oils and their hydrides, vegetable oils and their hydrides, animal waxes, vegetable waxes, mineral waxes, condensates of higher saturated fatty acids with higher saturated alcohols, polyethylenimine, polyalkylpolyamine alkyl linolenic acid derivatives, fatty acid amides, quaternary ammonium salts, and the like.
Examples of the animal oil include tallow and the like.
Examples of the vegetable oil include soybean oil, coconut oil, rapeseed oil, palm oil, and castor oil.
Examples of the animal wax include beeswax and wool.
Examples of the vegetable wax include candelilla wax and carnauba wax.
Examples of the mineral wax include paraffin wax and montan wax.
Examples of the condensate of the higher saturated fatty acid and the higher saturated alcohol include stearic acid esters such as lauryl stearate.
Examples of the fatty acid amide include dehydrated condensates of polyethylene polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine with fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid.
Examples of the fourth ammonium salt include alkyl trimethylammonium salts such as lauryl trimethylammonium chloride.
In this embodiment, the above-described lubricants may be used alone, or two or more kinds of the above-described lubricants may be used in combination.
Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. In this embodiment, the surfactant may be used alone, or two or more of the surfactants may be used in combination.
Examples of the nonionic surfactant include ethylene oxide propylene oxide alkyl ether, polyoxyethylene-polyoxypropylene-block copolymer, alkyl polyoxyethylene-polyoxypropylene-block copolymer ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid monoester, polyoxyethylene fatty acid diester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester ethylene oxide adduct, polyoxyethylene stearyl ether, hydrogenated castor oil ethylene oxide adduct, alkylamine ethylene oxide adduct, fatty acid amide ethylene oxide adduct, glycerin fatty acid ester, polyglycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyhydric alcohol alkyl ether, fatty acid alkanolamide, acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, and ethylene oxide adduct of acetylene alcohol.
Examples of the cationic surfactant include: alkyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium chloride, alkyl dimethyl ethyl ammonium ethyl sulfate, higher alkyl amine salts (acetate or hydrochloride, etc.), ethylene oxide adducts to higher alkyl amines, condensates of higher fatty acids with polyalkylene polyamines, ester salts of higher fatty acids with alkanolamines, salts of higher fatty acid amides, imidazoline type cationic surfactants, and alkylpyridinium salts.
Examples of the anionic surfactant include higher alcohol sulfate, higher alkyl ether sulfate, alpha-olefin sulfate, alkylbenzenesulfonate, alpha-olefin sulfonate, a reaction product of a fatty acid halide and N-methyltaurine, dialkyl sulfosuccinate, higher alcohol phosphate, and phosphate of a higher alcohol ethylene oxide adduct.
Examples of the amphoteric surfactant include amino acid type amphoteric surfactants such as alkali metal salt of alkylaminopropionic acid, betaine type amphoteric surfactants such as alkyldimethyl betaine, and imidazoline type amphoteric surfactants.
The glass fiber fabric of the present embodiment includes the glass fibers of the present embodiment described above. Specifically, the glass fiber fabric of the present embodiment can be produced by: the glass fiber according to the present embodiment is woven with a loom known per se as at least a part of warp yarn or weft yarn. Examples of the loom include: jet looms such as air jet looms and water jet looms, shuttle looms, rapier looms, and the like.
The weaving method of the loom includes, for example, a plain weave, a satin weave, a square weave, a twill weave, and the like, and from the viewpoint of manufacturing efficiency, a plain weave is preferably used. The glass fiber fabric of the present embodiment preferably uses the glass fibers of the present embodiment described above as warp yarns and weft yarns.
In the glass fiber fabric of the present embodiment, it is preferable that the glass fiber of the present embodiment has a mass of 0.9 to 69.0tex (g/km) in which 35 to 400 glass filaments having diameters in the range of 3.0 to 9.0 μm are bundled and 0 to 1.0 times/25 mm of twist is applied.
In the glass fiber fabric of the present embodiment, when the glass fibers of the present embodiment are used as warp yarns or weft yarns, the warp yarn density is preferably in the range of 40 to 120 pieces/25 mm, and the weft yarn density is preferably in the range of 40 to 120 pieces/25 mm.
