JP5809900B2 - Glass composition, glass filler for polycarbonate resin using the same, and polycarbonate resin composition - Google Patents

Description

  The present invention relates to a glass composition, and particularly to a glass composition that can be suitably used as a glass filler to be blended in a polycarbonate resin. Moreover, this invention relates to the glass filler for polycarbonate resins using the said glass composition, and a polycarbonate resin composition.

  The polycarbonate resin is a polycarbonate produced by copolymerization of bisphenol A [2,2-bis (4′-hydroxyphenyl) propane] with phosgene or carbonate. Polycarbonate resin is superior in mechanical strength, impact resistance, heat resistance, and transparency compared to other resin materials, and is used as an engineering plastic for electrical equipment casings, automotive parts, building materials, etc. Yes.

  In order to further improve the mechanical strength, heat resistance and the like of the polycarbonate resin, a filler may be blended with the polycarbonate resin. As a filler used for the purpose of reinforcing a polycarbonate resin or the like, a glass filler having a scale shape, a fiber shape, a powder shape, a bead shape, or the like is known. Examples of the glass composition constituting such a glass filler include glass compositions such as non-alkali silicate glass such as E glass, alkali-containing silicate glass such as C glass, and ordinary plate glass.

  However, when the glass filler which consists of said glass composition is added to polycarbonate resin, the performance of the obtained polycarbonate resin composition may fall. That is, when the composition as described above is used as the glass filler, the polycarbonate resin and the glass filler have different refractive indexes, so that light is scattered at the interface between the polycarbonate resin and the glass filler, and the polycarbonate resin composition The transparency of the is reduced.

  Against this background, glass fillers suitable for blending with polycarbonate resins have been developed.

For example, Patent Document 1 discloses a glass fiber whose composition is adjusted so that the refractive index n _D approaches the refractive index n _D of polycarbonate (about 1.585) for the purpose of ensuring the transparency of the polycarbonate resin composition. It is disclosed. The specific range of the refractive index n _D of this glass fiber is 1.570 to 1.600. This glass fiber contains 3% by weight or more of Na ₂ O and K ₂ O (the content of alkali metal oxide is 6% by weight or more).

In Patent Document 2, in order to ensure the transparency of the polycarbonate resin composition, the refractive index n _d of the glass fiber is brought close to the value of the refractive index n _d of the polycarbonate, and the Abbe number ν _d of the glass fiber is set to the Abbe number of the polycarbonate. The problem is to approach the number ν _d (about 30). Patent Document 2 discloses a glass fiber having a refractive index n _d of 1.570 to 1.600 and an Abbe number ν _d of 50 or less. The glass composition disclosed in Patent Document 2 also contains a considerable amount of alkali metal oxide (the content of alkali metal oxide in the examples is 16% or more).

  When the glass fiber disclosed in Patent Document 1 or 2 is added to the polycarbonate resin, the hydrolysis reaction is promoted by the alkali ions contained in the glass fiber, and the molecular weight of the polycarbonate resin is lowered.

Patent Documents 3 to 5 disclose glass fillers whose alkali metal oxide content is limited to 2% by mass or less. In the embodiment of Patent Document 3, a glass fiber having a refractive index n _D of 1.581 to 1.585 and an Abbe number ν _D of 58 to 59 is used. In the embodiment of Patent Document 4, a refractive index n _d of 1 is used. A glass composition having an Abbe number ν _d of 50 to 56 and a refractive index n _d of 1.582 to 1.596 and an Abbe number ν _d of Glass compositions that are 52-57 are described respectively. The Abbe number in each of the above examples is 50 or more, and the difference from the Abbe number (about 30) of the polycarbonate resin is slightly large.

In the comparative example of Patent Literature 4 and the comparative example of Patent Literature 5, glass compositions having an Abbe number of less than 50 are disclosed. Specifically, in the glass composition described in the comparative example of Patent Document 4, the refractive index n _d is 1.607 and the Abbe number ν _d is 44. In the glass composition described in the comparative example of Patent Document 5, the refractive index n _d is 1.612, and the Abbe number ν _d is 43. Each of the comparative examples has a refractive index n _d exceeding 1.600, which is largely different from the refractive index n _{d of} polycarbonate resin (about 1.585).

JP 58-60641 A JP-A-5-294671 JP 2007-153729 A International Publication No. 2008/156090 Pamphlet International Publication No. 2008/156091 Pamphlet

  In the glass compositions disclosed in Patent Documents 3 to 5, the content of the alkali metal oxide is suppressed to a very small amount (2% by mass or less). Therefore, a decrease in the molecular weight of the polycarbonate resin due to hydrolysis does not significantly affect the properties of the polycarbonate resin composition. However, in any of Patent Documents 3 to 5, both the refractive index and the Abbe number are controlled within a range particularly suitable for blending with a polycarbonate resin (refractive index: about 1.575 to 1.595, Abbe number of about 49 or less). I can't do it.

  When the characteristics of Examples and Comparative Examples of Patent Documents 4 and 5 are compared, in a glass composition in which the content of alkali metal oxide is kept low, the Abbe number increases when the refractive index is adjusted to an appropriate range. It can be understood that the refractive index becomes too high when the is adjusted to an appropriate range.

