JP4666459B2 - Polycarbonate resin composition and molded article using the same - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded article having a hue excellent in mechanical strength and transparency and having a good design.

  The polycarbonate resin molded article is transparent and excellent in mechanical strength such as heat resistance and impact resistance, and is widely used as an industrial transparent material in the electrical, mechanical and automotive fields. Moreover, it is used also for a lens, an optical disc, etc. as a plastic for optical materials.

  However, although the polycarbonate resin molded product is excellent in mechanical strength, it is lower than glass and ceramics. Therefore, when mechanical strength is required, a glass filler or the like is added for reinforcement.

  As such a glass filler, a glass fiber conventionally called E glass is mainly used, but the refractive index of the polycarbonate resin (refractive index in sodium D line: nD) is 1.580 to 1.590. On the other hand, since the refractive index of E glass is about 1.555, the polycarbonate resin molded product reinforced with E glass has a problem that transparency is lowered due to the difference in refractive index between the two.

  On the other hand, by changing the composition of the glass filler, the refractive index of the glass filler is brought close to the refractive index of the polycarbonate resin or substantially the same refractive index, thereby maintaining the transparency of the polycarbonate resin molded product. To be considered.

For example, in the following Patent Document 1, in terms of mass%, SiO ₂ is 50 to 65%, Al ₂ O ₃ is 0 to 6%, MgO is 0 to 5%, CaO is 3 to 10%, and BaO is 2 to 2. 10%, ZnO 0-7%, SrO 0-5%, Na ₂ O 3-8%, K ₂ O 3-8%, LiO 0-5%, ZrO ₂ 3-10%, A composition for reinforced glass fibers of polycarbonate resin, comprising TiO ₂ of 5.3 to 10%, is disclosed.

Further, in Patent Document 2 below, in terms of mass%, SiO ₂ : 54.0 to 62.0%, Al ₂ O ₃ : 8.0 to 12.0%, MgO: 0 to 5.0%, CaO : 18.0~22.0%, BaO: 0~5.0% , ZnO: 0~5.0%, Na 2 O + K 2 O + Li 2 O: 0~1.0%, ZrO 2: 0.6~ A glass composition comprising 5.0%, TiO ₂ : 0.5 to 1.9%, having a refractive index of 1.5700 to 1.6000 and used for reinforcing a polycarbonate resin is disclosed.

  In addition, it has been studied to improve a polycarbonate resin by using commercially available glass fibers. For example, in Patent Document 3 below, an aromatic using a reaction product of hydroxyaralkyl alcohol and lactone as a terminal terminator is disclosed. A resin composition containing a polycarbonate resin and a glass filler having a refractive index difference of 0.01 or less between the aromatic polycarbonate resin is disclosed.

  Patent Document 4 listed below discloses a resin composition comprising an aromatic polycarbonate resin, a glass fiber having a refractive index difference of 0.015 or less, and polycaprolactone.

On the other hand, a polycarbonate resin molded product having a hue like an interference color is also known. For example, in Patent Document 5 below, a resin added with glass flakes coated with a metal oxide containing titanium oxide, Ca, and Mg is disclosed. A molded article is disclosed.
JP 58-60641 A JP-A-5-155638 JP-A-7-118514 JP-A-9-165506 JP-A-10-279828

  The polycarbonate resin molded article using the glass compositions of Patent Documents 1 and 2 can be excellent in transparency and mechanical properties, but has not been devised in terms of design properties.

In addition, in the aromatic polycarbonate resin composition of Patent Document 3 and the aromatic polycarbonate resin composition of Patent Document 4, although transparency is improved, there is nothing regarding the design in a molded article using these compositions. There was no ingenuity.
Since it contains polycaprolactone, there is a problem that the heat resistance and mechanical properties of the molded product are likely to be lowered.

  On the other hand, as in Patent Document 5, by using a glass filler coated with a metal layer, a polycarbonate resin molded product having a hue like an interference color can be obtained, but the operation of coating the glass filler with the metal layer Since such a glass filler tends to be expensive, the resulting molded product becomes expensive. Moreover, it was difficult to maintain sufficient transparency.

  An object of the present invention is to provide a polycarbonate resin molded article having a hue excellent in mechanical strength and transparency and rich in design of interference color tone.

