Polycarbonate resin composition

Abstract

To provide a polycarbonate resin composition having extremely excellent transparency, and capable of being easily provided, a molded body of the same, and a method for producing the same.SOLUTION: A polycarbonate resin composition includes a glass filler (A), and a polycarbonate resin constituent (B), where the (B) is a polycarbonate resin constituent including two or more of aliphatic polycarbonate copolymers (Bn) including one or more selected from the group consisting of a structural unit (b1) expressed by a specific formula, a structural unit (b2) expressed by a specific formula, and a structural unit (b3) expressed by a specific formula, and the difference of refractive indices to light having a wave length of 589.3 nm of between the glass filler (A) and the polycarbonate resin constituent (B) is 0.0150 or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polycarbonate-based resin composition, a method for producing the polycarbonate-based resin composition, and a molded article thereof.

Background Art

[0002] Molded articles made of polycarbonate-based resins have high transparency and mechanical strengths such as excellent heat resistance and impact resistance. Therefore, they are widely used in the fields of electricity, machinery, automobiles, etc. as industrial transparent materials. They are also used for lenses, optical disks, etc. as plastics for optical materials.

[0003] When higher mechanical strength is required for molded articles made of polycarbonate-based resins, glass fillers or the like can be added to increase the mechanical strength. However, molded articles of polycarbonate-based resin compositions containing general glass fillers have a problem of reduced transparency. In response to this problem, attempts have been made to bring the refractive indices of the polycarbonate-based resin and the glass filler closer by changing the composition of the polycarbonate-based resin, adding additives to the polycarbonate-based resin composition, or changing the composition of the glass filler. Patent Documents 1 and 2 disclose a polycarbonate-based resin composition containing a polycarbonate-based resin having a specific structure and a glass filler having a specific composition. Patent Document 3 discloses a method for producing a polycarbonate-based resin composition by mixing an aliphatic polycarbonate-based resin having a specific structure and a specific aromatic thermoplastic resin under predetermined conditions.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] Although Patent Documents 1 to 3 disclose means for improving the transparency of a molded article, it is necessary to adjust the refractive index of the polycarbonate-based resin for each glass filler. In the disclosure of Patent Documents 1 to 3, it is necessary to manufacture a polycarbonate-based resin with a changed copolymer composition each time for adjusting the refractive index of the polycarbonate-based resin, and the simplicity is insufficient. Also, in the disclosure of Patent Documents 1 to 3, the economic efficiency is insufficient. Furthermore, examination of means for improving transparency by blending other components such as addition of an elastomer for the purpose of improving impact resistance, toughness, etc. is also desired.

[0006] An object of the present invention is to provide a polycarbonate-based resin composition and a molded article thereof that have extremely excellent transparency and can be provided simply, and a manufacturing method thereof, etc.

Means for Solving the Problems

[0007] As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by the following aspects. The present invention includes the following <1> to <17>. <1> A glass filler (A), and a structural unit (b1) represented by the following formula (1), and an aliphatic polycarbonate copolymer (B n ) containing at least one selected from the structural unit (b2) represented by the following formula (2) and the structural unit (b3) represented by the following formula (3), A polycarbonate-based resin composition (1) in which the difference in refractive index between the glass filler (A) and the polycarbonate-based resin component (B) with respect to light having a wavelength of 589.3 nm is 0.0150 or less.

[0008]

Chem.

[0009] <2> The polycarbonate resin component (B) satisfies one or more of the following conditions (i) and (ii), the polycarbonate resin composition (1) according to <1>. (i) The haze value is less than 1.5 at a thickness of 1 mm (ii) It has one glass transition temperature <3> The polycarbonate resin composition (1) according to <1> or <2>, obtained by melt-kneading under conditions that do not promote transesterification reaction. <4> The glass filler (A) is 50% by mass or more and 70% by mass or less of silicon dioxide (SiO2), More than 0% by mass and 25% by mass or less of aluminum oxide (Al2O3), 8% by mass or more and 25% by mass or less of boron oxide (B2O3), More than 0% by mass and 10% by mass or less of magnesium oxide (MgO), More than 0% by mass and 20% by mass or less of calcium oxide (CaO), More than 0% by mass and 5% by mass or less of sodium oxide (Na2O), More than 0% by mass and 5% by mass or less of potassium oxide (K2O), and Contains more than 0% by mass and 10% by mass or less of titanium oxide (TiO2), and The total content of the silicon dioxide (SiO2) and the aluminum oxide (Al2O3) in the glass filler (A) is more than 50% by mass and 90% by mass or less, and the total content of the sodium oxide (Na2O), the potassium oxide (K2O) and lithium oxide (Li2O) is more than 0% by mass and 15% by mass or less, the polycarbonate resin composition (1) according to any one of <1> to <3>. <5> The haze value at a thickness of 1 mm is 15.0 or less, the polycarbonate resin composition (1) according to any one of <1> to <4>. <6> The molded article of the polycarbonate resin composition (1) according to any one of <1> to <5>. <7> The molded article according to <6>, which is a sheet. <8> The method for producing a polycarbonate resin composition (1) according to any one of <1> to <5>, including a step (step A) of mixing the glass filler (A) and the polycarbonate resin component (B). <9> In the step A, the types of the structural unit (b1) represented by the formula (1), the structural unit (b2) represented by the formula (2), and the structural unit (b3) represented by the formula (3), the composition ratio of the structural units, and the blending ratio of two or more of the aliphatic polycarbonate copolymers (B n ) are adjusted so that the difference in refractive index with respect to light having a wavelength of 589.3 nm between the glass filler (A) and the polycarbonate resin component (B) is 0.0150 or less. The method for producing a polycarbonate resin composition (1) according to <8>. <10> A glass cloth (A'), An aliphatic polycarbonate copolymer (B n ) containing one or more selected from the structural unit (b1) represented by the following formula (1), the structural unit (b2) represented by the following formula (2), and the structural unit (b3) represented by the following formula (3), and a polycarbonate resin component layer (B') containing two or more of them are laminated, A laminate in which the difference in refractive index with respect to light having a wavelength of 589.3 nm between the glass cloth (A') and the polycarbonate resin component layer (B') is 0.0150 or less.

[0010]

Chemical formula

[0011] [Chemical formula]

[0012] <13> The glass filler (A) is 50% by mass or more and 70% by mass or less of silicon dioxide (SiO2), More than 0% by mass and 25% by mass or less of aluminum oxide (Al2O3), 8% by mass or more and 25% by mass or less of boron oxide (B2O3), More than 0% by mass and 10% by mass or less of magnesium oxide (MgO), More than 0% by mass and 20% by mass or less of calcium oxide (CaO), More than 0% by mass and 5% by mass or less of sodium oxide (Na2O), More than 0% by mass and 5% by mass or less of potassium oxide (K2O), and More than 0% by mass and 10% by mass or less of titanium oxide (TiO2), and The polycarbonate resin composition (2) according to <12>, wherein the total content of the silicon dioxide (SiO2) and the aluminum oxide (Al2O3) in the glass filler (A) is more than 50% by mass and 90% by mass or less, and the total content of the sodium oxide (Na2O), the potassium oxide (K2O), and lithium oxide (Li2O) is more than 0% by mass and 15% by mass or less. <14> The styrenic elastomer (C) is composed of a hard segment composed of a repetition of structural units derived from a styrenic compound and a soft segment composed of an elastomeric segment, and has an amine-modified end group, the polycarbonate resin composition (2) according to <12> or <13>. <15> The polycarbonate resin composition (2) according to <14>, wherein the styrenic elastomer (C) is a styrene-ethylene-butylene-styrene copolymer having an amine-modified end group. <16> The polycarbonate resin component (B'') is an aliphatic polycarbonate copolymer (B n ) containing at least one selected from the structural unit (b1) represented by the formula (1), and the structural unit (b2) represented by the formula (2) and the structural unit (b3) represented by the formula (3), the polycarbonate resin composition (2) according to any one of <12> to <15>. <17> A method for producing the polycarbonate resin composition (2) according to any one of <12> to <16>, including a step of mixing the glass filler (A), the polycarbonate resin component (B'') and the styrenic elastomer (C).

Advantages of the Invention

[0013] According to the present invention, there are provided a polycarbonate resin composition and a molded article thereof having extremely excellent transparency and capable of being easily provided, and a method for producing the same.