  Therefore, an object of the present invention is to provide a glass composition in which the content of alkali metal oxide is limited to be low and the refractive index and Abbe number can be adjusted to a range particularly suitable for blending with a polycarbonate resin.

The present invention
Expressed in mass%,
45 ≦ SiO ₂ ≦ 65,
0.5 ≦ B ₂ O ₃ <2,
5 ≦ Al ₂ O ₃ ≦ 15,
5 ≦ CaO ≦ 25,
0.1 ≦ MgO ≦ 10,
7 <TiO ₂ ≦ 12,
0 ≦ (Li ₂ O + Na ₂ O + K ₂ O) <2,
A glass composition containing the components of:
I will provide a.

  In the glass composition of the present invention, the content of alkali metal oxide is kept low. For this reason, even if the glass composition of this invention is mix | blended with a polycarbonate resin, the hydrolysis reaction of a polycarbonate resin does not occur easily. Moreover, according to this invention, the refractive index and Abbe number of a glass composition can be approximated to the refractive index and Abbe number of polycarbonate resin.

Schematic diagram of an example of scaly glass Schematic diagram of an example of scale glass manufacturing equipment Schematic diagram of an example of chop strand production equipment Schematic diagram of an example of chop strand production equipment

  Hereinafter, embodiments of the present invention will be described.

[Glass composition]
The glass composition of the present embodiment includes, as essential components, silicon dioxide (SiO ₂ ), boron oxide (B ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), calcium oxide (CaO), magnesium oxide (MgO), And titanium oxide (TiO ₂ ). The glass composition may optionally include lithium oxide (Li ₂ O), it may include at least one selected from sodium oxide (Na ₂ O) and potassium oxide (K ₂ O). The content of each component is expressed in mass%,
45 ≦ SiO ₂ ≦ 65,
0.5 ≦ B ₂ O ₃ <2,
5 ≦ Al ₂ O ₃ ≦ 15,
5 ≦ CaO ≦ 25,
0.1 ≦ MgO ≦ 10,
7 <TiO ₂ ≦ 12,
0 ≦ (Li ₂ O + Na ₂ O + K ₂ O) <2,
Set to

  The glass composition may further contain strontium oxide (SrO) as necessary. The content of strontium oxide is preferably 20% by mass or less. Furthermore, components such as barium oxide (BaO) and zinc oxide (ZnO) may be contained in the glass composition.

  Each component which comprises this glass composition is demonstrated in detail below.

(SiO ₂ )
Silicon dioxide (SiO ₂ ) is a main component that forms a glass skeleton. In this specification, a main component means a component with the highest content rate. Silicon dioxide is a component that adjusts the devitrification temperature and viscosity of the glass, and is also a component that improves water resistance. If the silicon dioxide content in the glass composition is 45% by mass or more, an increase in the devitrification temperature is suppressed, and a glass with less devitrification is likely to be produced (if less than 45% by mass, ΔT (“working temperature−loss (Temperature permeation ”, details will be described later) tends to be lower than 0 ° C., and the refractive index n _d tends to be higher than 1.595). Moreover, the water resistance and acid resistance of glass are also improved. On the other hand, if the content of silicon dioxide is 65% by mass or less, the melting point of the glass becomes low and the glass is easily melted uniformly (if the content exceeds 65% by mass, the working temperature tends to be higher than 1300 ° C.).

  Therefore, the lower limit of the content of silicon dioxide is 45% by mass or more, preferably 48% by mass or more, more preferably 50% by mass or more, and most preferably 52% by mass or more. On the other hand, the upper limit of the content of silicon dioxide is 65% by mass or less, preferably 60% by mass or less, and more preferably 58% by mass or less. The range of the content of silicon dioxide is selected from any combination of these upper and lower limits. Specifically, it is 45% by mass to 65% by mass, and preferably 48% by mass to 60% by mass.

(B ₂ O ₃ )
Diboron trioxide (B ₂ O ₃ ) is a component that forms a glass skeleton. Moreover, it is a component which adjusts the devitrification temperature and viscosity of glass, and also is a component which improves water resistance. If the content rate of diboron trioxide in a glass composition is 0.1 mass% or more, adjustment of devitrification temperature and a viscosity will become easy. Furthermore, since such glass can suppress elution of alkali ions, it is difficult to reduce the molecular weight of the polycarbonate resin even when blended with the polycarbonate resin as a filler. If the content of diboron trioxide is less than 2% by mass, it will not significantly reduce the lifetime of the kiln by melting the furnace wall of the melting kiln or heat storage kiln when the glass is melted (more than 2% by mass) In this case, it is conceivable that ΔT tends to be smaller than 0 ° C.).

Further, diboron trioxide has the effect of lowering the refractive index n _d of the glass composition. Viewpoint of adjusting the refractive index n _d of the glass composition in a suitable range (in particular, titanium oxide as described later (by the action of TiO _2), in view of reducing the refractive index n _d of excessively increased) from this embodiment In the form, the content rate of diboron trioxide is set to 0.5 mass% or more.