The glass fiber fabric of the present embodiment may be subjected to a deoiling treatment, a surface treatment, and a fiber opening treatment after weaving.
The deoiling treatment may be the following treatment: placing the glass fiber fabric in a heating furnace with the atmosphere temperature ranging from 350 ℃ to 400 ℃ for 40 to 80 hours, and carrying out heating decomposition treatment on the organic matters attached to the glass fibers.
As the surface treatment, the following treatments can be mentioned: the glass fiber fabric is immersed in a solution containing the silane coupling agent or a solution containing the silane coupling agent and the surfactant, and after removing excess water, is dried by heating at a temperature ranging from 80 to 180 ℃ for a time ranging from 1 to 30 minutes.
As the fiber opening treatment, for example, the following treatments can be mentioned: opening by water pressure, opening by high-frequency vibration using liquid as a medium, opening by fluid pressure having face pressure, opening by pressing by rollers, etc. are performed while applying tension in the range of 30 to 200N to the warp yarn of the glass fiber fabric, thereby widening the line widths of the warp yarn and the weft yarn.
The glass fiber fabric of the present embodiment preferably has a weight of 7.0 to 190.0g/m 2 The mass per unit area in the range is 8.0-200.0 μm.
The yarn width of the warp yarn of the glass fiber fabric of the present embodiment is preferably in the range of 110 to 600. Mu.m, and the yarn width of the weft yarn is preferably in the range of 110 to 600. Mu.m.
The glass fiber fabric of the present embodiment may further include a surfactant containing the silane coupling agent or a surface treatment layer containing the silane coupling agent and the surfactant. When the glass fiber fabric of the present embodiment contains the surface treatment layer, the surface treatment layer may have a mass ranging from 0.03 to 1.50 mass% relative to the total mass of the glass fiber fabric containing the surface treatment layer, for example.
The glass fiber-reinforced resin composition of the present embodiment contains the glass fibers of the present embodiment described above. Specifically, the glass fiber-reinforced resin composition of the present embodiment contains glass fibers in an amount ranging from 10 to 90 mass% relative to the total amount of the glass fiber-reinforced resin composition in the glass fiber-reinforced resin composition containing a thermoplastic resin, a thermosetting resin, glass fibers, and other additives. The glass fiber reinforced resin composition of the present embodiment contains a resin in a range of 90 to 10 mass% and other additives in a range of 0 to 40 mass% relative to the total amount of the glass fiber reinforced resin composition.
Here, examples of the thermoplastic resin include: polyethylene, polypropylene, polystyrene, styrene/maleic anhydride resin, styrene/maleimide resin, polyacrylonitrile, acrylonitrile/styrene (AS) resin, acrylonitrile/butadiene/styrene (ABS) resin, chlorinated polyethylene/acrylonitrile/styrene (ACS) resin, acrylonitrile/ethylene/styrene (AES) resin, acrylonitrile/styrene/methyl acrylate (ASA) resin, styrene/acrylonitrile (SAN) resin, methacrylic resin, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polycarbonate, polysulfide, polyethersulfone (PES), polyphenylene sulfone (PPSU), polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyaryletherketone, liquid Crystal Polymer (LCP), fluorine resin, polyetherimide (PEI), polyarylate (PAR), polysulfone (PSF), polyamideimide (PAI), polyaminobisimide (PAI), thermoplastic Polyimide (PAI), thermoplastic bis (tpbm), polyethylene naphthalate (ethylene/vinyl acetate), ethylene/butadiene (EVA), styrene/butadiene (EVA) resin, styrene/butadiene (IO) resin, polybutene, polymethylpentene, olefin/vinyl alcohol resins, cyclic olefin resins, cellulose resins, polylactic acid, and the like.
Specifically, examples of the polyethylene include: high Density Polyethylene (HDPE), medium density polyethylene (LDPE), low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), ultra high molecular weight polyethylene, and the like.
The polypropylene may be: isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, mixtures of the foregoing and the like.
Examples of the polystyrene include general-purpose polystyrene (GPPS) which is atactic polystyrene having an atactic structure, high Impact Polystyrene (HIPS) in which a rubber component is added to GPPS, and syndiotactic polystyrene having a syndiotactic structure.