Modes for Carrying Out the Invention

[0014] In this specification, the "refractive index at each wavelength" and the "Abbe number" are values measured and calculated in accordance with JIS K 7142:2014, Method B. In this specification, the regulations that are considered preferable can be arbitrarily adopted, and combinations of preferable ones can be said to be more preferable. In this specification, the description of "XX to YY" means "XX or more and YY or less".

[0015] [Polycarbonate resin composition (1)] The polycarbonate resin composition (1) which is one of the aspects of the present invention includes a glass filler (A), and an aliphatic polycarbonate copolymer (B n ) containing at least one selected from the structural unit (b1) represented by the following formula (1), the structural unit (b2) represented by the following formula (2), and the structural unit (b3) represented by the following formula (3), and the difference in refractive index with respect to light of a wavelength of 589.3 nm between the glass filler (A) and the polycarbonate resin component (B) is 0.0150 or less.

[0016] [Chemical formula]

[0017] [Glass filler (A)] The glass filler (A) is used to enhance the mechanical properties of the polycarbonate resin component (B) described later. As the glass filler (A), various forms such as glass fiber, glass powder, glass flake, milled fiber, or glass beads can be adopted. From the viewpoint of the reinforcing effect, the glass filler (A) is preferably glass fiber.

[0018] As the glass fiber, for example, the glass fiber used for manufacturing fiber reinforced plastics (FRP) which are conventional printed wiring boards and structural members of automobiles, airplanes, etc. can be used. It is also called glass fiber or glass long fiber. The glass fiber can be manufactured using a conventionally known spinning method for glass long fiber. For example, first, a raw material mixture (referred to as a raw material batch) prepared and mixed so as to have a target composition is put into a melting furnace, and the glass is heated by burning heavy oil or gas burners or by directly applying electricity to advance the melting from the surface of the batch and gradually obtain a glass melt. Subsequently, the molten glass is supplied to a forming device called a bushing (also referred to as a spinning furnace). The bushing is a device having a substantially rectangular appearance with a number of nozzle parts (or orifice parts), and the temperature is controlled so that the viscosity of the molten glass at the tip of the bushing nozzle becomes about 103 dPa·s. The temperature at which the viscosity of the molten glass becomes 103 dPa·s is called the forming temperature TX, and the smaller the temperature difference ΔTXL between TX and the liquidus temperature TL, the more likely devitrified substances are to occur in the glass melt at the tip of the bushing nozzle, and the more likely yarn breakage is to occur. Therefore, it is preferable that ΔTXL is larger. Thereafter, the molten glass is spun to produce glass fibers. Specifically, the molten glass supplied to the bushing is continuously drawn out from the tip of the bushing nozzle and rapidly cooled to form it into a filament shape, and at the same time, it is bundled for each predetermined number to obtain glass fibers. Such a method for producing glass fibers is described, for example, in Japanese Patent Application Laid-Open No. 2007-39320. The average fiber diameter of the glass fibers is not particularly limited. The average fiber diameter is preferably 3 μm or more and 25 μm or less. If the average fiber diameter is 3 μm or more, the contact area between the glass fibers and the aliphatic polycarbonate copolymer (B) is adjusted and diffuse reflection is suppressed, and the transparency of the molded body is good. If the average fiber diameter is 25 μm or less, the strength of the glass fibers is good, and as a result, the strength of the molded body is good. When obtaining a molded body by injection molding, the ratio (aspect ratio) of the average fiber length to the average fiber diameter of the glass fibers in the molded body is preferably used to be 2 or more and 150 or less. If the aspect ratio is 2 or more, the mechanical strength is improved, and if the aspect ratio is 150 or less, high transparency of the molded body is obtained and the appearance of the molded body is improved. From the above viewpoints, the average fiber diameter of the glass fibers in the molded body is preferably 3 μm or more, more preferably 5 μm or more, still more preferably 7 μm or more, and preferably 25 μm or less, more preferably 15 μm or less. Also, the aspect ratio of the glass fibers in the molded body is more preferably 2.5 or more, still more preferably 3 or more, and more preferably 120 or less, still more preferably 100 or less. The average fiber diameter of the glass fiber is a value measured in accordance with the method specified in JIS A 9505:1977. Specifically, the diameter of the glass fiber is measured with a microscope equipped with a filar micrometer eyepiece, and the average value is obtained. When obtaining a glass cloth from glass fibers, it can be obtained by weaving the glass long fibers obtained by spinning into a cloth shape, for example, by a plain weave method. When obtaining an injection molded article containing glass fibers, it can be obtained, for example, by using chopped strands obtained by cutting glass long fibers. There is no limit to the length of the chopped strands, but those with a length of 1 mm or more, preferably 3 mm or more, and 10 mm or less, preferably 5 mm or less can be used.

[0019] The glass powder is obtained by a conventionally known manufacturing method. For example, the glass raw material is melted in a melting furnace, the obtained melt is poured into water and granulated, or formed into a sheet shape with a cooling roll and then the sheet is pulverized to obtain a powder with a desired particle size. The particle size of the glass powder is not particularly limited. The particle size of the glass powder is preferably 1 μm or more and 100 μm or less.

[0020] The glass flake is obtained by a conventionally known manufacturing method. For example, the glass raw material is melted in a melting furnace, the obtained melt is drawn out in a tube shape, and after making the film thickness of the glass constant, it is pulverized with a roll to obtain a frit with a specific film thickness. By pulverizing this frit, flakes having a desired aspect ratio can be obtained. The thickness and aspect ratio of the glass flake are not particularly limited. The thickness of the glass flake is preferably 0.1 μm or more and 10 μm or less, and the aspect ratio is preferably 5 or more and 150 or less.

[0021] The mild fiber can be obtained by using a conventionally known method for manufacturing a mild fiber. For example, the mild fiber can be obtained by pulverizing strands of glass fiber with a hammer mill or a ball mill. The fiber diameter and aspect ratio of the mild fiber are not particularly limited. The fiber diameter and aspect ratio of the mild fiber are preferably those with a fiber diameter of 3 μm or more and 25 μm or less, and an aspect ratio of 2 or more and 150 or less. The average fiber diameter of the mild fiber is more preferably 5 μm or more and 20 μm or less, and even more preferably 7 μm or more and 15 μm or less. Also, the aspect ratio of the mild fiber is more preferably 2.5 or more and 90 or less, and even more preferably 3 or more and 70 or less.

[0022] The glass beads can be obtained by a conventionally known manufacturing method. For example, the glass raw material can be melted in a melting furnace, and the obtained melt can be sprayed with a burner to obtain glass beads having a desired particle size. The particle size of the glass beads is not particularly limited. The particle size of the glass beads is preferably 5 μm or more and 300 μm or less.

[0023] In order to increase the affinity between the glass filler (A) and the polycarbonate resin component (B) and increase the adhesion, and thereby suppress the decrease in the transparency of the molded body due to void formation, it is preferable to surface-treat the glass filler with a treating agent containing a coupling agent.

[0024] As the coupling agent, a silane-based coupling agent, a borane-based coupling agent, an aluminate-based coupling agent, a titanate-based coupling agent, or the like can be used. In particular, from the viewpoint of improving the adhesion between the polycarbonate resin and the glass filler, it is preferable to use a silane-based coupling agent. As the silane-based coupling agent, an amino silane-based coupling agent, an epoxy silane-based coupling agent, an acrylic silane-based coupling agent, or the like can be used. Among them, the amino silane-based coupling agent is most preferable.

[0025] Examples of components other than the coupling agent contained in the treatment agent include a film former, a lubricant, an antistatic agent, etc., and these may be used alone or in combination of two or more. 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, surfactants of aliphatic ester type, aliphatic ether type, aromatic ester type or aromatic ether type can be used. As the antistatic agent, inorganic salts such as lithium chloride and potassium iodide, or quaternary ammonium salts such as ammonium chloride and ammonium ethosulfate can be used.