  As mentioned above, the minimum of the content rate of diboron trioxide is 0.5 mass% or more, and 0.6 mass% or more is preferable. On the other hand, the upper limit of the content of diboron trioxide is less than 2 mass%, preferably less than 1.8 mass%, more preferably 1.6 mass% or less, and may be 1.5 mass% or less. . The range of the content ratio of diboron trioxide is selected from any combination of these upper and lower limits, specifically 0.5 mass% or more and less than 2 mass%, and 0.5 mass% or more and 1.8 mass%. It is preferable that it is less than mass%.

(Al ₂ O ₃ )
Aluminum oxide (Al ₂ O ₃ ) is a component that forms a glass skeleton. Moreover, it is a component which adjusts the devitrification temperature and viscosity of glass, and also is a component which improves water resistance. If the content of aluminum oxide in the glass composition is 5% by mass or more, the devitrification temperature and viscosity can be easily adjusted (if it is less than 5% by mass, ΔT tends to be smaller than 0 ° C., and the refractive index n _d tends to be higher than 1.595). Furthermore, since such glass can suppress elution of alkali ions, it is difficult to reduce the molecular weight of the polycarbonate resin even when blended with the polycarbonate resin as a filler. If the content of aluminum oxide is 15% by mass or less, the melting point of the glass is lowered and the glass is easily melted uniformly (if it exceeds 15% by mass, the working temperature tends to be higher than 1300 ° C.).

  Therefore, the lower limit of the aluminum oxide content is 5% by mass or more, preferably 8% by mass or more, and more preferably 10% by mass or more. On the other hand, the upper limit of the content of aluminum oxide is 15% by mass or less, and preferably 14.5% by mass or less. The range of the content of aluminum oxide is selected from any combination of these upper and lower limits. Specifically, it is 5% by mass to 15% by mass, and preferably 8% by mass to 15% by mass.

(CaO)
Calcium oxide (CaO) is a component that adjusts the devitrification temperature and viscosity of glass. If the content rate of the calcium oxide in a glass composition is 5 mass% or more, adjustment of a devitrification temperature and a viscosity will become easy. If the content of calcium oxide is 25% by mass or less in the glass composition, it is easy to suppress an increase in the devitrification temperature and easily produce a glass with less devitrification (less than 5% by mass or more than 25% by mass). And ΔT tends to be smaller than 0 ° C.).

  Therefore, the lower limit of the content of calcium oxide is 5% by mass or more, preferably 8% by mass or more, and more preferably 10% by mass or more. The upper limit of the content of calcium oxide is 25% by mass, preferably 23% by mass or less, more preferably 20% by mass or less, and most preferably 18% by mass or less. The range of the content of calcium oxide is selected from any combination of these upper and lower limits. Specifically, it is 5% by mass or more and 25% by mass or less, and preferably 8% by mass or more and 23% by mass or less. .

(MgO)
Magnesium oxide (MgO) is a component that adjusts the devitrification temperature and viscosity of glass. If the content rate of magnesium oxide in a glass composition is 0.1 mass% or more, adjustment of devitrification temperature and a viscosity will become easy. If the content of magnesium oxide in the glass composition is 10% by mass or less, it is easy to suppress an increase in the devitrification temperature, and a glass with less devitrification can be easily produced (less than 0.1% by mass or 10% by mass). If it exceeds, ΔT tends to be smaller than 0 ° C.).

  Accordingly, the lower limit of the magnesium oxide content is 0.1% by mass or more, preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit of the content of magnesium oxide is 10% by mass or less, preferably less than 9% by mass, more preferably less than 8% by mass, and most preferably 5% by mass or less. The range of the content of magnesium oxide is selected from any combination of these upper and lower limits, and is specifically 0.1% by mass or more and 10% by mass or less, and 1% by mass or more and less than 9% by mass. Is preferred.

(TiO ₂ )
Titanium oxide (TiO ₂ ) is a component that adjusts the refractive index n _d and Abbe number ν _d of glass. Moreover, it is a component which adjusts the devitrification temperature and viscosity of glass, and also is a component which improves water resistance. If the content of titanium oxide in the glass composition is greater than 7% by mass, the refractive index n _d and the Abbe number ν _d can be easily adjusted (if the content is less than 7% by mass, the Abbe number ν _d tends to be 50 or more). Furthermore, since such glass can suppress elution of alkali ions, it is difficult to reduce the molecular weight of the polycarbonate resin even when blended with the polycarbonate resin as a filler. On the other hand, if the content of titanium oxide is 12% by mass or less, it is easy to suppress an increase in the devitrification temperature, and a glass with less devitrification can be easily manufactured (If it exceeds 12% by mass, ΔT becomes smaller than 0 ° C. easy).

  Therefore, the lower limit of the content of titanium oxide is more than 7% by mass, preferably more than 7.3% by mass, and more preferably 7.7% by mass or more. On the other hand, the upper limit of the content of titanium oxide is 12% by mass or less, preferably 10% by mass or less, more preferably 9% by mass or less, and most preferably 8% by mass or less. The range of the content of titanium oxide is selected from any combination of these upper and lower limits. Specifically, it is greater than 7% by mass and not greater than 12% by mass, and greater than 7% by mass and not greater than 10% by mass. Is more preferable, and it is especially preferable that it is larger than 7 mass% and 9 mass% or less. Moreover, it is preferable that the content rate of diboron trioxide is 0.5 mass% or more and less than 1.8 mass%, and the content rate of titanium oxide is larger than 7 mass% and 10 mass% or less. It is more preferable that the content of is 0.5% by mass or more and less than 1.8% by mass and the content of titanium oxide is greater than 7% by mass and 9% by mass or less.