The methacrylic resin may be: a polymer obtained by polymerizing one kind of methacrylic resin selected from acrylic acid, methacrylic acid, styrene, methyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate and vinyl ester of fatty acid alone, or a polymer obtained by copolymerizing two or more kinds of the above methacrylic resins.
The polyvinyl chloride may be: vinyl chloride homopolymers polymerized by a conventionally known method such as emulsion polymerization, suspension polymerization, micro-suspension polymerization, or bulk polymerization, copolymers with a monomer copolymerizable with vinyl chloride monomers, or graft copolymers obtained by graft polymerizing vinyl chloride monomers to a polymer.
The polyamide may be: polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 410), polyhexamethylene adipamide (nylon 56), polyhexamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyhexamethylene adipamide (nylon 106), polyhexamethylene sebacamide (nylon 1010), polyhexamethylene dodecamide (nylon 1012), polyhexamethylene adipamide (nylon 11), polyhexamethylene adipamide (nylon 116), polydodecyl amide (nylon 12), polyditoluamide (nylon D6), polyditoluamide sebacamide (nylon MXD 10), polymetaxylylene (nylon MXD 6), parylene adipamide (nylon PXD 6), parylene benzamide (nylon 4T), polyhexamethylene terephthalamide (nylon 5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene terephthalamide (nylon I), polyhexamethylene terephthalamide (nylon 9), polyhexamethylene terephthalamide (nylon T9), one or a combination of two or more of the above components such as poly bis (3-methyl-4-aminohexyl) methane terephthalamide (nylon PACMT), poly bis (3-methyl-4-aminohexyl) methane isophthalamide (nylon PACMI), poly bis (3-methyl-4-aminohexyl) methane dodecanamide (nylon PACM 12), poly bis (3-methyl-4-aminohexyl) methane tetradecanoamide (nylon PACM 14), and a mixture of the above components and the above copolymer.
Examples of the polyacetal include: homopolymers having an oxymethylene unit as a main repeating unit, copolymers which are mainly composed of an oxymethylene unit and contain an oxyalkylene unit having 2 to 8 adjacent carbon atoms in the main chain, and the like.
Examples of the polyethylene terephthalate include a polymer obtained by polycondensing ethylene glycol with terephthalic acid or a derivative thereof.
Examples of the polybutylene terephthalate include a polymer obtained by polycondensing 1, 4-butanediol with terephthalic acid or a derivative thereof.
Examples of the polytrimethylene terephthalate include a polymer obtained by polycondensing 1, 3-propanediol with terephthalic acid or a derivative thereof.
The polycarbonate may be: a polymer obtained by a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted in a molten state, or a polymer obtained by a phosgene method in which a dihydroxyaryl compound and phosgene are reacted.
Examples of the polyarylene sulfide include linear polyphenylene sulfide, crosslinked polyphenylene sulfide having a high molecular weight by a curing reaction after polymerization, polyphenylene sulfide sulfone, polyphenylene sulfide ether, and polyphenylene sulfide ketone.
Examples of the polyphenylene ether include: poly (2, 3-dimethyl-6-ethyl-1, 4-phenylene ether), poly (2-methyl-6-chloromethyl-1, 4-phenylene ether), poly (2-methyl-6-hydroxyethyl-1, 4-phenylene ether), poly (2-methyl-6-n-butyl-1, 4-phenylene ether), poly (2-ethyl-6-isopropyl-1, 4-phenylene ether), poly (2-ethyl-6-n-propyl-1, 4-phenylene ether), poly (2, 3, 6-trimethyl-1, 4-phenylene ether), poly [2- (4' -methylphenyl) -1, 4-phenylene ether ], poly (2-bromo-6-phenyl-1, 4-phenylene ether), poly (2-methyl-6-phenyl-1, 4-phenylene ether), poly (2-chloro-1, 4-phenylene ether), poly (2-methyl-1, 4-phenylene ether), poly (2-ethyl-6-n-propyl-1, 4-phenylene ether), poly (2-methyl-1, 6-phenylene ether), poly (2-bromo-6-phenyl-1, 4-phenylene ether), 6-di-n-propyl-1, 4-phenylene ether), poly (2-methyl-6-isopropyl-1, 4-phenylene ether), poly (2-chloro-6-methyl-1, 4-phenylene ether), poly (2-methyl-6-ethyl-1, 4-phenylene ether), poly (2, 6-dibromo-1, 4-phenylene ether), poly (2, 6-dichloro-1, 4-phenylene ether), poly (2, 6-diethyl-1, 4-phenylene ether), poly (2, 6-dimethyl-1, 4-phenylene ether), and the like.