  In order to achieve the above object, the polycarbonate resin composition of the present invention is a polycarbonate resin molded product containing a polycarbonate resin and a glass filler, wherein the difference in refractive index between the glass filler and the polycarbonate resin is light having a wavelength of 486 nm. 0.004 to 0.015 with respect to the light with a wavelength of 589 nm, 0.002 or less with respect to the light with a wavelength of 656 nm, and the glass filler content is 2 to 40 mass% And the total light transmittance is 75% or more and the haze is 35% or less when the molded product is formed into a flat plate shape.

Further, in the present invention, the glass filler is silicon dioxide _(SiO 2) 50-60 wt%, aluminum oxide _{(Al 2} O 3) _10~15 wt%, calcium oxide (CaO) 15-25 wt% of titanium oxide (TiO ₂ ) 2 to 10% by mass, boron oxide (B ₂ O ₃ ) 2 to 8% by mass, magnesium oxide (MgO) 0 to 5% by mass, zinc oxide (ZnO) 0 to 5% by mass, barium oxide (BaO) ) 0-5% by weight, zirconium oxide _(ZrO 2) 0-5 mass% of lithium oxide _(Li 2 O) 0 to 2 wt%, sodium oxide _(Na 2 O) 0 to 2 wt%, potassium oxide _{(K 2} O) 0 to 2% by mass, and the total of the lithium oxide (Li ₂ O), the sodium oxide (Na ₂ O), and the potassium oxide (K ₂ O) is 0 to 2% by mass. composition Or silicon dioxide _(SiO 2) 50-60 wt%, aluminum oxide _{(Al 2} O 3) _10~15 wt%, calcium oxide (CaO) 15-25 wt%, titanium oxide _(TiO 2) 2 to 5 wt% , Magnesium oxide (MgO) 0-5 mass%, zinc oxide (ZnO) 0-5 mass%, barium oxide (BaO) 0-5 mass%, zirconium oxide (ZrO ₂ ) 2-5 mass%, lithium oxide (Li ₂ O) 0 to 2% by mass, sodium oxide (Na ₂ O) 0 to 2% by mass, potassium oxide (K ₂ O) 0 to 2% by mass, and substantially containing boron oxide (B ₂ O ₃ ) does not contain, and it is preferable that the a composition sum of the potassium oxide and lithium oxide _(Li 2 O) wherein the sodium oxide _{(Na 2 O) (K 2} O) is 0 to 2 wt%.

And the polycarbonate resin composition of this invention shape | molds this resin composition in a 2 mm-thick flat plate, and fluctuates the light reception angle (beta) of the variable angle color difference meter at the time of transmitted light in the range of -20 degrees-20 degrees. When the measured hue (L ^* a ^* b ^* ) is β = 0 °, the a ^* value is smaller than 0 and the b ^* value is larger than 0, and 0 ° <β ≦ 20 ° and − When 20 ° ≦ β <0 °, the a ^* value is preferably larger than 0 and the b ^* value is preferably smaller than 0.

  On the other hand, the polycarbonate resin molded product of the present invention is obtained by molding the polycarbonate resin composition.

  The polycarbonate resin molded article using the polycarbonate resin composition of the present invention has a hue excellent in mechanical strength and transparency and having a rich design of interference color, for example, display of electrical equipment and electronic equipment. It can be suitably used as a molded product that requires transparency and design, such as a cover of a part.

  The polycarbonate resin composition of the present invention contains a glass filler and a polycarbonate resin. The difference between the refractive index of the polycarbonate resin and the refractive index of the glass filler is 0.004 to 0.015 for light with a wavelength of 486 nm, 0.002 or less for light with a wavelength of 589 nm, and for light with a wavelength of 656 nm. The difference between the refractive index of the polycarbonate resin and the refractive index of the glass filler for light with a wavelength of 486 nm is preferably 0.004 to 0.010, more preferably 0. 0.005 to 0.010. The difference between the refractive index of the polycarbonate resin and the refractive index of the glass filler with respect to light having a wavelength of 589 nm is preferably 0.001 or less. The difference between the refractive index of the polycarbonate resin and the refractive index of the glass filler with respect to light having a wavelength of 656 nm is preferably 0.001 or less.