(SrO)
Strontium oxide (SrO) is a component that adjusts the devitrification temperature and viscosity of the glass. Although strontium oxide is not an essential component, the devitrification temperature and viscosity can be easily adjusted if the content of the glass composition is 20% by mass or less.

  Therefore, the upper limit of the content of strontium oxide is preferably 20% by mass, more preferably 15% by mass or less, further preferably 12% by mass or less, and most preferably 10% by mass or less. Specifically, the range of the content of strontium oxide is preferably 0% by mass to 20% by mass, and more preferably 0% by mass to 15% by mass.

(BaO)
Barium oxide (BaO) has a large specific gravity, and when used as a glass filler blended in a polycarbonate resin, the dispersibility with respect to the polycarbonate resin is deteriorated. Furthermore, barium oxide (BaO) requires high considerations in handling the raw material and is expensive. Therefore, it is preferable that barium oxide is not substantially contained.

(ZnO)
Zinc oxide (ZnO) is likely to volatilize and thus may be scattered when the glass is melted. Therefore, it is preferable that zinc oxide is not substantially contained. Thereby, the composition fluctuation | variation of the glass at the time of melting of glass is suppressed.

(Li ₂ O, Na ₂ O, K ₂ O)
Alkali metal oxides (Li ₂ O, Na ₂ O, K ₂ O) are components that adjust the devitrification temperature and viscosity during glass formation.

Alkali metal oxides are not essential, but if the total content of lithium oxide, sodium oxide and potassium oxide (Li ₂ O + Na ₂ O + K ₂ O) is less than 2% by mass, the glass transition temperature will increase, Heat resistance is improved. In addition, the working temperature is higher than the devitrification temperature, and a glass with less devitrification can be easily manufactured. Furthermore, since such glass can suppress elution of alkali ions, it is difficult to reduce the molecular weight of the polycarbonate resin even if blended as a filler.

Therefore, the upper limit of the total content of lithium oxide, sodium oxide and potassium oxide (Li ₂ O + Na ₂ O + K ₂ O) is preferably less than 2% by mass, preferably 1.5% by mass or less, and less than 1% by mass Is more preferable, and 0.8% by mass or less is most preferable.

(ZrO ₂ )
Zirconium oxide (ZrO ₂ ) is generally a component that adjusts the devitrification temperature and viscosity of the glass. However, in the glass composition of this embodiment, the devitrification temperature is increased and the melting point of the glass is increased. . Considering this, the range of the content of zirconium oxide is preferably 0% by mass or more and 1% by mass or less. Further, it is more preferable that zirconium oxide is not substantially contained.

(Fe)
Usually, iron (Fe) contained in glass exists in the state of Fe ³⁺ or Fe ²⁺ . Fe ³⁺ is a component that improves the ultraviolet absorption property of the glass, and Fe ²⁺ is a component that improves the heat ray absorption property of the glass. Even if iron is not intentionally included, it may inevitably be mixed into the glass composition from other industrial raw materials. If there is little iron content, the coloring of glass can be suppressed. When such glass is used as a filler, the transparency of the polycarbonate resin composition is hardly impaired.

Therefore, it is preferable that the iron content is small, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and substantially not contained in terms of iron sesquioxide (Fe ₂ O ₃ ). Is more preferable.

(SO ₃ )
Sulfur trioxide (SO ₃ ) is not an essential component, but may be used as a fining agent. When a sulfate raw material is used, sulfur trioxide may be contained in the glass composition in an amount of 0.5% by mass or less.

(F)
Fluorine (F) tends to volatilize, so it is scattered when the glass is melted, which may cause fluctuations in the composition of the glass when the glass is melted, and has a problem that it is difficult to manage the content in the glass. . In addition, fluorine needs to be handled with care and is expensive. Therefore, it is preferable that fluorine is not substantially contained. Further, it is more preferable that zinc oxide and fluorine are not substantially contained, and it is particularly preferable that zirconium oxide, barium oxide, zinc oxide and fluorine are not substantially contained.

  Here, the phrase “not substantially contained” means that it is not intentionally included unless, for example, it is inevitably mixed from industrial raw materials. Specifically, it means that the content is less than 0.1% by mass in the glass composition. This content is preferably less than 0.05% by mass, more preferably less than 0.03% by mass, and even more preferably less than 0.01% by mass.

[Physical properties of glass composition]
Next, the physical properties of the glass composition will be described.

(Melting characteristics)
The temperature when the viscosity of the molten glass is 1000 dPa · sec (1000 poise) is called the working temperature of the glass, and is the most suitable temperature for forming the glass. When producing glass flakes or glass fibers, if the working temperature of the glass is 1100 ° C. or higher, variations in the glass flake thickness and glass fiber diameter can be reduced. On the other hand, if the working temperature is 1300 ° C. or lower, the fuel cost for melting the glass can be reduced. In addition, the glass manufacturing apparatus is not easily corroded by heat, and the life of the apparatus is extended.