Examples of the modified polyphenylene ether include: a polymer alloy of poly (2, 6-dimethyl-1, 4-phenylene) ether and polystyrene, a polymer alloy of poly (2, 6-dimethyl-1, 4-phenylene) ether and a styrene/butadiene copolymer, a polymer alloy of poly (2, 6-dimethyl-1, 4-phenylene) ether and a styrene/maleic anhydride copolymer, a polymer alloy of poly (2, 6-dimethyl-1, 4-phenylene) ether and polyamide, a polymer alloy of poly (2, 6-dimethyl-1, 4-phenylene) ether and a styrene/butadiene/acrylonitrile copolymer, a modified polyphenylene ether in which functional groups such as amino groups, epoxy groups, carboxyl groups, and styrene groups are introduced at the polymer chain ends of the polyphenylene ether, and a modified polyphenylene ether in which functional groups such as amino groups, epoxy groups, carboxyl groups, styrene groups, and methacryloyl groups are introduced at the side chains of the polymer chain of the polyphenylene ether.
Examples of the polyaryletherketone include: polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetheretherketone (PEEKK), and the like.
The Liquid Crystal Polymer (LCP) may be a (co) polymer comprising at least one structural unit selected from the following: an aromatic hydroxycarbonyl unit, an aromatic dihydroxy unit, an aromatic dicarbonyl unit, an aliphatic dihydroxy unit, an aliphatic dicarbonyl unit, and the like as the thermotropic liquid crystalline polyester.
The fluororesin may be: polytetrafluoroethylene (PTFE), perfluoroalkoxy resin (PFA), fluorinated ethylene propylene resin (FEP), fluorinated ethylene tetrafluoroethylene resin (ETFE), polyethylene fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene/chlorotrifluoroethylene resin (ECTFE), and the like.
Examples of Ionomer (IO) resins include: and a polymer obtained by neutralizing a part of carboxyl groups with metal ions, which is a copolymer of an olefin or styrene and an unsaturated carboxylic acid.
Examples of the olefin/vinyl alcohol resin include: ethylene/vinyl alcohol copolymer, propylene/vinyl alcohol copolymer, ethylene/vinyl acetate copolymer saponified product, propylene/vinyl acetate copolymer saponified product, etc.
The cyclic olefin resin may be: and polymers of a single ring such as cyclohexene, a multi-ring such as tetracyclic cycloolefin, and a cyclic olefin monomer.
The polylactic acid may be: poly-L-lactic acid as a homopolymer of the L-form, poly-D-lactic acid as a homopolymer of the D-form, or stereocomplex polylactic acid as a mixture thereof.
As the cellulose resin, there may be mentioned: methylcellulose, ethylcellulose, hydroxycellulose, hydroxymethyl cellulose, hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, cellulose acetate, cellulose propionate, cellulose butyrate, and the like.
The thermosetting resin may be: unsaturated polyester resins, vinyl ester resins, epoxy (EP) resins, melamine (MF) resins, phenolic resins (PF), polyurethane resins (PU), polyisocyanates, polyisocyanurates, polyimides (PI), urea (UF) resins, silicon (SI) resins, furan (FR) resins, benzoguanamine (BR) resins, alkyd resins, xylene resins, bismaleimide Triazine (BT) resins, diallyl phthalate resins (PDAP), and the like.
Specifically, the unsaturated polyester resin is a resin obtained by esterification of an aliphatic unsaturated dicarboxylic acid and an aliphatic diol.
Examples of the vinyl ester resin include: a divinyl ester resin and a novolak-based vinyl ester resin.