  When the difference in refractive index between the glass filler and the polycarbonate resin is larger than 0.002 with respect to the wavelength of light having a wavelength of 589 nm or the wavelength of light having a wavelength of 656 nm, the transparency of the molded product tends to be insufficient. is there. Further, when the difference in refractive index between the glass filler and the polycarbonate resin is smaller than 0.004 with respect to light having a wavelength of 486 nm, a transparent molded product can be obtained, but the hue of interference color tone is provided. If it exceeds 0.015, the transparency of the molded product tends to be insufficient.

  By setting the difference in refractive index between the glass filler and the polycarbonate resin within the above range, it is possible to provide an interference hue while maintaining sufficient transparency.

  Here, the hue of the interference color tone in the present invention is a hue that slightly changes due to the interference color effect of light, and indicates polychromaticity that changes depending on the observation angle.

One preferable example of the glass filler that can be used in the polycarbonate resin composition of the present invention is 50 to 60% by mass of silicon dioxide (SiO ₂ ), 10 to 15% by mass of aluminum oxide (Al ₂ O ₃ ), calcium oxide ( CaO) 15-25% by mass, titanium oxide (TiO ₂ ) 2-10% by mass, boron oxide (B ₂ O ₃ ) 2-8% by mass, magnesium oxide (MgO) 0-5% by mass, zinc oxide (ZnO) 0-5 wt%, barium oxide (BaO) 0-5% by weight, zirconium oxide _(ZrO 2) 0-5 wt%, ₍₂ O Li) 0~2 wt% of lithium oxide, sodium oxide _(Na 2 O) 0 to 2% by weight, containing 0-2 wt% of potassium oxide _(K 2 O), and wherein said oxide lithium oxide _(Li 2 O) and the and the sodium oxide _(Na 2 O) potassium The sum of _(K 2 O) is made of the composition is 0-2% by weight.

Also preferred another example of the glass filler used in the present invention, silicon _(SiO 2) 50-60% by weight dioxide, aluminum oxide _{(Al 2} O 3) _10~15 wt%, calcium oxide (CaO) 15-25 mass%, titanium oxide _(TiO 2) 2 to 5 wt%, magnesium oxide (MgO) 0-5% by weight, 0 to 5 wt% of zinc oxide (ZnO), barium oxide (BaO) 0-5% by weight, zirconium oxide (ZrO ₂ ) 2 to 5% by mass, lithium oxide (Li ₂ O) 0 to 2% by mass, sodium oxide (Na ₂ O) 0 to 2% by mass, potassium oxide (K ₂ O) 0 to 2% by mass However, boron oxide (B ₂ O ₃ ) is not substantially contained, and the total of the lithium oxide (Li ₂ O), the sodium oxide (Na ₂ O), and the potassium oxide (K ₂ O) is 0 It consists composition is 2% by mass.

In the composition of the glass filler, silicon dioxide (SiO ₂ ) is preferably 50 to 60% by mass. If the SiO ₂ content is less than 50% by mass, the strength of the glass filler may be reduced, and if it exceeds 60% by mass, the solubility as glass may be reduced.

Aluminum oxide _(Al 2 _{O 3)} is preferably 10 to 15 wt%. If Al ₂ O ₃ is less than 10% by mass, chemical durability such as water resistance may be lowered, and if it exceeds 15% by mass, solubility is lowered and the resulting glass filler is inhomogeneous. It becomes easy to become.

The content of boron oxide (B ₂ O ₃ ) is preferably 2 to 8% by mass or substantially not contained. That is, the present invention can also be applied to a case where 2 to 8% of B ₂ O ₃ is contained as in the standard E glass. In this case, if the content of B ₂ O ₃ exceeds 8%, the strength as a glass filler may be reduced. Also applicable to a case that does not substantially contain B ₂ O ₃ as ECR glass composition, which is excellent in acid resistance and alkali resistance. In the present invention, “substantially not containing B ₂ O _3” means that the content of B ₂ O ₃ is 0.1% by mass or less.

  Calcium oxide (CaO) is preferably 15 to 25% by mass. If the CaO content is less than 15% by mass, the glass solubility may be reduced. If the CaO content exceeds 25% by mass, crystallization is likely to occur and transparency may be reduced.