  Therefore, the lower limit of the working temperature is preferably 1100 ° C. or higher, more preferably 1150 ° C. or higher. The upper limit of the working temperature is preferably 1300 ° C. or less, more preferably 1280 ° C. or less, and further preferably 1260 ° C. or less. The working temperature range is selected from any combination of these upper and lower limits. For example, the working temperature is preferably 1100 to 1300 ° C, more preferably 1100 to 1280 ° C, and even more preferably 1100 to 1260 ° C.

  Further, as the temperature difference ΔT obtained by subtracting the devitrification temperature from the working temperature increases, devitrification is less likely to occur at the time of glass forming, and a homogeneous glass can be produced with a high yield. Therefore, ΔT is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. On the other hand, when ΔT is less than 150 ° C., the glass composition can be easily adjusted. Therefore, ΔT is more preferably 120 ° C. or less, and further preferably 100 ° C. or less. For example, ΔT is preferably 0 to 150 ° C., more preferably 0 to 120 ° C.

  In addition, devitrification means producing cloudiness by the crystal | crystallization which produced | generated and grew in the molten glass base material. In the glass produced from such a molten glass substrate, a crystallized lump may exist, which is not preferable as a filler for polycarbonate resin.

(optical properties)
If the refractive indexes of the glass filler and the polycarbonate resin are equal, there is no light scattering at the interface between the glass filler and the polycarbonate resin, so that the transparency of the polycarbonate resin can be maintained. For this reason, it is preferable that the refractive index of a glass composition is near the refractive index of polycarbonate resin. Refractive index n _d of polycarbonate resin measured with a yellow helium d line (wavelength of light 587.6 nm) is normally about 1.585. Accordingly, the refractive index n _d of the glass composition is preferably from 1.575 to 1.595, more preferably 1.580 to 1.590, more preferably 1.582 to 1.588, 1.583 to 1. 587 is most preferred. Difference in the refractive index n _d of the glass composition and polycarbonate resin is preferably 0.010 or less, more preferably 0.005 or less, more preferably 0.003 or less, most preferably 0.002 or less.

Further, the refractive index n _D of the polycarbonate resin measured with yellow sodium D-line (light wavelength 589.3 nm) is usually about 1.585. Accordingly, the refractive index n _D of the glass filler is preferably 1.575 to 1.595, more preferably 1.580 to 1.590, still more preferably 1.582 to 1.588, and 1.583 to 1.587. Is most preferred. The difference in refractive index n _D between the glass filler and the polycarbonate resin is preferably 0.010 or less, more preferably 0.005 or less, further preferably 0.003 or less, and most preferably 0.002 or less.

The Abbe number ν _d is an amount representing the degree of dispersion of a transparent body such as glass and is the reciprocal of the dispersion rate. If the Abbe number ν _d between the glass filler and the polycarbonate resin is close, the transparency of the polycarbonate resin composition can be maintained when the polycarbonate resin composition is formed by blending the glass filler with the polycarbonate resin. Therefore, the Abbe number [nu _d of the glass composition is preferably close to the Abbe number [nu _d of polycarbonate resin. The Abbe number ν _d of the polycarbonate resin is usually about 30. Therefore, the Abbe number ν _d of the glass composition is preferably 49 or less. The lower limit of the Abbe number ν _d is preferably about 40, but may be 45 or more practically. Therefore, the Abbe number ν _d is preferably 40 to 49, for example 45 to 49.

In particular, the easy to close both the refractive index n _d and the Abbe number [nu _d of the glass composition while limiting the total limit of the content of alkali metal oxide to the refractive index n _d and the Abbe number [nu _d of polycarbonate resin is not. This is because the refractive index n _d and the Abbe number ν _d basically have a so-called trade-off relationship in the glass composition in which the content of the alkali metal oxide is kept low. However, according to the glass composition of the present embodiment, it is possible to adjust both the refractive index n _d and the Abbe number ν _d of the glass composition to a preferable range for blending with the polycarbonate resin.

Specifically, a glass composition having a refractive index n _d of 1.575 to 1.595 and an Abbe number ν _d of 45 to 49, and a refractive index n _d of 1.585 to 1.592. A glass composition having an Abbe number ν _d of 47 to 49 can be provided.

[Glass filler]
The glass filler which consists of a glass composition of this embodiment is suitable for the use as a glass filler for polycarbonate resins for mix | blending with polycarbonate resin. A glass composition is shape | molded into predetermined forms, such as scale-like glass, a chopped strand, a milled fiber, glass powder, a glass bead, and is used as a glass filler, for example.

  Fig.1 (a) is a perspective view which shows scale-like glass typically, and FIG.1 (b) is a top view which shows the scale-like glass. The glass flakes 10 are, for example, flaky particles having an average thickness t of 0.1 to 15 μm, an average particle diameter a of 0.2 to 15000 μm, and an aspect ratio (average particle diameter a / average thickness t) of 2 to 1000. It is. In addition, S in FIG.1 (b) is an area when the scale-like glass 10 is planarly viewed.

  Here, the average thickness of the glass flakes means that at least 100 glass flakes are extracted, the thicknesses of those glass flakes are measured using a scanning electron microscope (SEM), and the total thickness is calculated as follows. Means the value divided by the number of glass flakes measured. The average particle diameter of the glass flakes means a particle diameter (D50) corresponding to a cumulative volume percentage of 50% in the particle size distribution measured based on the laser diffraction scattering method.