Examples of the epoxy resin include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4, 4' - (1, 3-phenylenediisopropylene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4, 4' - (1, 4-phenylenediisopropylene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4, 4' -cyclohexylidenediphenol type epoxy resin), phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetraphenolethyl type novolak type epoxy resin, novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure, biphenyl type epoxy resin, xylylene type epoxy resin or phenylarylalkyl type epoxy resin, naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalene diol type epoxy resin, 2-functional or 4-functional epoxy type naphthalene resin, binaphthyl type epoxy resin, naphtalene aralkyl type epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamantyl type epoxy resin, etc.
Examples of the melamine resin include a polymer comprising polycondensation of melamine (2, 4, 6-triamino-1, 3, 5-triazine) and formaldehyde.
As the phenolic resin, there may be mentioned: a novolak type phenol resin such as a phenol novolak resin, a cresol novolak resin and a bisphenol A type novolak resin, a resol type phenol resin such as a methylol resol type phenol resin, a dimethylene ether type phenol resin, a resol type phenol resin such as an arylalkylene type phenol resin, or a combination of two or more resins.
As the urea-formaldehyde resin, a resin obtained by condensing urea and formaldehyde can be mentioned.
The thermoplastic resin or the thermosetting resin may be used alone, or two or more resins may be used in combination.
The glass fiber reinforced resin composition of the present embodiment is preferably used for applications requiring low dielectric characteristics, such as epoxy resins, modified polyphenylene ethers, polybutylene terephthalate, polypropylene, fluorine resins, and Liquid Crystal Polymers (LCP) as the above resins.
Examples of the other additives include: reinforcing fibers other than glass fibers, fillers other than glass fibers, flame retardants, ultraviolet absorbers, heat stabilizers, antioxidants, antistatic agents, fluidity improvers, antiblocking agents, lubricants, nucleating agents, antibacterial agents, pigments, and the like.
Examples of the reinforcing fibers other than glass fibers include carbon fibers and metal fibers.
Examples of fillers other than glass fibers include glass powder, talc, and mica.
The glass fiber reinforced resin composition of the present embodiment may be a prepreg obtained by impregnating the glass fiber woven fabric of the present embodiment with the resin by a method known per se and semi-curing the resin.
The glass fiber reinforced resin composition of the present embodiment can be molded by a known molding method such as injection molding, injection compression molding, two-color molding, hollow molding, foam molding (including supercritical fluid), insert molding, in-mold coating molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, compression molding, blow molding, press molding, melting, hand lay-up molding, spraying, resin transfer molding, sheet molding, bulk molding, pultrusion, filament winding, etc., to obtain various glass fiber reinforced resin molded products. Further, by curing the prepreg, a glass fiber reinforced resin molded article can be obtained.
Examples of the use of such a molded article include: electronic equipment housings, electronic parts, vehicle exterior parts, vehicle interior parts, vehicle engine peripheral parts, muffler related parts, high-pressure tanks, and the like.
Examples of the electronic component include a printed wiring board.
Examples of the vehicle exterior member include a bumper, a fender, an engine cover, an air barrier, and a wheel cover.
As the vehicle interior member, door trim, roof material, and the like can be given.
Examples of the vehicle engine peripheral components include an oil pan, a hood, an intake manifold, and an exhaust manifold.
As the muffler related member, a muffler member and the like can be mentioned.
The glass fiber of the present embodiment can be used for the glass fiber reinforced resin composition of the present embodiment, and can be used for reinforcing materials for inorganic materials such as gypsum and cement. For example, when the glass fiber-reinforced gypsum composite material is used as a reinforcing material for gypsum, particularly for gypsum boards having a thickness in the range of 4 to 60mm, the gypsum contains glass fiber having the above composition in the range of 0.1 to 4.0 mass% relative to the total mass of the gypsum.
Next, examples of the present invention and comparative examples are shown.
Examples
First, glass raw materials were mixed to obtain a glass batch so that the glass compositions after melt-solidification became the respective compositions of examples 1 to 8 and comparative examples 1 to 5 shown in table 1.