  Magnesium oxide (MgO) is an optional component and can be contained in an amount of 0 to 5% by mass. By containing MgO, a part of Ca in the above CaO can be replaced with Mg, and durability such as tensile strength can be improved. If the content of MgO exceeds 5% by mass, the solubility as glass may be reduced.

When 2 to 8% by mass of boron oxide (B ₂ O ₃ ) is contained, the content of titanium oxide (TiO ₂ ) is preferably 2 to 10% by mass. By setting the content in this range, the refractive index can be sufficiently improved even if the alkali component described later is 1% or less. If the TiO ₂ content is less than 2% by mass, the refractive index is not sufficiently improved, and if it exceeds 10% by mass, the glass tends to be devitrified and the strength of the glass filler may be reduced. Further, the glass filler tends to yellow. The content of TiO ₂ is preferably 8% by mass or less, more preferably 6% by mass or less, because it suppresses the yellowness of the glass filler.

When B ₂ O ₃ is not substantially contained, TiO ₂ is preferably ₂ to 5%. This is because B ₂ O ₃ is a component that lowers the refractive index, and the content of TiO ₂ , which is a component that raises the refractive index, can be reduced. If TiO ₂ is less than 2%, it is insufficient to increase the refractive index. Moreover, when it exceeds 5 mass%, a refractive index will rise too much and the difference with the refractive index of polycarbonate resin will become large.

Zinc oxide (ZnO), barium oxide (BaO), and zirconium oxide (ZrO ₂ ) are also optional components and can be contained in amounts of 0 to 5% by mass, respectively.

  By containing ZnO and BaO, the refractive index can be increased and devitrification can be suppressed. When each content exceeds 5 mass%, liquidus temperature will rise and it will become easy to devitrify.

ZrO ₂ can also be contained in an amount of 0 to 5% by mass. When B ₂ O ₃ is not substantially contained, it is preferably contained in an amount of 2 to 5% by mass. By containing ZrO ₂ , the refractive index can be increased and chemical durability can be improved. When content exceeds 5 mass%, the solubility as glass will fall and it will become easy to devitrify.

_{Incidentally,} if it contains B 2 _{O 3} 2 to 8% by weight, preferably the sum of ZnO and BaO and ZrO ₂ described above, a 0-5 wt% based on the entire glass filler, 2-5 More preferably, it is mass%. _Further, when not containing B 2 _{O 3} substantially is the sum of ZnO and BaO and ZrO ₂ described above, is preferably 2 to 5 wt% based on the entire glass filler. Since these components contain heavy elements such as Zn, Ba, and Zr, if the total exceeds 5 mass%, the specific gravity of the glass increases and the weight of the molded article increases.

Lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), and potassium oxide (K ₂ O), which are alkali components, can each be contained in an amount of 0 to 2% by mass, and the total of these can be based on the entire glass filler. It is preferable that it is 0-2 mass% or less.

  When the total content of the alkali components exceeds 2% by mass, the water resistance of the glass is lowered, and the alkali is easily eluted. And the molecular weight of polycarbonate resin may fall with the eluted alkaline component, and it becomes a factor of the physical-property fall of a molded article.

Thus, even if the content of the alkali component is low, when 2 to 8% by mass of B ₂ O ₃ is contained as described above, ₂ to 10% by mass of TiO ₂ is contained, and B ₂ O ₃ In the present invention, the refractive index can be sufficiently improved by containing ₂ to 5% by mass of TiO ₂ . And by reducing an alkali component, the molecular weight fall by decomposition | disassembly of polycarbonate resin can be prevented, and physical property fall, such as the intensity | strength of a molded article, can be prevented.

  And the glass filler which can be used for this invention may further contain the following component in the range which does not exert a bad influence on the moldability, water resistance, etc. of the glass filler which consists of said composition. For example, as a component for increasing the refractive index of the glass filler, lanthanum (La), Y (yttrium), gadolinium (Gd), bismuth (Bi), antimony (Sb), tantalum (Ta), niobium (Nb) or tungsten (W An oxide containing an element such as) may be contained. Moreover, you may contain the oxide containing elements, such as cobalt (Co), copper (Cu), or neodymium (Nd), as a component which discolors yellow of glass.