  The scale-like glass 10 can be manufactured using, for example, the manufacturing apparatus shown in FIG. As shown in FIG. 2, a glass substrate 11 having a glass composition melted in a refractory kiln 12 is swelled into a balloon shape by a gas fed into a blow nozzle 13 to form a hollow glass film 14. By crushing the hollow glass film 14 with a pair of pressing rolls 15, the scale-like glass 10 is obtained.

  The chopped strand is a glass fiber having a fiber diameter of 1 to 50 μm and an aspect ratio (fiber length / fiber diameter) of 2 to 1000. The chopped strand can be manufactured using, for example, the apparatus shown in FIGS.

  As shown in FIG. 3, a glass base melted in a refractory kiln (not shown) is drawn out from a bushing 20 having a large number (for example, 2400 nozzles) at the bottom, and a large number of glass filaments 21 are formed. The Cooling water is sprayed onto the glass filament 21, and then a binder (bundling agent) 24 is applied by the application roller 23 of the binder applicator 22. A large number of glass filaments 21 to which the binder 24 is applied are focused by a reinforcing pad 25 as three strands 26 each made of, for example, about 800 glass filaments 21. Each strand 26 is wound around a cylindrical tube 29 fitted to a collet 28 while traversing with a traverse finger 27. Then, the cylindrical tube 29 around which the strand 26 is wound is removed from the collet 28 to obtain a cake (strand wound body) 30.

  Next, as shown in FIG. 4, the cake 30 is accommodated in the creel 31, the strand 26 is pulled out from the cake 30, and bundled as a strand bundle 33 by the focusing guide 32. Water or a treatment liquid is sprayed onto the strand bundle 33 from the spraying device 34. Further, the strand bundle 33 is cut by the rotary blade 36 of the cutting device 35 to obtain a chopped strand 37.

  The milled fiber is a glass fiber having a fiber diameter of 1 to 50 μm and an aspect ratio (fiber length / fiber diameter) of 2 to 500. Although the description of the method for producing the milled fiber is omitted here, a known method may be followed.

  A glass powder having an average particle diameter of 1 to 500 μm is preferable for use as a glass filler. Here, the average particle diameter is defined as the diameter of a sphere having the same volume as the glass powder particles. Such glass powder can be produced according to a known method.

  Glass beads having a particle diameter of 1 to 500 μm are preferable for use as glass fillers. Here, the particle diameter is defined as the diameter of a sphere having the same volume as the glass bead particle. Such glass beads can be produced according to a known method.

[Polycarbonate resin composition]
A glass filler formed from a glass composition constitutes a polycarbonate resin composition by being blended with the polycarbonate resin. Although the content rate of the glass filler in a polycarbonate resin composition is suitably set according to the objective, 10-50 mass% is preferable, for example. The glass filler formed from the glass composition has a small difference in refractive index from that of the polycarbonate resin, little elution of alkali components, and excellent chemical durability. Therefore, the obtained polycarbonate resin composition has transparency equivalent to that of the polycarbonate resin and mechanical strength and heat resistance superior to those of the polycarbonate resin.

  The polycarbonate resin composition can be produced according to a known method. Specifically, the polycarbonate resin and the glass filler may be melt-kneaded while heating using a mixer or the like. Known polycarbonate resins can be used. The form of the glass filler is not limited to one type, and a plurality of types may be combined and blended. Moreover, you may mix | blend various coupling agents and additives as needed for the purpose of improving the performance of a polycarbonate resin composition. The temperature for melt kneading is preferably not higher than the heat resistance temperature of the polycarbonate resin.

  By molding such a polycarbonate resin composition into a molded body, it can be suitably used for casings of electrical equipment, automobile parts, building materials, and the like. The molding may be performed according to a known method, and an extrusion molding method, an injection molding method, a press molding method, a sheet molding method by calendar molding, and the like are employed. In addition, it is preferable that the heating temperature at the time of shaping | molding is below the heat-resistant temperature of polycarbonate resin.

  Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples.

(Examples 1-9 and Comparative Examples 1-3)
Normal glass materials, such as silica sand, were prepared so that it might become a composition shown in Table 1-Table 2, and the batch of the glass material was produced for every Example and Comparative example. Using an electric furnace, each batch was heated to 1400-1600 ° C. and melted, and maintained for about 4 hours until the composition became uniform. Thereafter, the molten glass (glass melt) was poured onto an iron plate, and gradually cooled to room temperature in an electric furnace to obtain a glass composition (bulk: plate-like product).

  Moreover, about the glass composition, the relationship between a viscosity and temperature was investigated by the normal platinum ball pulling-up method, and working temperature was calculated | required from the result. Here, the platinum ball pulling method refers to the relationship between the load load (resistance) when pulling a platinum ball immersed in molten glass at a constant speed and the gravity and buoyancy acting on the platinum ball. In this method, the viscosity is measured by applying the Stokes' law, which shows the relationship between the viscosity when dropping inside and the falling speed.