[0026] The glass filler (A) preferably has a composition of 50% by mass or more and 70% by mass or less of silicon dioxide (SiO2), more than 0% by mass and 25% by mass or less of aluminum oxide (Al2O3), 8% by mass or more and 25% by mass or less of boron oxide (B2O3), more than 0% by mass and 10% by mass or less of magnesium oxide (MgO), more than 0% by mass and 20% by mass or less of calcium oxide (CaO), more than 0% by mass and 5% by mass or less of sodium oxide (Na2O), more than 0% by mass and 5% by mass or less of potassium oxide (K2O), and more than 0% by mass and 10% by mass or less of titanium oxide (TiO2), and the total content of the silicon dioxide (SiO2) and the aluminum oxide (Al2O3) in the glass filler (A) is more than 50% by mass and 90% by mass or less, and the total content of the sodium oxide (Na2O), the potassium oxide (K2O) and lithium oxide (Li2O) is more than 0% by mass and 15% by mass or less.

[0027] In the preferred composition of the glass filler (A) described above, the content of silicon dioxide (SiO2) is preferably 50% by mass or more and 70% by mass or less in 100% by mass of the glass filler (A). If the content of silicon dioxide (SiO2) is 50% by mass or more, it is easy to adjust to the desired refractive index. Also, if it is 70% by mass or less, it has excellent solubility when made into glass. From this viewpoint, the content of silicon dioxide (SiO2) is more preferably 51% by mass or more, still more preferably 53% by mass or more, and is more preferably 65% by mass or less, still more preferably 60% by mass or less.

[0028] In the preferred composition of the glass filler (A) described above, the content of aluminum oxide (Al2O3) is preferably more than 0% by mass and 25% by mass or less in 100% by mass of the glass filler (A). By the content of aluminum oxide (Al2O3) being 25% by mass or less, it has excellent solubility when making the raw material into glass, and the resulting glass filler has excellent uniformity. From this viewpoint, the content of aluminum oxide (Al2O3) is more preferably 5% by mass or more, still more preferably 10% by mass or more, and is more preferably 23% by mass or less, still more preferably 20% by mass or less.

[0029] In the preferred composition of the glass filler (A) described above, the total content of the silicon dioxide (SiO2) and the aluminum oxide (Al2O3) is preferably more than 50% by mass and 90% by mass or less, more preferably 55% by mass or more and 80% by mass or less, still more preferably 60% by mass or more and 70% by mass or less in 100% by mass of the glass filler (A).

[0030] In the preferred composition of the glass filler (A) described above, the content of boron oxide (B2O3) is preferably 8% by mass or more and 25% by mass or less in 100% by mass of the glass filler (A). When the content of boron oxide (B2O3) in the glass filler is 8% by mass or more, the solubility of the glass is improved, and the water resistance of the glass and the like are improved. If the content of boron oxide (B2O3) is 25% by mass or less, the glass filler is excellent in strength. From this viewpoint, the content of boron oxide (B2O3) is more preferably 10% by mass or more, still more preferably 12% by mass or more, and more preferably 23% by mass or less, still more preferably 20% by mass or less.

[0031] In the preferred composition of the glass filler (A) described above, the content of magnesium oxide (MgO) is preferably more than 0% by mass and 10% by mass or less in 100% by mass of the glass filler (A). When the glass filler (A) contains magnesium oxide (MgO), the physical properties such as the tensile strength of the glass filler and the chemical durability are improved. If the content of magnesium oxide (MgO) is 10% by mass or less, the solubility of the glass does not decrease. From this viewpoint, the content of magnesium oxide (MgO) is more preferably 1% by mass or more, still more preferably 2% by mass or more, and more preferably 8% by mass or less, still more preferably 6% by mass or less.

[0032] In the preferred composition of the glass filler (A) described above, the content of calcium oxide (CaO) is preferably more than 0% by mass and 20% by mass or less in 100% by mass of the glass filler (A). When calcium oxide (CaO) is included, the processability into fibers and the like is excellent, and if the content is 20% by mass or less, it is easy to adjust to a desired refractive index. From this viewpoint, the content of calcium oxide (CaO) is more preferably 2% by mass or more, and more preferably 15% by mass or less, still more preferably 10% by mass or less.

[0033] In the preferred composition of the glass filler (A) described above, the content of sodium oxide (Na2O) is preferably more than 0% by mass and 5% by mass or less in 100% by mass of the glass filler (A). If the content of sodium oxide (Na2O) is 5% by mass or less, the glass is excellent in water resistance and the elution of alkali is suppressed. When the alkali component elutes, the polycarbonate copolymer is hydrolyzed, causing a decrease in molecular weight, which is not preferable because it causes a deterioration in the physical properties of the molded body. From this viewpoint, the content of sodium oxide (Na2O) is more preferably 4% by mass or less, and even more preferably 2% by mass or less.

[0034] In the preferred composition of the glass filler (A) described above, the content of potassium oxide (K2O) is preferably more than 0% by mass and 5% by mass or less in 100% by mass of the glass filler (A). When the glass filler (A) contains potassium oxide (K2O), the solubility of the glass is improved. If the content is 5% by mass or less, the glass is excellent in water resistance, the elution of alkali is suppressed, and the crystallization of the glass is also suppressed. From this viewpoint, the content of potassium oxide (K2O) is more preferably 4% by mass or less, and even more preferably 2% by mass or less.

[0035] In the preferred composition of the glass filler (A) described above, the content of titanium oxide (TiO2) is preferably more than 0% by mass and 10% by mass or less in 100% by mass of the glass filler (A). When the glass filler (A) contains titanium oxide (TiO2), the solubility of the glass is improved, and the water resistance of the glass is also improved. If titanium oxide (TiO2) is 10% by mass or less, the crystallization of the glass is suppressed. If the content of titanium oxide (TiO2) is 8% by mass or less, the coloring of the glass in the presence of iron oxide (Fe2O3) contained as an impurity can be suppressed. From this viewpoint, titanium oxide (TiO2) is more preferably 0% by mass or more and 8% by mass or less, and even more preferably 0% by mass or more and 5% by mass or less.

[0036] The glass filler (A) can further contain zinc oxide (ZnO), strontium oxide (SrO), and barium oxide (BaO) as optional components. Zinc oxide (ZnO), strontium oxide (SrO), and barium oxide (BaO) are optional components, and each is preferably contained in an amount of 0% by mass or more and 10% by mass or less. By replacing zinc oxide (ZnO), strontium oxide (SrO), and / or barium oxide (BaO) with calcium oxide (CaO), the solubility of the glass can be improved, and the crystallization of the glass can be suppressed. From this perspective, zinc oxide (ZnO), barium oxide (BaO), and strontium oxide (SrO) are each more preferably contained in an amount of 0% by mass or more and 8% by mass or less, and even more preferably 0% by mass or more and 5% by mass or less.

[0037] The total of calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), and strontium oxide (SrO) is preferably 0% by mass or more and 20% by mass or less. If the total is 20% by mass or less, it is easy to adjust to the desired refractive index. If the total is 5% by mass or more, the solubility of the glass is improved. The total content of calcium oxide (CaO), zinc oxide (ZnO), barium oxide (BaO), and strontium oxide (SrO) is more preferably 3% by mass or more and 18% by mass or less, and even more preferably 5% by mass or more and 15% by mass or less.

[0038] The glass filler (A) can further contain lithium oxide (Li2O) and cesium oxide (Cs2O). Lithium oxide (Li2O) and cesium oxide (Cs2O) are optional components, and each can be contained in an amount of 0% by mass or more and 5% by mass or less. By containing lithium oxide (Li2O) and cesium oxide (Cs2O) together with potassium oxide (K2O) and replacing at least a part of sodium oxide (Na2O), the solubility of the glass can be improved. By setting the content of each to 5% by mass or less, the water resistance of the glass is improved and the elution of alkali is suppressed. It is not preferable because the polycarbonate-based resin is hydrolyzed by the eluted alkali component, causing a decrease in molecular weight and a factor in the deterioration of the physical properties of the molded body. Also, the glass becomes more likely to crystallize. From this viewpoint, lithium oxide (Li2O) and cesium oxide (Cs2O) are more preferably contained in an amount of 0% by mass or more and 4% by mass or less, and still more preferably 0% by mass or more and 2% by mass or less, respectively.