Further, the glass raw material required to obtain a glass filler, since suppressing the coloration, as impurities in the raw material, Fe ₂ O ₃ content of an oxide basis is less than 0.01 wt% based on the entire glass It is preferable that

  In the present invention, the glass filler can be used in various forms such as glass fiber, glass powder, glass flake, milled fiber, or glass bead, but is preferably used as glass fiber from the viewpoint of the reinforcing effect.

  The glass fiber can be obtained by using a conventionally known method for spinning long glass fibers. For example, the glass raw material is continuously vitrified in a melting furnace and guided to the forehearth, and the direct melting (DM) method in which a bushing is attached to the bottom of the forehearth for spinning, or the molten glass is processed into a marble, cullet, or rod shape. The glass can be made into fiber using various methods such as a remelting method in which it is remelted and spun. The average diameter of the glass fiber is not particularly limited, but a glass fiber having a diameter of 3 to 25 μm is preferably used. If it is thinner than 3 μm, the contact area between the glass fiber and the resin increases, causing irregular reflection, and the transparency of the molded product may decrease. When it is thicker than 25 μm, the strength of the glass fiber becomes weak, and as a result, the strength of the molded product may be lowered.

  Glass powder is obtained by a conventionally known production method. For example, a glass raw material is melted in a melting furnace, the melt is poured into water and crushed, or formed into a sheet shape with a cooling roll, and the sheet is pulverized. Can be. Although the particle size of glass powder is not specifically limited, A thing of 1-100 micrometers is used preferably.

  Glass flakes are obtained by a conventionally known production method. For example, a glass raw material is melted in a melting furnace, the melt is drawn into a tube shape, the glass film thickness is made constant, and then crushed with a roll to obtain a frit having a specific film thickness. It can be ground into flakes having the desired aspect ratio. The thickness and aspect ratio of the glass flake are not particularly limited, but those having a thickness of 0.1 to 10 μm and an aspect ratio of 5 to 150 are preferably used.

  The milled fiber can be obtained using a conventionally known milled fiber manufacturing method. For example, a glass fiber strand can be made into a milled fiber by pulverizing with a hammer mill or a ball mill. The fiber diameter and aspect ratio of the milled fiber are not particularly limited, but those having a fiber diameter of 3 to 25 μm and an aspect ratio of 2 to 150 are preferably used.

  Glass beads are obtained by a conventionally known production method. For example, a glass raw material can be melted in a melting furnace, and the melt can be sprayed with a burner to form glass beads having a desired particle size. The particle size of the glass beads is not particularly limited, but those having 5 to 300 μm are preferably used.

  Then, in order to increase the affinity between the polycarbonate resin and the glass filler, increase the adhesion, and suppress the decrease in transparency of the molded product due to void formation, the glass filler is surface-treated with a treatment agent containing a coupling agent. It is preferable.

  As the coupling agent, a silane coupling agent, a borane coupling agent, an aluminate coupling agent, a titanate coupling agent, or the like can be used. In particular, it is preferable to use a silane coupling agent from the viewpoint of good adhesion between the polycarbonate resin and glass. As the silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, an acrylic silane coupling agent, or the like can be used. Of these silane coupling agents, aminosilane coupling agents are most preferably used.

  Examples of components other than the coupling agent contained in the treatment agent include a film former, a lubricant, and an antistatic agent. These may be used alone or in combination with a plurality of components. As the film former, polymers such as vinyl acetate resin, urethane resin, acrylic resin, polyester resin, polyether resin, phenoxy resin, polyamide resin, epoxy resin or polyolefin resin, or modified products thereof can be used. . As the lubricant, aliphatic ester-based, aliphatic ether-based, aromatic ester-based or aromatic ether-based surfactants can be used. As the antistatic agent, inorganic salts such as lithium chloride and potassium iodide or quaternary ammonium salts such as ammonium chloride type and ammonium ethosulphate type can be used.

  The polycarbonate resin that can be used in the present invention is not particularly limited, and for example, those obtained by reacting bisphenol A and phosgene can be used. The viscosity average molecular weight is preferably 12000 to 35000.