Next, glass batches corresponding to the glass compositions for glass fibers of examples 1 to 8 or comparative examples 1 to 5 were placed in a platinum crucible having a diameter of 80mm, heated at a temperature of 1550 ℃ for 4 hours, further heated at a temperature of 1650 ℃ for 2 hours, and melted, and then taken out of the crucible to obtain a homogeneous glass gob and glass cullet. Next, the obtained glass gob and glass cullet were annealed at a temperature of 620℃for 8 hours to obtain a test piece.
The dielectric constant and dielectric loss tangent of the test piece obtained above were then evaluated by the methods shown below. The water resistance was evaluated by the method shown below using the glass chips obtained during the test piece production process. Further, using the glass cullet obtained during the test piece production process, the 1000 poise temperature and the liquid phase temperature were measured by the following methods, and the working temperature range was calculated using these values. The results are shown in Table 1.
[ method for evaluating Water resistance ]
The glass cullet obtained in the above manner was put into a small cylindrical platinum sleeve having 1 circular nozzle head at the bottom of the vessel, and after being heated to a predetermined temperature to be melted, the molten glass discharged from the nozzle head was wound around a stainless steel collet at a predetermined speed, and thereby was cooled and solidified while being drawn, to obtain glass fibers having a circular cross section of a perfect circle and a fiber diameter of 13 μm. About 1g of the glass fiber (test glass fiber) obtained above was collected from the collet, dried at 120℃for 1 hour, and the mass (mass before handling) was measured. Next, the glass fiber for test was allowed to stand in 100ml of distilled water at a temperature of 80℃for 24 hours. Then, the test glass fiber was obtained using a metal mesh having openings of about 150 μm, washed with distilled water, and dried at 120℃for 1 hour, and the mass (mass after operation) was measured.
From the above-described pre-operation mass and post-operation mass, a mass reduction rate (100× (1- (post-operation mass/pre-operation mass)) was calculated. The content of glass fiber which has a mass reduction rate of 2.0% or less and hardly dissolves in water was set as OK; the mass reduction rate was set to NG when the glass fiber component was significantly eluted in water in excess of 2.0%.
[ method for measuring dielectric constant and dielectric loss tangent ]
The test piece was polished to obtain a polishing test piece of 80 mm. Times.3 mm (thickness 1 mm). Next, the prepared polishing test piece was oven-dried and stored in a room at a temperature of 23℃and a humidity of 60% for 24 hours. Next, the dielectric constant (dielectric constant Dk) and dielectric loss tangent (dissipation factor Df) of the polishing test piece obtained above at 10GHz were measured by using a cavity resonator method dielectric constant measuring device (trade name: ADM01Oc1, manufactured by AET Co., ltd.) in accordance with JIS C2565:1992.
[ method for measuring 1000 poise temperature ]
The 1000 poise temperature was determined by: the glass cullet was melted in a platinum crucible using a high-temperature electric furnace (manufactured by Zhimau systems Co., ltd.) equipped with a rotary viscometer, and the viscosity of the molten glass was continuously measured using a rotary brookfield viscometer while changing the melting temperature, and the temperature corresponding to the rotation viscosity of 1000 poise was measured.
[ method for measuring liquid phase temperature ]
Glass scraps were crushed, 40g of glass particles having a particle diameter in the range of 0.5 to 1.5mm were placed in a platinum vessel of 180mm×20mm×15mm, heated in a tubular electric furnace provided with a temperature gradient in the range of 1000 to 1550 ℃ for 8 hours or more, and then taken out from the tubular electric furnace, and observed with a polarizing microscope to determine the position where crystals (devitrification) derived from the glass began to precipitate. The temperature in the tubular electric furnace was measured using a type B thermocouple, and the temperature at the position where the crystallization started to precipitate was obtained and used as the liquid phase temperature.