[0039] In the glass filler (A) according to the present invention, it is preferable that the total content of lithium oxide (Li2O), sodium oxide (Na2O), and potassium oxide (K2O) is more than 0% by mass and 15% by mass or less. If the total of sodium oxide (Na2O), potassium oxide (K2O), and lithium oxide (Li2O) is 15% by mass or less, the water resistance of the glass does not decrease and the elution of alkali can be suppressed. When the alkali component elutes, the polycarbonate copolymer may be hydrolyzed, causing a decrease in molecular weight and a factor in the deterioration of the physical properties of the molded body, which is not preferable. Also, from the viewpoint of the ease of adjusting the refractive index of the glass filler (A) to a desired range, the total amount of the alkali components is preferably 0.01% by mass or more. From these viewpoints, the total content of lithium oxide (Li2O), sodium oxide (Na2O), and potassium oxide (K2O) is preferably 0.01% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[0040] In order to suppress the coloring of the glass filler, the content of iron oxide (Fe2O3) as an impurity in the raw materials is preferably 0% by mass or more and 0.1% by mass or less with respect to the entire glass. In order to suppress the coloring of the glass filler, it is also preferable to contain antimony trioxide (Sb2O3) in an amount of 0% by mass or more and 2% by mass or less with respect to the entire glass. Further, in order to improve the solubility of the glass filler, it is preferable to contain fluorine (F2) in an amount of 0% by mass or more and 1% by mass or less with respect to the entire glass.

[0041] The glass filler (A) according to the present invention may further contain the following components as long as it does not adversely affect the adjustment of the refractive index, glass physical properties, glass formability, etc. For example, as a component for adjusting the refractive index of the glass filler, an oxide containing an element such as zirconium (Zr), lanthanum (La), yttrium (Y), gadolinium (Gd), bismuth (Bi), antimony (Sb), tantalum (Ta), niobium (Nb), or tungsten (W) may be contained. Also, as a component for adjusting and decoloring the color of the glass, an oxide containing an element such as cobalt (Co), copper (Cu), neodymium (Nd), or antimony (Sb) may be contained. Zirconium dioxide (ZrO2) is an optional component and is preferably contained in an amount of 0% by mass or more and 10% by mass or less. When the zirconium dioxide (ZrO2) exceeds 10% by mass, the solubility when forming the glass may decrease.

[0042] From the viewpoint of weight reduction, the specific gravity of the glass filler (A) is preferably 2.75 or less.

[0043] The refractive index of the glass filler (A) with respect to light having a wavelength of 589.3 nm is preferably 1.4850 or more and 1.5200 or less. If the refractive index with respect to light having a wavelength of 589.3 nm is within the above range, the refractive index difference from the polycarbonate resin component (B) can be set within a specific range, and the transparency of the resulting molded body is excellent. Further, from the viewpoint of improving the transparency of the molded body made of the polycarbonate resin composition, the refractive index of the glass filler (A) at a wavelength of 589.3 nm is more preferably 1.4900 or more, still more preferably 1.5000 or more, and more preferably 1.5150 or less, still more preferably 1.5140 or less.

[0044] The Abbe number (V d ) of the glass filler (A) is preferably 52.5 or more and 65.0 or less from the viewpoint of reducing the chromatic aberration of the resulting molded body. The Abbe number (V d ) of the glass filler (A) is more preferably 53.0 or more and 64.0 or less, and even more preferably 56.0 or more and 63.0 or less.

[0045] <Polycarbonate resin component (B)> The polycarbonate resin component (B) contains an aliphatic polycarbonate copolymer (B n ) containing one or more selected from the structural unit (b1) represented by the following formula (1), the structural unit (b2) represented by the following formula (2), and the structural unit (b3) represented by the following formula (3).

Chemical formula

[0046] The structural unit (b1) preferably contains the structural unit (b1’) represented by the following formula (1’), and more preferably consists only of the structural unit (b1’).

[0047]

Chemical formula

[0048] The structural unit (b1) is a carbonate structural unit derived from isosorbide (ISB), the structural unit (b2) is a carbonate structural unit derived from 1,4 - cyclohexanedimethanol (CHDM), and the structural unit (b3) is a carbonate structural unit derived from tricyclodecane dimethanol (TCDDM).

[0049] The polycarbonate resin component (B) can contain a carbonate structural unit (X) other than the structural units (b1), (b2), and (b3). The carbonate structural unit (X) is represented by the following general formula (x).

[0050] [Chemical formula]

[0051] (In the formula, X 1 represents a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 22 carbon atoms, or a divalent hydrocarbon residue containing an aromatic group. The divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and / or at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among the divalent hydrocarbon residues containing an aromatic group, at least one heteroatom selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom; at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and one or more groups selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 5 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms may be included.)

[0052] X 1 Examples of the divalent alicyclic hydrocarbon group containing a heteroatom in X include a divalent oxygen - or nitrogen - containing saturated heterocyclic group having 4 to 20 carbon atoms, etc.

[0053] The polycarbonate resin component (B) contains two or more aliphatic polycarbonate copolymers (B n ). The number of types of aliphatic polycarbonate copolymers (B n ) that constitute the polycarbonate resin component (B) is preferably 2 or more and 5 or less, more preferably 2 or 3, and even more preferably 2. Aliphatic polycarbonate copolymers (B n ) of different types differ in at least one of the combination of structural units that constitute them and the molar ratio of the structural units that constitute them. The molar ratio of the structural units can be calculated, for example, by nuclear magnetic resonance (NMR) measurement. It can also be determined from the charging ratio during production.

[0054] Each aliphatic polycarbonate copolymer (B n ) contains the structural unit (b1) and one or more selected from the structural unit (b2) and the structural unit (b3). That is, each aliphatic polycarbonate copolymer (B n ) must contain the structural unit (b1), and further contains one or more selected from the structural unit (b2) and the structural unit (b3).

[0055] Specific examples of the combination of structural units that constitute each aliphatic polycarbonate copolymer (B n ) include a combination containing two types of the structural unit (b1) and the structural unit (b2) and not containing the structural unit (b3); a combination containing two types of the structural unit (b1) and the structural unit (b3) and not containing the structural unit (b2); and a combination of three types of the structural unit (b1), the structural unit (b2), and the structural unit (b3).

[0056] In each aliphatic polycarbonate copolymer (B n ), the content of the structural unit (b1) is preferably 30 mol% or more and 95 mol% or less, more preferably 40 mol% or more and 80 mol% or less, based on 100 mol% of all carbonate structural units. The total carbonate structural units refer to the structural unit (b1), the structural unit (b2), the structural unit (b3), and carbonate structural units (X) other than the structural unit (b1), the structural unit (b2), and the structural unit (b3). In each aliphatic polycarbonate copolymer (B n ), the total content of the structural unit (b2) and the structural unit (b3) is preferably 5 mol% or more and 70 mol% or less, more preferably 20 mol% or more and 60 mol% or less, based on 100 mol% of the total carbonate structural units. In each aliphatic polycarbonate copolymer (B n ), the content of carbonate structural units (X) other than the structural unit (b1), the structural unit (b2), and the structural unit (b3) is preferably 0 mol% or more and 8 mol% or less, more preferably 0 mol% or more and 5 mol% or less, based on 100 mol% of the total carbonate structural units. In one preferred embodiment, each aliphatic polycarbonate copolymer (B n ) does not contain carbonate structural units (X).

[0057] The viscosity average molecular weight of each aliphatic polycarbonate copolymer (B n ) is preferably 10,000 or more and 50,000 or less. When within this range, the balance between mechanical properties and fluidity is excellent. More preferably, it is 12,000 or more and 35,000, and even more preferably 14,000 or more and 22,000 or less. The viscosity average molecular weight (Mv) is measured by measuring the viscosity of a methylene chloride solution at 20 °C using an Ubbelohde viscometer, obtaining the intrinsic viscosity [η] therefrom, and calculating it using the following Schnell's formula.

Equation

[0058] The refractive index of each aliphatic polycarbonate copolymer (B n ) with respect to light having a wavelength of 589.3 nm is preferably 1.4800 or more and 1.5200 or less. If the refractive index is within this range, the refractive index difference at each wavelength from the glass filler (A) can be made as small as possible. Each aliphatic polycarbonate copolymer (B n ) has a refractive index for light with a wavelength of 589.3 nm preferably of 1.5000 or more and 1.5190 or less, more preferably 1.5010 or more and 1.5160 or less, still more preferably 1.5100 or more and 1.5150 or less, and particularly preferably 1.5100 or more and 1.5140 or less.

[0059] Each aliphatic polycarbonate copolymer (B n ) has a difference (nF - nC) between the refractive index (nF) for light with a wavelength of 486.1 nm and the refractive index (nC) for light with a wavelength of 656.3 nm preferably of 0.0130 or less, more preferably 0.0110 or less, and still more preferably 0.0100 or less.