  Furthermore, the glass composition is pulverized to a particle size of 1.0 to 2.8 mm, put into a platinum boat, and heated in an electric furnace with a temperature gradient (800 to 1400 ° C.) for 2 hours, so that crystals appear. The devitrification temperature was calculated from the maximum temperature of the electric furnace corresponding to the position. Here, the particle diameter is a value measured by a sieving method. Note that different temperatures (temperature distribution in the electric furnace) depending on the location in the electric furnace are measured in advance, and the glass placed in a predetermined location in the electric furnace is measured in advance. Heated at the place temperature. ΔT is a temperature difference obtained by subtracting the devitrification temperature from the working temperature.

The refractive index of the glass composition, by using a Pulfrich refractometer to determine the refractive index n _d of yellow helium d line (wavelength of light 587.6 nm).

Abbe number [nu _d of the glass composition was determined by the following equation (1) using the refractive index n _d of the glass composition.

ν _d = (n _d −1) / (n _F −n _C ) (Formula 1)
Here, n _d is the refractive index of the d-line (wavelength 587.6 nm), n _F is the refractive index of the F-line (wavelength 486.1 nm), and n _C is the refraction of the C-line (wavelength 656.3 nm). Rate.

These measurement results are shown in Tables 1 and 2. Incidentally, the value of glass compositions in the table are all values expressed in percent by weight (e.g., Table 1, the content of TiO ₂ in the glass composition of Example 1 is 7.80 wt% Show).

The working temperature of the glass compositions obtained in Examples 1-9 was 1247-1275 ° C. Accordingly, these glass compositions are suitable for forming glass fillers. ΔT (working temperature−devitrification temperature) of the glass compositions obtained in Examples 1 to 9 was 13 to 61 ° C. Therefore, these glass compositions do not easily cause devitrification in the glass filler manufacturing process. Refractive index n _d of the glass composition obtained in Example 1-9 was 1.587 to 1.592. The Abbe numbers ν _d of the glass compositions obtained in Examples 1 to 9 were 48 to 49.

From the above, the glass compositions obtained in Examples 1 to 9 have melting characteristics suitable for molding of glass filler, together with refractive index n _d and Abbe number ν _d suitable for blending with polycarbonate resin as filler. It can be seen that

On the other hand, the glass composition obtained in Comparative Example 1 has the composition of a conventional plate glass, and the contents of SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , TiO ₂ and alkali metal are defined in the present invention. It was outside the composition range. Therefore, the refractive index n _d of the glass composition obtained in Comparative Example 1 is 1.517, lower than the refractive index n _d of Example 1-9. The Abbe number ν _d was 59, which was higher than those in Examples 1-9.

The glass composition obtained in Comparative Example 2 has the composition of conventional C glass, and the contents of SiO ₂ , B ₂ O ₃ , Al ₂ O ₃ , TiO ₂ and alkali metal are defined in the present invention. It was outside the composition range. Therefore, the refractive index n _d of the glass composition obtained in Comparative Example 2 is 1.523, lower than the refractive index n _d of the glass composition obtained in Example 1-9. The Abbe number ν _d was 60, which was higher than those in Examples 1-9.

The glass composition obtained in Comparative Example 3 had the composition of conventional E glass, and the content ratios of B ₂ O ₃ and TiO ₂ were outside the composition range defined in the present invention. Therefore, the refractive index n _d of the glass composition obtained in Comparative Example 3 is 1.561, lower than the refractive index n _d of the glass composition obtained in Example 1-9. The Abbe number ν _d was 59, which was higher than those in Examples 1-9.

(Examples 10 to 18)
In Examples 10-18, scaly glass was produced using the glass compositions (bulk) obtained in Examples 1-9, respectively (Example 10 is in Example 1 and Example 11 is in Example 2. ... Embodiment 18 corresponds to Embodiment 9). That is, the glass composition (bulk) was remelted in an electric furnace and then formed into pellets while cooling. This pellet was put into the manufacturing apparatus shown in FIG. 2 to produce scale-like glass having an average thickness of 0.5 to 1 μm. The average thickness of the scaly glass is measured from the cross-section of the scaly glass with respect to 100 scaly glasses using an electron microscope (manufactured by Keyence Corporation, Real Surface View Microscope, VE-7800). Determined by averaging them. Since the aspect ratio of the glass flakes produced by the above method is in the range of 2 to 1000, the average particle diameter is considered to be in the range of 1 to 1000 μm.

The refractive index n _{D of the} glass flakes obtained in Examples 10 to 18 was measured. As the refractive index of the glass flakes, the refractive index n _D of yellow sodium D-line (light wavelength 589.3 nm) was determined by the immersion method. The results are shown in Table 3.

  Each of these scaly glasses (glass fillers) was blended with a polycarbonate resin to prepare a polycarbonate resin composition. As a result, the scaly glass had good dispersibility, and a good polycarbonate resin composition was obtained. The content of the glass flakes in the polycarbonate resin composition was 30% by mass.

From the results shown in Table 3, the refractive index (n _D ) of Examples 10 to 18 is in the range of 1.581 to 1.589, and is close to the refractive index of the polycarbonate resin (n _D : 1.585). Indicated.