  And it is essential that content of the glass filler contained in polycarbonate resin is 2-40 mass%, Preferably it is 5-35 mass%, More preferably, it is 10-30 mass%. If the content is less than 2% by mass, the effect of improving the mechanical properties cannot be sufficiently obtained. If the content exceeds 40% by mass, the contact interface between the resin and the glass is increased and the transparency of the molded product is lowered. It will decline. By setting the amount of the glass filler contained in the polycarbonate resin composition within the above range, a molded article having a hue of interference color tone having both high transparency and good mechanical properties can be obtained.

  Furthermore, a well-known additive can be used for the polycarbonate resin composition of this invention in the range which does not impair characteristics, such as refractive index. For example, the antioxidant can suppress the decomposition of the resin at the time of production or molding of the polycarbonate resin composition.

  The polycarbonate resin composition of the present invention can be produced using a conventionally known method. For example, the method of mixing the said polycarbonate resin, the said glass filler, and arbitrary additives using a mixer etc., melt-kneading with an extruder, and pelletizing can be used preferably.

  The method for producing a polycarbonate resin molded product of the present invention can be obtained by molding a polycarbonate resin composition by a conventionally known molding method, for example, injection molding, extrusion molding, compression molding, calendar molding, or the like. Moreover, you may shape | mold using the metal mold | die with which the inside was covered with the resin film or the resin sheet.

  In that case, the thickness of the molded product can be arbitrarily set according to the application, and in particular when the transparency of the molded product is required, 0.5 to 4.0 mm is preferable. If the thickness of the molded product is less than 0.5 mm, warpage is likely to occur, and the mechanical strength is low. Moreover, when larger than 4.0 mm, transparency will be impaired.

  The molded article is preferably provided with a hard coat film, an antifogging film, an antistatic film, or an antireflection film, and may be a composite film of two or more types.

  Among them, it is particularly preferable that a hard coat film is formed since weather resistance is good and wear of the surface of the molded article over time can be prevented. The material of the hard coat film is not particularly limited, and known materials such as an acrylate hard coat agent, a silicone hard coat agent, and an inorganic hard coat agent can be used.

  The production conditions of the polycarbonate resin composition and the molding conditions of the polycarbonate resin molded product can be appropriately selected and are not particularly limited, but the heating temperature during melt-kneading and the resin temperature during injection molding are the decomposition of the resin. Therefore, it is usually preferable to select appropriately from the range of 220 ° C to 300 ° C.

  When at least a part of the glass filler is present on the outermost surface of the molded product, the surface roughness of the molded product increases, and irregular reflection on the surface of the molded product increases, resulting in deterioration of the transparency of the molded product. is there. For this reason, as a method of reducing the surface roughness of the molded product, there is a method of reducing the surface roughness of the molded product by forming a layer (skin layer) having a high resin content ratio on the outermost surface of the molded product. is there. As a method for forming this skin layer, in the case of injection molding, the temperature of the mold is set to a temperature higher than general conditions, so that the resin in contact with the mold can easily flow, and the outermost surface of the molded product The surface roughness can be reduced. In the case of press molding, the surface roughness of the outermost surface of the molded product can be reduced by setting the pressure during molding to a pressure higher than the general conditions. By reducing the surface roughness of the molded product using the above-described method, irregular reflection on the surface of the molded product is reduced, haze is reduced, and as a result, the transparency of the molded product can be improved.

  And when the polycarbonate resin molded product obtained in this way is formed into a flat plate, it is necessary that the total light transmittance for visible light is 75% or more and the haze is 35% or less. The total light transmittance is preferably 80% or more, particularly preferably 83% or more. The haze is preferably 30% or less, and particularly preferably 25% or less. Since the polycarbonate resin molded article having the optical properties is excellent in transparency, it can be used in applications requiring high transparency. In addition, the total light transmittance with respect to visible light can be measured according to JIS-K7361, and haze can be measured according to JIS-K7105.