[0060] Each aliphatic polycarbonate copolymer (B n ) has an Abbe number (Vd) preferably of 45 or more, more preferably 48 or more, and still more preferably 51 or more, and preferably 65 or less. When the Abbe number of the aliphatic polycarbonate resin (A) is within the above range, the color aberration of the obtained molded article can be reduced.

[0061] Each aliphatic polycarbonate copolymer (B n ) preferably has a glass transition temperature of 75 to 150°C, more preferably 80 to 140°C, and still more preferably 100 to 130°C. When the glass transition temperature of each aliphatic polycarbonate copolymer (B n ) is at or above the lower limit, it can be suitably used for a plurality of applications. When the glass transition temperature is at or below the upper limit, it has excellent melt fluidity during molding and can be molded in a temperature range with less polymer decomposition.

[0062] (Method for producing an aliphatic polycarbonate copolymer (B n )) Each aliphatic polycarbonate copolymer (B nThere are no particular restrictions on the production method of . For example, an interfacial polycondensation method or a melting method (transesterification method) can be mentioned. That is, an interfacial polycondensation method in which a dihydroxy compound and a carbonate precursor such as phosgene are reacted in the presence of a terminal stopper, or a reaction is carried out by a transesterification method between a dihydroxy compound and a diester carbonate in the presence of a terminal stopper, etc., can be used. The aliphatic polycarbonate resin (B n ) according to the present invention is preferably produced by a transesterification method.

[0063] · Dihydroxy compound As the dihydroxy compound, one or more selected from the group consisting of isosorbide (ISB) that forms the structural unit (b1), 1,4-cyclohexanedimethanol (CHDM) that forms the structural unit (b2), and tricyclodecanedimethanol (TCDDM) that forms the structural unit (b3) are used. In addition, when a carbonate structural unit (X) other than isosorbide (ISB) that forms the structural unit (b1), 1,4-cyclohexanedimethanol (CHDM) that forms the structural unit (b2), and tricyclodecanedimethanol (TCDDM) that forms the structural unit (b3) is included, the corresponding dihydroxy compound is used.

[0064] · Diester carbonate The diester carbonate is at least one compound selected from diaryl carbonate compounds, dialkyl carbonate compounds, and alkylaryl carbonate compounds. The diaryl carbonate compound is a compound represented by the following general formula (14) or a compound represented by the following general formula (15).

[0065]

Chemical formula

[0066] In formula (14), Ar 1 and Ar 2 each represent an aryl group, and they may be the same as or different from each other. In formula (15), Ar 3 and Ar 4 each represent an aryl group, which may be the same as or different from each other, and D 1 represents the residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound.

[0067] The dialkyl carbonate compound is a compound represented by the following general formula (16) or a compound represented by the following general formula (17).

[0068]

Chemical formula

[0069] In formula (16), R 21 and R 22 each represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, which may be the same as or different from each other. In formula (17), R 23 and R 24 each represent an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, which may be the same as or different from each other, and D 2 represents the residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound.

[0070] The alkyl aryl carbonate compound is a compound represented by the following general formula (18) or a compound represented by the following general formula (19).

[0071]

Chemical formula

[0072] In formula (18), Ar 5 is an aryl group, and R 25 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms. In formula (19), Ar 6 is an aryl group, and R 26is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, D 1 represents the residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound.

[0073] Specifically, examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, bis(m-cresyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, bisphenol A bisphenyl carbonate, and the like. Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate, and the like. Examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate, and the like. In the present invention, as the carbonic acid diester, one or more of the above-mentioned compounds are appropriately selected and used. Among these, it is preferable to use diphenyl carbonate.

[0074] In the transesterification method, raw materials other than the dihydroxy compound and the carbonic acid diester may be used. For example, as the diesters of the dihydroxy compound, examples include bisphenol A diacetate, bisphenol A dipropionate, bisphenol A dibutyrate, bisphenol A dibenzoate, and the like. In addition, as the dicarbonic acid esters of the dihydroxy compound, examples include bisphenol A bismethyl carbonate, bisphenol A bisethyl carbonate, bisphenol A bisphenyl carbonate, and the like. Examples of the monocarbonic esters of the dihydroxy compound include bisphenol A monomethyl carbonate, bisphenol A monoethyl carbonate, bisphenol A monopropyl carbonate, bisphenol A monophenyl carbonate, and the like.

[0075] (Terminal terminator) In the production of the aliphatic polycarbonate copolymer (B n ), a terminal terminator can be used as needed. As the terminal terminator, known terminal terminators in the production of the aliphatic polycarbonate copolymer (B n ) can be used. For example, specific compounds thereof include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. These monohydric phenols can be used alone or in combination of two or more.

[0076] (Branching agent) In the production of the aliphatic polycarbonate copolymer (B n ), a branching agent can also be used as needed. Examples of the branching agent include phloroglucin; trimellitic acid; 1,1,1-tris(4-hydroxyphenyl)ethane; 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4''-hydroxyphenyl)ethyl]benzene; α,α',α''-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene; isatin bis(o-cresol); and the like.

[0077] (Transesterification method) The aliphatic polycarbonate copolymer (B n) can be produced by the ordinary transesterification method. For example, a transesterification reaction can be carried out using a dihydroxy compound and a diester carbonate, and if necessary, a terminal stopper or a branching agent, etc., to obtain a polycarbonate resin. Specifically, the reaction may be allowed to proceed according to a known transesterification method. The procedures and conditions of a preferred production method are specifically shown below.

[0078] A transesterification reaction is carried out between the dihydroxy compound and the diester carbonate at a ratio such that the diester carbonate is 0.9 to 1.5 times the molar amount of the dihydroxy compound. In addition, depending on the situation, the ratio is preferably 0.98 to 1.20 times the molar amount. In the above transesterification reaction, when the amount of the terminal stopper such as the monohydric phenol is in the range of 0.05 to 10 mol% with respect to the dihydroxy compound, the hydroxyl group terminals of the resulting polycarbonate are sealed, so that a polycarbonate having sufficiently excellent heat resistance and water resistance can be obtained. Such a terminal stopper such as the monohydric phenol may be added in the total amount to the reaction system in advance, or a part of it may be added to the reaction system in advance, and the remainder may be added as the reaction proceeds. Further, in some cases, it may be added in the total amount to the reaction system after the transesterification reaction between the dihydroxy compound and the diester carbonate has proceeded partially.

[0079] There is no particular limitation on the reaction temperature when carrying out the transesterification reaction, and it is usually selected in the range of 100 to 330 °C, preferably in the range of 180 to 300 °C. More preferably, a method of gradually raising the temperature to the temperature range of 180 to 300 °C as the reaction proceeds is good. If the temperature of this transesterification reaction is 100 °C or higher, the reaction rate becomes fast, while if it is 330 °C or lower, side reactions do not occur, and problems such as coloring of the resulting polycarbonate are less likely to occur. In addition, the reaction pressure is set according to the vapor pressure of the monomers used and the reaction temperature. This may be set so that the reaction can be carried out efficiently and is not limited. Usually, at the initial stage of the reaction, the atmospheric pressure (normal pressure) or pressurized state up to 1 to 50 atm (760 to 38,000 torr) is maintained, and in the later stage of the reaction, the pressure is usually reduced, preferably finally to 1.33 to 1.33×104 Pa (0.01 to 100 torr). The reaction time may be carried out until the target molecular weight is reached, and is usually about 0.2 to 10 hours.

[0080] The above transesterification reaction is usually carried out in the absence of an inert solvent. If necessary, it may be carried out in the presence of an inert solvent in an amount of 1 to 150% by mass of the resulting polycarbonate. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene; and cycloalkanes such as tricyclo(5,2,1,0)decane, cyclooctane, and cyclodecane. In addition, if necessary, it may be carried out under an inert gas atmosphere. Examples of the inert gas include gases such as argon, carbon dioxide, nitrous oxide, and nitrogen, various alkanes such as chlorofluorohydrocarbons, ethane, and propane, and alkenes such as ethylene and propylene.

[0081] In the transesterification method, a polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, metal compounds, or a combination of a nitrogen-containing organic basic compound and a quaternary phosphonium salt containing an aryl group.