(Examples 19 to 27)
In Examples 19 to 27, chopped strands that can be used as glass fillers were produced using the glass compositions (bulk) obtained in Examples 1 to 9, respectively. That is, the glass composition (bulk) was remelted in an electric furnace and then formed into pellets while cooling. This glass pellet was put into the production apparatus shown in FIGS. 3 and 4 to produce a chopped strand having an average fiber diameter of 10 to 20 μm and a length of 3 mm.

  Each of these chopped strands was blended with a polycarbonate resin to prepare a polycarbonate resin composition. As a result, the chopped strands were excellent in dispersibility and a good polycarbonate resin composition was obtained. The content of chopped strands in the polycarbonate resin composition was 30% by mass.

  If the glass composition of this invention is mix | blended with polycarbonate resin, the polycarbonate resin composition which can be used conveniently for the housing | casing of an electric equipment, a motor vehicle part, a building material, etc. can be comprised.

DESCRIPTION OF SYMBOLS 10 Scale glass 11 Glass base 12 Refractory kiln 13 Blow nozzle 14 Hollow glass film 15 Press roll 20 Bushing 21 Glass filament 22 Binder applicator 23 Application roller 24 Binder 25 Reinforcement pad 26 Strand 27 Traverse finger 28 Collet 29 Cylindrical tube 30 Cake 31 Crill 32 Converging guide 33 Strand bundle 34 Spraying device 35 Cutting device 36 Rotary blade 37 Chopped strand

Claims (14)

Expressed in mass%,
45 ≦ SiO ₂ ≦ 65,
0.5 ≦ B ₂ O ₃ <2,
5 ≦ Al ₂ O ₃ ≦ 15,
5 ≦ CaO ≦ 25,
0.1 ≦ MgO ≦ 10,
7 <TiO ₂ ≦ 12,
0 ≦ (Li ₂ O + Na ₂ O + K ₂ O) <2,
A glass composition containing the following components:
The refractive index n _d of the glass composition is 1.575 to 1.595,
The glass composition whose Abbe number (nu) _d of the said glass composition is 45-49. Expressed in mass%,
45 ≦ SiO ₂ ≦ 65,
0.5 ≦ B ₂ O ₃ <2,
5 ≦ Al ₂ O ₃ ≦ 15,
5 ≦ CaO ≦ 25,
0.1 ≦ MgO ≦ 10,
7 <TiO ₂ ≦ 12,
0 ≦ (Li ₂ O + Na ₂ O + K ₂ O) <2,
A glass composition containing the following components:
A glass composition substantially free of ZnO and F. Expressed in mass%,
45 ≦ SiO ₂ ≦ 65,
0.5 ≦ B ₂ O ₃ <2,
5 ≦ Al ₂ O ₃ ≦ 15,
5 ≦ CaO ≦ 25,
0.1 ≦ MgO ≦ 10,
7 <TiO ₂ ≦ 12,
0 ≦ (Li ₂ O + Na ₂ O + K ₂ O) <2,
A glass composition containing the following components:
The glass composition whose working temperature of the said glass composition is 1100-1300 degreeC. Expressed in mass%,
45 ≦ SiO ₂ ≦ 65,
0.5 ≦ B ₂ O ₃ <2,
5 ≦ Al ₂ O ₃ ≦ 15,
5 ≦ CaO ≦ 25,
0.1 ≦ MgO ≦ 10,
7 <TiO ₂ ≦ 12,
0 ≦ (Li ₂ O + Na ₂ O + K ₂ O) <2,
A glass composition containing the following components:
The glass composition whose temperature difference (DELTA) T which deducted devitrification temperature from the working temperature of the said glass composition is 0-150 degreeC. The refractive index n _d of the glass composition is 1.585 to 1.592,
The glass composition as described in any one of Claims 1-4 whose Abbe number (nu) _d of the said glass composition is 47-49. Expressed in mass%,
0.5 ≦ B ₂ O ₃ <1.8,
The glass composition as described in any one of Claims 1-5 containing the component of these. Expressed in mass%,
7 <TiO ₂ ≦ 9,
The glass composition as described in any one of Claims 1-6 containing the component of these. Expressed in mass%,
0 ≦ ZrO ₂ ≦ 1,
The glass composition as described in any one of Claims 1-7 containing these components. Not containing ZrO ₂ substantially glass composition according to claim 8.   The glass composition as described in any one of Claims 1-9 which does not contain BaO substantially. ZrO _2, BaO, substantially free of ZnO and F, the glass composition according to any one of claims 1 to 10. Expressed in mass%,
45 ≦ SiO ₂ ≦ 65,
0.5 ≦ B ₂ O ₃ <2,
5 ≦ Al ₂ O ₃ ≦ 15,
5 ≦ CaO ≦ 25,
0.1 ≦ MgO ≦ 10,
7 <TiO ₂ ≦ 12,
0 ≦ (Li ₂ O + Na ₂ O + K ₂ O) <2,
The glass filler for polycarbonate resins which consists of a glass composition containing these components, or consists of a glass composition as described in any one of Claims 1-11.   The glass filler for polycarbonate resin according to claim 12, which is at least one selected from scale-like glass, chopped strands, milled fiber, glass powder, and glass beads. The polycarbonate resin composition containing a polycarbonate resin and the glass filler for polycarbonate resins of Claim 12 or 13.

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