[ method for calculating working temperature Range ]
The operating temperature range is calculated using the difference between the 1000 poise temperature and the liquid phase temperature.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8
SiO 2 (mass%: S) 58.90 56.30 56.20 57.30 56.90 56.60 56.40 56.90
B 2 O 3 (mass%) 22.20 22.80 22.90 22.50 22.90 22.80 22.90 22.90
Al 2 O 3 (mass%: A) 10.80 12.00 12.00 11.90 12.00 11.40 12.00 12.00
P 2 O 5 (mass%: P) 2.10 2.10 3.60 2.20 1.60 2.10 1.00 1.60
TiO 2 (mass percent T) 3.10 3.10 1.60 3.20 3.10 3.60 4.20 2.60
CaO (mass%: C) 2.20 2.20 2.20 2.20 2.20 2.60 2.20 2.20
MgO (mass%: M) 0 0 0 0 0 0 0 0
F 2 (mass%) 0.70 1.50 1.50 0.70 1.30 0.90 1.30 1.30
Cl 2 (mass%) 0 0 0 0 0 0 0 0
F 2 +Cl 2 (mass%) 0.70 1.50 1.50 0.70 1.30 0.90 1.30 1.30
Na 2 O+K 2 O+Li 2 O 0 0 0 0 0 0 0 0
SrO (mass%) 0 0 0 0 0 0 0 0
MnO 2 (mass%) 0 0 0 0 0 0 0 0.50
ZrO 2 (mass%) 0 0 0 0 0 0 0 0.0
Sum up 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00
(S/A) 2 ×(P×T)(1 2) /(C+M) 3 7.13 5.27 4.94 5.78 4.70 3.86 4.25 4.31
Water resistance OK OK OK OK OK OK OK OK
1000 poise temperature (. Degree. C.) 1463 1424 1446 1449 1416 1436 1395 1414
Liquid phase temperature (. Degree. C.) 1208 1270 1275 1270 1300 1289 1332 1292
Operating temperature Range (. Degree. C.) 255 154 171 179 116 147 63 122
Dielectric constant 4.0 4.0 4.0 4.0 4.0 4.1 4.1 4.1
Dielectric loss tangent 0.0010 0.0010 0.0010 0.0010 0.0010 0.0011 0.0011 0.0011
TABLE 2
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
SiO 2 (mass%: S) 60.10 55.30 52.50 59.60 62.20
B 2 O 3 (mass%) 22.30 22.90 26.20 20.20 22.30
Al 2 O 3 (mass%: A) 8.40 13.00 1210 11.60 8.30
P 2 O 5 (mass%: P) 2.00 1.00 3.40 0.30 0
TiO 2 (mass percent T) 2.90 4.20 3.40 4.10 3.10
CaO (mass%: C) 3.30 2.30 1.90 3.70 3.10
MgO (mass%: M) 0 0 0 0 0
F 2 (mass%) 1.00 1.30 0.50 0.50 1.00
Cl 2 (mass%) 0 0 0 0 0
F 2 +Cl 2 (mass%) 1.00 1.30 0.50 0.50 1.00
Na 2 O+K 2 O+Li 2 O 0 0 0 0 0
SrO (mass%) 0 0 0 0 0
MnO 2 (mass%) 0 0 0 0 0
ZrO 2 (mass%) 0 0 0 0 0
Sum up 100.00 100.00 100.00 100.00 100.00
(S/A) 2 ×(P×T) (1/2) /(C+M) 3 3.43 3.05 9.33 0.58 0.00
Water resistance OK OK NG OK OK
1000 poise temperature (. Degree. C.) 1507 1376 1414 1443 1504
Liquid phase temperature (. Degree. C.) 1100 1334 1239 1215 1120
Operating temperature Range (. Degree. C.) 407 42 175 228 384
Dielectric constant 4.0 4.2 4.0 4.1 4.0
Dielectric loss tangent 0.0010 0.0011 0.0010 0.0012 0.0009
As is clear from table 1, according to the glass compositions for glass fibers of examples 1 to 8 below, the glass compositions for glass fibers can be used to obtain glass fibers having excellent water resistance and excellent dielectric characteristics such as a dielectric constant of 4.1 or less and a dielectric loss tangent of 0.0011 or less in a high frequency region of a measurement frequency of 10GHz while reducing the temperature per se to less than 1500 ℃. Examples 1 to 8 contain SiO in an amount of 50.00 to 61.00 mass% based on the total glass composition for glass fibers 2 B in a range of 16.00 to 27.00 mass% 2 O 3 Al in a range of 7.00 to 14.00 mass% 2 O 3 P in the range of 0.20 to 4.00 mass% 2 O 5 TiO in the range of 0.50 to 5.00 mass percent 2 CaO in a range of 0.10 to 5.00 mass%, mgO in a range of 0 to 4.00 mass%, and F in a total range of 0 to 2.00 mass% 2 And Cl 2 The SiO is 2 Content (mass%) S of the Al 2 O 3 Contains (1)Rate (mass%) A, P 2 O 5 P, the content of TiO is as follows 2 The content (mass%) T of CaO, the content (mass%) C of CaO, and the content (mass%) M of MgO satisfy the formula (1).