[0082] Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol, etc.

[0083] Examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, barium diacetate, etc.

[0084] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides having alkyl, aryl groups, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, etc. Tertiary amines such as triethylamine, dimethylbenzylamine, triphenylamine, etc., and imidazoles such as 2-methylimidazole, 2-phenylimidazole, benzimidazole, etc. Further, bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, etc. are included.

[0085] Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, etc. These compounds may be used alone or in combination of two or more.

[0086] Examples of the combination of the nitrogen-containing organic basic compound and the quaternary phosphonium salt containing an aryl group include the combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate.

[0087] The usage amount of these polymerization catalysts is preferably selected in the range of 1×10 -9 ~1×10 -2 equivalent, preferably 1×10 -8 ~1×10 -2 equivalent, more preferably 1×10 -7 ~1×10 -3 equivalent with respect to 1 mol of the dihydroxy compound.

[0088] A catalyst deactivator can also be added in the later stage of the reaction. As the catalyst deactivator to be used, known catalyst deactivators are effectively used. Among these, ammonium salts and phosphonium salts of sulfonic acid are preferable. Further, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate and salts of p-toluenesulfonic acid such as tetrabutylammonium p-toluenesulfonate are preferable.

[0089] As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, etc. are also preferably used.

[0090] Among these, tetrabutylphosphonium dodecylbenzenesulfonate or butyl p-toluenesulfonate is most preferably used. When at least one polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds is used, the amount of these catalyst deactivators is preferably in a ratio of 0.5 to 50 moles, more preferably 0.5 to 10 moles, and still more preferably 0.8 to 5 moles per mole of the catalyst.

[0091] The reaction in the transesterification method may be carried out either continuously or batchwise. The reaction apparatus used for melt polymerization may be either a vertical reaction apparatus equipped with an anchor-type stirring blade, a max blend stirring blade, a helical ribbon-type stirring blade, etc., or a horizontal reaction apparatus equipped with a paddle blade, a grid blade, a glasses blade, etc. Further, an extruder type equipped with a screw may also be used. In the case of continuous operation, it is preferable to use such reaction apparatuses in appropriate combination.

[0092] (Interfacial polycondensation method) In the present invention, in the production of polycarbonate by the ordinary interfacial polycondensation method, for example, in an inert solvent such as methylene chloride, in the presence of a known acid acceptor and a molecular weight regulator, and further, if necessary, a catalyst and a branching agent are added, and the dihydroxy compound and a carbonate precursor such as phosgene are reacted.

[0093] As a catalyst in the interfacial polycondensation method, a phase transfer catalyst, for example, a tertiary amine or its salt, a quaternary ammonium salt, a quaternary phosphonium salt, etc. can be preferably used. Examples of the tertiary amine include triethylamine, tributylamine, N,N-dimethylcyclohexylamine, pyridine, dimethylaniline, etc. Examples of the tertiary amine salt include hydrochloride, bromate, etc. of these tertiary amines. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, etc. Examples of the quaternary phosphonium salt include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, etc. These catalysts may be used alone or in combination of two or more. Among the above catalysts, tertiary amines are preferred, and triethylamine is particularly preferred.

[0094] Examples of the inert organic solvent include chlorinated hydrocarbons such as dichloromethane (methylene chloride), trichloromethane, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, chlorobenzene, and toluene, acetophenone, etc. These organic solvents may be used alone or in combination of two or more. Among these, methylene chloride is particularly preferred.

[0095] <Other components> The polycarbonate resin composition (1) of the present invention can contain other components as long as the properties such as refractive index are not impaired. For example, the antioxidant can suppress the decomposition of the resin during the production or molding of the polycarbonate resin composition. Depending on the use and necessity, additives such as heat stabilizers, plasticizers, light stabilizers, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, mold release agents, etc. can be included.

[0096] <Content> The content of the glass filler (A) in the polycarbonate resin composition (1) of the present invention is preferably 2 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin component (B). When the content of the glass filler (A) is 2 parts by mass or more, the mechanical properties of the molded body are excellent. Further, when the content of the glass filler (A) is 50 parts by mass or less, the contact interface between the polycarbonate resin component (B) and the glass filler (A) is properly adjusted, high transparency of the molded body is achieved, and the solid component of the glass component is properly adjusted and the fluidity during molding is excellent. As a result, the moldability is excellent. The content of the glass filler (A) in 100 parts by mass of the polycarbonate resin component (B) is more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, particularly preferably 30 parts by mass or less.

[0097] The content of the polycarbonate resin component (B) in the polycarbonate resin composition (1) is preferably 50% by mass or more and 98% by mass or less with respect to 100% by mass of the polycarbonate resin composition (1). More preferably 60% by mass or more, still more preferably 65% by mass or more, particularly preferably 70% by mass or more, and more preferably 97% by mass or less, still more preferably 95% by mass or less.

[0098] By setting the contents of the glass filler (A) and the polycarbonate resin component (B) contained in the polycarbonate resin composition (1) within the above ranges, a molded body having extremely high transparency and good mechanical properties can be obtained. The polycarbonate resin composition of the present invention can achieve an improvement in strength such as elastic modulus and a low coefficient of linear expansion by blending a glass filler while maintaining the excellent transparency inherent in the polycarbonate resin.

[0099] <Difference in refractive index> In the polycarbonate resin composition (1), the difference in refractive index of the glass filler (A) and the polycarbonate resin component (B) with respect to light having a wavelength of 589.3 nm is 0.0150 or less. The difference being 0.0150 or less means that the absolute value of the difference is 0.0150 or less, that is, the difference is -0.0150 or more and 0.0150 or less. By setting the difference in refractive index with respect to light having a wavelength of 589.3 nm within the above range, a molded article having extremely excellent transparency can be obtained. The difference in refractive index with respect to light having a wavelength of 589.3 nm is preferably 0.0100 or less, more preferably 0.0080 or less, still more preferably 0.0050 or less, and even more preferably 0.0030 or less.

[0100] From the same viewpoint, the difference in refractive index of the glass filler (A) and the polycarbonate resin component (B) with respect to light having a wavelength of 486.1 nm is preferably 0.0300 or less, more preferably 0.0100 or less, still more preferably 0.0080 or less, and even more preferably 0.0070 or less. From the same viewpoint, the difference in refractive index of the glass filler (A) and the polycarbonate resin component (B) with respect to light having a wavelength of 656.3 nm preferably needs to be 0.0100 or less, more preferably 0.0080 or less, still more preferably 0.0070 or less, and even more preferably 0.0060 or less.

[0101] The difference in refractive index can be obtained by dissolving and separating the polycarbonate resin composition (1) using a solvent such as methylene chloride or chloroform to obtain the glass filler (A) and the polycarbonate resin component (B), and measuring the respective refractive indices. Alternatively, the glass filler (A) and the polycarbonate resin component (B) which are raw materials constituting the polycarbonate resin composition (1) may be used, and their respective refractive indices may be measured. In this case, for the polycarbonate resin component (B), the refractive index is measured after melt-kneading two or more aliphatic polycarbonate copolymers (B n ) in advance.

[0102] <Condition (i) and Condition (ii)> In a preferred embodiment of the present invention, the polycarbonate resin component (B) satisfies one or more of the following conditions (i) and (ii). Preferably, both of the conditions (i) and (ii) are satisfied. (i) The haze value is less than 1.5 at a thickness of 1 mm (ii) It has one glass transition temperature

[0103] (Condition (i)) The haze value is a value measured using a molded body with a thickness of 1 mm in accordance with ASTM D1003. If the haze of the polycarbonate resin component (B) is less than 1.5, the polycarbonate resin component (B) is transparent without visual turbidity. The haze value is preferably 1.0 or less, more preferably 0.8 or less, and still more preferably 0.5 or less.

[0104] (Condition (ii)) The glass transition temperature is the midpoint glass transition temperature at the point where a straight line equidistant from the vertical axis direction intersects the curve of the stepwise change portion of the glass transition with a straight line obtained by extending each of the baseline on the high temperature side and the baseline on the low temperature side in the differential scanning calorimetry (DSC) curve measured in accordance with JIS K 7121:2012. The glass transition temperature being one means that in the DSC curve, only one step-like change (baseline shift) indicating the glass transition temperature appears. From another perspective, it means that when the polycarbonate resin component (B) is measured by dynamic viscoelasticity measurement (dynamic viscoelasticity measurement according to Method A of JIS K 7244-4:1999) at a strain of 0.1% and a frequency of 10 Hz, there is one maximum value of the loss tangent (tanδ).