Further, when the polycarbonate resin molded product was molded into a flat plate having a thickness of 2 mm, the hue (L ^*) measured by varying the light receiving angle β of the variable angle color difference meter during transmitted light in the range of −20 ° to 20 ° ^. a ^* b ^*) is small and ^{b *} value than the ^{a *} value is 0 when the beta = 0 ° is larger than 0, 0 ° <β ≦ 20 ° and -20 ° ≦ β <0 The a ^* value at 0 ° is preferably larger than 0 and the b ^* value is preferably smaller than 0.

The a ^* value when β = 0 ° is more preferably smaller than −5, and even more preferably smaller than −10. Further, the b ^* value is more preferably greater than 5 and even more preferably greater than 10.

The a ^* value when 0 ° <β ≦ 20 ° and −20 ° ≦ β <0 ° is more preferably greater than 0.05, and even more preferably greater than 0.1. Further, the b ^* value is more preferably less than -0.05, and even more preferably a value less than -0.1.

  Here, the goniochromimeter is a device that measures the transmission / reflection distribution of the sample due to the change in the angle between the projector and the receiver. For example, an object such as mica paint that changes its color when the viewing direction changes. It is used to measure the optical properties of In general, the projection angle α of the projector can be arbitrarily selected within a range of 0 to 80 °.

  The polycarbonate resin molded product of the present invention is a member that requires transparency and design, for example, 1) a television, a radio cassette, a video camera, a video tape recorder, an audio player, a DVD player, a telephone, a display, Various parts for computers, registers, copiers, printers, facsimiles, etc., parts for outer panels and housings, etc. 2) Mobile phones, PDAs, cameras, slide projectors, clocks, calculators, measuring instruments, display devices It can be suitably used for precision machine parts such as cases and covers such as precision machines such as.

  Hereinafter, the present invention will be described in more detail with reference to examples.

[Manufacture of glass fiber]
Glass fibers of Production Examples 1 to 4 were produced with the composition (% by mass) shown in Table 1.

  The glass fiber was spun at a fiber diameter of 15 μm by a conventionally known method, and aminosilane + urethane was adhered as a binder to 0.5 mass%. Table 1 shows the refractive index (nF) of the glass fiber with respect to light with a wavelength of 486 nm, the refractive index with respect to light with a wavelength of 589 nm (nD), the refractive index with respect to light with a wavelength of 656 nm (nC), and the specific gravity. Here, the refractive index of the glass fiber is a value obtained by measuring the test piece by the immersion method according to the method B of JIS-K7142, and the specific gravity is a value measured by the Archimedes method.

[Manufacture of glass fiber reinforced polycarbonate resin molded products]
The glass fibers of Production Examples 1 to 4 were compounded under the following conditions to produce glass fiber reinforced polycarbonate resin molded products of Examples 1 to 6 and Comparative Examples 1 to 4.

(Compound conditions)
Polycarbonate resin: Lexan 121R (manufactured by Nippon GE Plastics, molecular weight 21000, nD = 1.585)
Glass fiber: 15 [mu] m diameter, 3 mm long chopped strand, 400 bundled extruder: TEM-35B (manufactured by Toshiba Machine Co., Ltd.)
Extrusion temperature: 280 ° C

(Injection conditions)
Molding machine: IS-80G (Toshiba Machine Co., Ltd.)
Cylinder temperature: 300 ° C
Mold temperature: 120 ° C

  The physical properties of the polycarbonate resin molded product are summarized in Table 2. Here, the total light transmittance, which is an optical property of the molded product, is a value obtained by measuring a sample having a thickness of 2 mm according to JIS-K7361 using an NDH sensor manufactured by Nippon Denshoku Co., Ltd. It is the value which measured the sample of thickness 2mm according to JIS-K7105 method a using the NDH sensor by Color Co., Ltd. Moreover, the bending strength and bending elasticity which are mechanical physical properties are values measured using a sample having a thickness of 3 mm in accordance with ASTM D-790, respectively.

Further, using the polycarbonate resin molded products of Examples 2, 4, 5, 6 and Comparative Examples 2 and 4, a 2 mm-thick flat plate sample was fixed at a projection angle α of transmitted light at 0 °, The hue (L ^* a ^* b ^* ) was measured by changing the light receiving angle β in the range of −20 ° to 20 °. Table 3 shows the a ^* value and b ^* value measured at each light receiving angle. Here, a variable angle color difference meter (trade name; “GC 5000”) manufactured by Nippon Denshoku Co., Ltd. was used to measure the hue of the molded product.