On the other hand, as is apparent from Table 2, according to the glass compositions for glass fibers of comparative examples 1, 2 and 4, the 1000 poise temperature per se exceeds 1500 ℃, or the dielectric constant of glass fibers obtained from the glass compositions for glass fibers exceeds 4.1, or the dielectric loss tangent exceeds 0.0011; according to the glass composition for glass fibers of comparative example 3 in which S, A, P, T, C and M exceed the range of formula (1), sufficient water resistance cannot be obtained. In comparative examples 1, 2 and 4, siO was contained in an amount of 50.00 to 61.00 mass% based on the total glass composition for glass fibers 2 B in a range of 16.00 to 27.00 mass% 2 O 3 Al in a range of 7.00 to 14.00 mass% 2 O 3 P in the range of 0.20 to 4.00 mass% 2 O 5 TiO in the range of 0.50 to 5.00 mass percent 2 CaO in a range of 0.10 to 5.00 mass%, mgO in a range of 0 to 4.00 mass%, and F in a total range of 0 to 2.00 mass% 2 And Cl 2 But the S, A, P, T, C and M are smaller than the range of formula (1).
Further, it is apparent that the 1000 poise temperature of the glass composition for glass fiber according to comparative example 5 below exceeds 1500 ℃. In comparative example 5, siO was contained in an amount exceeding 61.00 mass% with respect to the total glass composition for glass fibers 2 ，P 2 O 5 The content of (2) is less than 0.20 mass%, and the above S, A, P, T, C and M are less than the range of formula (1).

Claims (7)

1. A glass composition for glass fibers, characterized in that,
contains SiO in an amount ranging from 50.00 to 61.00 mass% relative to the total amount of the glass composition for glass fibers 2 B in a range of 16.00 to 27.00 mass% 2 O 3 Al in a range of 7.00 to 14.00 mass% 2 O 3 0.20% by mass to the maximumP in the range of 4.00% by mass 2 O 5 TiO in the range of 0.50 to 5.00 mass% 2 CaO in a range of 0.10 to 5.00 mass%, mgO in a range of 0 to 4.00 mass%, and F in a total range of 0 to 2.00 mass% 2 And Cl 2 ，
The SiO is 2 Content (mass%) S of the Al 2 O 3 Content (mass%) A of the above P 2 O 5 P, the content of TiO is as follows 2 The content (mass%) T of CaO, the content (mass%) C of MgO, and the content (mass%) M of MgO satisfy the following formula (1):
3.65≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤8.25…(1)。
2. The glass composition for glass fibers according to claim 1, wherein,
the S, the a, the P, the T, the C, and the M satisfy the following formula (2):
4.51≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.32…(2)。
3. the glass composition for glass fibers according to claim 1 or 2,
the S, the a, the P, the T, the C, and the M satisfy the following formula (3):
4.87≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.20…(3)。
4. the glass composition for glass fibers according to any of claim 1 to 3,
the S, the a, the P, the T, the C, and the M satisfy the following formula (4):
5.96≤(S/A) 2 ×(P×T) 1/2 /(C+M) 3 ≤7.16…(4)。
5. a glass fiber is characterized in that,
which is composed of the glass composition for glass fibers according to any one of claims 1 to 4.
6. A glass fiber fabric is characterized in that,
comprising the glass fiber of claim 5.
7. A glass fiber reinforced resin composition comprising the glass fiber of claim 5.
CN202280008408.6A 2021-02-24 2022-02-09 Glass composition for glass fibers, glass fiber fabric, and glass fiber reinforced resin composition Pending CN116670091A (en)

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