[0105] Satisfying at least one of the above conditions (i) and (ii) means, in other words, that each aliphatic polycarbonate copolymer (B n ) is mutually compatible at the molecular level in the polycarbonate resin composition (1) and does not form a sea-island structure. Such a state is also referred to as "complete compatibility".

[0106] The measurement of haze for the above condition (i) and the glass transition temperature for the above condition (ii) can be measured using the polycarbonate resin component (B) obtained by dissolving and separating the polycarbonate resin composition (1) with a solvent such as methylene chloride or chloroform. Alternatively, the same one as the polycarbonate resin component (B) constituting the polycarbonate resin composition (1) can be used to measure haze and the glass transition temperature. In this case, after melt-kneading two or more aliphatic polycarbonate copolymers (B n ), haze and the glass transition temperature are measured.

[0107] The polycarbonate resin composition (1) of the present invention has extremely excellent transparency. Transparency can be evaluated, for example, by the haze value. The haze value is a value measured using a molded body with a thickness of 1 mm in accordance with ASTM D1003. The polycarbonate resin composition (1) is a resin composition in which the haze value that can be measured when a molded body with a thickness of 1 mm is formed from the resin composition is preferably 15.0 or less, more preferably 13.0 or less, and still more preferably 11.0 or less.

[0108] [Method for Producing Polycarbonate Resin Composition (1)] The polycarbonate resin composition (1) of the present invention can be produced using a known method and can be easily provided. The method for producing the polycarbonate resin composition (1) of the present invention preferably includes a step of mixing the glass filler (A) and the polycarbonate resin component (B) (step A). In the step A, other components can optionally be mixed.

[0109] The order of mixing the components in the step A is not limited. Specifically, the glass filler (A), two or more aliphatic polycarbonate copolymers (B n ) and other components that are optionally added may be mixed simultaneously, or two or more aliphatic polycarbonate copolymers (B n ) that constitute the polycarbonate resin component (B) may be premixed to obtain the polycarbonate resin component (B), and then the obtained polycarbonate resin component (B), the glass filler (A), and other components that are optionally added may be mixed.

[0110] By the production method, a polycarbonate resin composition (1) in which the difference in refractive index between the glass filler (A) and the polycarbonate resin component (B) with respect to light having a wavelength of 589.3 nm is 0.0150 or less can be obtained.

[0111] As an example of means for achieving the difference in refractive index, in the step A, the types of the structural unit (b1) represented by the formula (1), the structural unit (b2) represented by the formula (2), and the structural unit (b3) represented by the formula (3), the composition ratio of the structural units, and the blending ratio of two or more of the aliphatic polycarbonate copolymers (B n ) are adjusted so that the difference in refractive index with respect to light having a wavelength of 589.3 nm between the glass filler (A) and the polycarbonate resin component (B) containing two or more of the aliphatic polycarbonate copolymers (B n ) is 0.0150 or less. As a means for adjusting the composition ratio of the structural units, adjustment of the composition ratio of the structural units constituting each aliphatic polycarbonate copolymer (B n ) can be mentioned.

[0112] In one of the preferred embodiments of the present invention, two types of aliphatic polycarbonate copolymers (B n ) are used. More preferably, the first aliphatic polycarbonate copolymer (B n ) has two types of structural units, (b1) and (b2), and the second aliphatic polycarbonate copolymer (B n ) has two types of structural units, (b1) and (b3). The first aliphatic polycarbonate copolymer (B n ) has a refractive index for light with a wavelength of 589.3 nm smaller than that of the glass filler (A), and the second aliphatic polycarbonate copolymer (B n ) has a refractive index for light with a wavelength of 589.3 nm larger than that of the glass filler (A). The primary structure of the resin is designed so that by changing the content ratio of the first aliphatic polycarbonate copolymer (B n ) and the second aliphatic polycarbonate copolymer (B n ), the refractive index of the polycarbonate resin component (B) can be adjusted to match that of the glass filler (A).

[0113] In a preferred embodiment of the present invention, the refractive index of the polycarbonate resin component (B) approximates the total value of the product of the refractive index of each aliphatic polycarbonate copolymer (B n ) and the content ratio of that aliphatic polycarbonate copolymer (B n ).

[0114] The method of mixing each component in Project A is preferably melt-kneading. Melt-kneading can be carried out by methods commonly used, such as methods using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a kneader, a multi-screw extruder, etc. The heating temperature during melt-kneading is usually 150°C or higher and 300°C or lower, preferably 220°C or higher and 300°C or lower. The melt-kneading time is not particularly limited and is, for example, 1 minute or more and 30 minutes or less, preferably 2 minutes or more and 15 minutes or less.

[0115] The melt-kneading is preferably melt-kneading carried out under conditions that do not promote transesterification. Conditions that do not promote transesterification are preferably conditions under which no transesterification catalyst is used. Specifically, it is a condition under which a transesterification reaction between a plurality of aliphatic polycarbonate copolymers does not substantially proceed during melt-kneading. Specific examples of the transesterification catalyst include at least one selected from the group consisting of metal oxides, alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and phosphorus-containing compounds. Examples of the metal oxide include, from the viewpoints of raw material availability and safety, for example, zinc oxide, tin oxide, iron oxide, zirconium oxide, and lead oxide. Among these, zinc oxide is mentioned. Examples of the alkali metal compound include hydroxides, inorganic salts, organic salts, halides, and hydrides of alkali metals. Examples of the alkaline earth metal compound include hydroxides, inorganic salts, organic salts, halides, and hydrides of alkaline earth metals. Examples of the nitrogen-containing compound include amines. Examples of the phosphorus-containing compound include various phosphonium salts. More specifically, examples include sodium hydroxide, potassium hydroxide, cesium hydroxide, barium hydroxide, calcium hydroxide, magnesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, barium carbonate, calcium carbonate, magnesium carbonate, lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, tertiary amines (e.g., triethylamine and triphenylamine), tetraphenylphosphonium bromide, and tetraphenylphosphonium chloride.

[0116] [Molded article of polycarbonate resin composition (1)] The molded article made of the polycarbonate resin composition (1) of the present invention can be produced using a known molding method. For example, the polycarbonate resin composition (1) can be molded by injection molding, extrusion molding, compression molding, calender molding, etc. to obtain a molded article. It may also be molded using a mold covered with a resin film or a resin sheet inside.

[0117] The molded article made of the polycarbonate resin composition (1) of the present invention has extremely excellent transparency. The transparency can be evaluated, for example, by the haze value. The haze value is a value measured using a molded article with a thickness of 1 mm in accordance with ASTM D1003. The molded article made of the polycarbonate resin composition (1) preferably has a haze value at a thickness of 1 mm of 15.0 or less, more preferably 13.0 or less, and still more preferably 11.0 or less.

[0118] The thickness of the molded body can be arbitrarily set according to the application and is not limited. Particularly when transparency of the molded body is required, the molded body is preferably a sheet, and the thickness is preferably 0.2 mm or more, more preferably 0.3 mm or more, preferably 4.0 mm or less, more preferably 3.0 mm or less, and still more preferably 2.0 mm or less. If the thickness of the molded body is 0.2 mm or more, the glass filler is less likely to appear on the sheet surface and warping is less likely to occur, so a sheet with excellent appearance can be obtained, and furthermore, a homogeneous and less uneven film can be obtained regardless of the molding conditions. Also, if the thickness of the molded body is 4.0 mm or less, higher transparency can be obtained.

[0119] If necessary, a coating such as a hard coat film, an anti-fog film, an antistatic film, or an anti-reflection film may be formed on the molded body, or a composite coating of two or more types may be used. Among them, since the weather resistance is good and wear of the surface of the molded body over time can be prevented, it is particularly preferable that a hard coat film is formed. The material of the hard coat film is not particularly limited, and known materials such as acrylate-based hard coat agents, silicone-based hard coat agents, and inorganic-based hard coat agents can be used.

[0120] The production conditions of the polycarbonate-based resin composition (1) and the molding conditions of the molded body made of the polycarbonate-based resin composition (1) can be appropriately selected and are not particularly limited. For example, from the viewpoint of suppressing resin decomposition, the heating temperature during melt kneading and the resin temperature during injection molding are preferably appropriately selected from the range of usually 150°C or more and 300°C or less.