  From the results of Table 2, it can be seen that the molded articles of the examples have mechanical properties comparable to or higher than those of the comparative examples, and the haze is lower than that of the comparative examples, and the transparency is excellent. Moreover, it can be seen from the results in Table 3 that the molded products of the examples change in hue depending on the observation angle.

  The polycarbonate resin molded product of the present invention can be suitably used for parts that require mechanical strength, transparency and design, for example, a cover of a display unit of an electric device or an electronic device.

Claims (4)

In a polycarbonate resin composition containing a polycarbonate resin and a glass filler,
The glass filler is 50 to 60% by mass of silicon dioxide (SiO ₂ ), 10 to 15% by mass of aluminum oxide (Al ₂ O ₃ ), 15 to 25% by mass of calcium oxide (CaO), and _{2 to} 2 of titanium oxide (TiO ₂ ). 10 _{wt%, (2 O 3 B)} 2~8 wt% boron oxide, magnesium oxide (MgO) 0-5% by weight, 0 to 5 wt% of zinc oxide (ZnO), barium oxide (BaO) 0-5% by weight , Zirconium oxide (ZrO ₂ ) 0 to 5% by mass, lithium oxide (Li ₂ O) 0 to 2% by mass, sodium oxide (Na ₂ O) 0 to 2% by mass, potassium oxide (K ₂ O) 0 to ₂ % by mass And the total amount of the lithium oxide (Li ₂ O), the sodium oxide (Na ₂ O), and the potassium oxide (K ₂ O) is 0 to 2% by mass,
The difference in refractive index between the glass filler and the polycarbonate resin is 0.004 to 0.015 for light with a wavelength of 486 nm, 0.002 or less for light with a wavelength of 589 nm, and 0 for light with a wavelength of 656 nm. .002 or less,
The content of the glass filler is 2 to 40% by mass,
A polycarbonate resin composition characterized by having a total light transmittance of 75% or more and a haze of 35% or less when the composition is formed into a flat plate shape. In a polycarbonate resin composition containing a polycarbonate resin and a glass filler,
  The glass filler is silicon dioxide (SiO 2 ₂ ) 50-60% by mass, aluminum oxide (Al ₂ O ₃ ) 10-15 mass%, calcium oxide (CaO) 15-25 mass%, titanium oxide (TiO ₂ ) 2-5% by mass, magnesium oxide (MgO) 0-5% by mass, zinc oxide (ZnO) 0-5% by mass, barium oxide (BaO) 0-5% by mass, zirconium oxide (ZrO) ₂ ) 2-5% by mass, lithium oxide (Li ₂ O) 0-2% by mass, sodium oxide (Na ₂ O) 0-2% by mass, potassium oxide (K ₂ O) 0 to 2% by mass, boron oxide (B ₂ O ₃ ) And the lithium oxide (Li ₂ O) and sodium oxide (Na ₂ O) and potassium oxide (K) ₂ O) and the total amount is 0 to 2% by mass,
  The difference in refractive index between the glass filler and the polycarbonate resin is 0.004 to 0.015 for light with a wavelength of 486 nm, 0.002 or less for light with a wavelength of 589 nm, and 0 for light with a wavelength of 656 nm. .002 or less,
  The content of the glass filler is 2 to 40% by mass,
  A polycarbonate resin composition characterized by having a total light transmittance of 75% or more and a haze of 35% or less when the composition is formed into a flat plate shape. Hue (L ^* a ^* b ^*) measured when the polycarbonate resin composition was molded into a flat plate having a thickness of 2 mm, and the light receiving angle β of the variable angle color difference meter during transmitted light was varied in the range of −20 ° to 20 ° ^. ) is small and b ^* value than the a ^* value is 0 when the beta = 0 ° is larger than 0, 0 ° <beta ≦ 20 ° and -20 ° ≦ beta <0 when the ° The polycarbonate resin composition according to claim 1 or 2 , wherein the a ^* value is larger than 0 and the b ^* value is smaller than 0. The polycarbonate resin molded product shape | molded using the polycarbonate resin composition in any one of Claims 1-3 .