[0121] When at least a part of the glass filler exists on the outermost surface of the molded article, the surface roughness of the molded article increases, diffuse reflection on the surface of the molded article increases, and as a result, the transparency of the molded article may deteriorate. As a method for reducing the surface roughness of the molded article, there is a method of forming a layer (skin layer) having a high resin content ratio on the outermost surface of the molded article to reduce the surface roughness of the molded article. As a method for forming the skin layer, for example, in the case of injection molding, by setting the temperature of the mold to a higher temperature than general conditions, the resin in contact with the mold is made easier to flow, and the skin layer is formed on the outermost surface of the molded article. can be mentioned. In the case of press molding, by setting the pressure during molding to a higher pressure than general conditions, a skin layer can be formed on the outermost surface of the molded article, and the surface roughness of the molded article can be reduced. By reducing the surface roughness of the molded article, diffuse reflection on the surface of the molded article is reduced, haze is reduced, and as a result, the transparency of the molded article can be further improved.

[0122] When the molded article of the obtained polycarbonate resin composition (1) is molded into a flat plate with a thickness of 1 mm, it is preferable that the total light transmittance for visible light is 80% or more and the haze is 10% or less. The total light transmittance is more preferably 85% or more, still more preferably 89% or more. The haze is more preferably 8% or less, still more preferably 6% or less.

[0123] Since the molded article having the above optical properties is extremely excellent in transparency, it is suitable for applications that require high transparency. The total light transmittance for visible light can be measured according to JIS K 7361-1:1997, and the haze can be measured according to ASTM D1003. By using an aliphatic polycarbonate resin containing an aliphatic carbonate repeating unit, the molded article of the polycarbonate resin system obtained by the present invention is excellent in scratch resistance, weather resistance, and parallel light transmittance compared to a polycarbonate resin composed only of an aromatic carbonate repeating unit. A molded body can be obtained.

[0124] The molded article made of the polycarbonate resin composition (1) of the present invention is a member that requires transparency, rigidity, further scratch resistance and weather resistance, for example, 1) automotive parts such as sunroofs, door visors, rear windows, side windows, etc., 2) architectural parts such as architectural glass, soundproof walls, carports, sunrooms and gratings, etc., 3) windows for railway vehicles and ships, 4) various parts such as TVs, radio cassettes, video cameras, video tape recorders, audio players, DVD players, telephones, displays, computers, registers, copiers, printers, facsimiles, etc., parts for electrical equipment such as outer plates and various parts of housings, 5) parts for precision machinery such as cases and covers for mobile phones, PDAs, cameras, slide projectors, watches, calculators, measuring instruments, display devices, etc., 6) agricultural parts such as vinyl houses and greenhouses, 7) furniture parts such as lighting covers, blinds, interior fixtures, etc. It can be preferably used for.

[0125] [Laminate] In another aspect of the present invention, the laminate is composed of a glass cloth (A') and one or more selected from the structural unit (b1) represented by the following formula (1), and the structural unit (b2) represented by the following formula (2) and the structural unit (b3) represented by the following formula (3) An aliphatic polycarbonate copolymer (B n ) is laminated to form a polycarbonate resin component layer (B') containing two or more kinds, is laminated to form The difference in refractive index with respect to light having a wavelength of 589.3 nm between the glass cloth (A') and the polycarbonate resin component layer (B') is 0.0150 or less. [Chemical formula]

[0126] [Glass cloth (A‘)] The glass cloth (A') can be obtained by a conventionally known manufacturing method. For example, a sizing agent is applied to glass fibers to obtain strands with a desired number of sized fibers. The sized strands are further twisted and used as warp and / or weft of the glass cloth. When used as warp, it is preferable to adjust the number, length, density, etc. according to the fabric design. The sized warp and the bobbin for the weft are mounted on a loom, and the glass cloth can be manufactured by a weaving process. Examples of the weaving method of the glass cloth include plain weave, twill weave, satin weave, damask weave, leno weave, imitation gauze weave, etc., and plain weave is preferable. Regarding the preferable composition and physical properties of the glass fibers constituting the glass cloth, they are the same as those of the aforementioned "glass filler (A)".

[0127] <Polycarbonate resin component layer (B’)> Regarding the two or more aliphatic polycarbonate copolymers (B n ) constituting the polycarbonate resin component layer (B’) and their preferable embodiments, they are the same as those of the "polycarbonate resin component (B)".

[0128] <Laminated body structure and thickness> In the laminated body of the present invention, the glass cloth (A’) and the polycarbonate resin component layer (B’) are alternately laminated. For example, embodiments in which the glass cloth (A’) and the polycarbonate resin component layer (B’) are laminated as (A’) / (B’) / (A’), (A’) / (B’) / (A’) / (B’) / (A’) / (B’) / (A’), etc. are exemplified. The laminated body of the present invention preferably has a thickness of 0.05 mm or more and 5 mm or less, more preferably 0.1 mm or more and 5 mm or less. The thickness of the glass cloth (A’) is preferably 0.01 mm or more and 1 mm or less, more preferably 0.03 mm or more and 0.5 mm or less.

[0129] <Manufacturing method of laminated body> (Manufacture of the sheet of the polycarbonate resin component layer (B’)) The polycarbonate resin component layer (B’) can obtain a resin sheet, for example, by introducing a kneaded mixture of resin components, preferably into a single-screw extruder or a twin-screw extruder, and melt-extruding it from a T-die. In this case, the resin sheet is continuously extruded in a sheet form and obtained as a continuous resin sheet. In another aspect, a resin sheet can also be obtained by press-molding the resin component in a molten state. Specifically, press-molding is performed using a press-molding machine with a spacer of a predetermined thickness sandwiched therein. The thickness of the resin sheet is, for example, 0.01 mm or more and 1.0 mm or less.

[0130] (Press-molding) The laminate of the present invention can be manufactured by press-molding a glass cloth (A’) and a polycarbonate resin component layer (B’). The press temperature, press pressure, and press holding time can be set as appropriate. The press temperature is preferably 200°C to 300°C, more preferably 210°C to 280°C, and still more preferably 220°C to 260°C. The press pressure is preferably 1 to 10 MPa, more preferably 2 to 7 MPa, and still more preferably 3 to 5 MPa. The press time is the time after reaching a predetermined press temperature, and is preferably 0.5 to 20 minutes, more preferably 1 to 15 minutes, and still more preferably 2 to 10 minutes.

[0131] [Polycarbonate resin composition (2)] The polycarbonate resin composition (2), which is another aspect of the present invention, contains a glass filler (A), a polycarbonate resin component (B’’) containing two or more selected from the group consisting of a structural unit (b1) represented by the following formula (1), a structural unit (b2) represented by the following formula (2), and a structural unit (b3) represented by the following formula (3), and a styrene-based elastomer (C), and the differences in refractive index with respect to light of a wavelength of 589.3 nm between the glass filler (A), the polycarbonate resin component (B’’), and the styrene-based elastomer (C) are each 0.0150 or less. [Chemical]

[0132] <Glass filler (A)> The glass filler (A) and its preferred embodiments are the same as those of the aforementioned polycarbonate resin composition (1).

[0133] <Polycarbonate resin component (B'')> The polycarbonate resin component (B'') contains two or more, preferably all three, selected from the group consisting of the structural unit (b1) represented by the aforementioned formula (1), the structural unit (b2) represented by the aforementioned formula (2), and the structural unit (b3) represented by the aforementioned formula (3). The polycarbonate resin component (B'') contains one or more aliphatic polycarbonate copolymers (B n ), and preferably contains two or more aliphatic polycarbonate copolymers (B n ). The preferred embodiment of the polycarbonate resin component (B'') is the same as that of the aforementioned polycarbonate resin composition (1).

[0134] <Styrene-based elastomer (C)> Specifically, the styrene-based elastomer (C) is a styrene-based thermoplastic elastomer having a styrene-based segment as a hard segment and an elastomer segment as a soft segment. The styrene-based elastomer (C) is generally a block copolymer.

[0135] In the styrene-based elastomer (C), the styrene-based segment is composed of a repetition of structural units derived from a styrene-based compound. The styrene-based segment is not particularly limited as long as it functions as a hard segment in the styrene-based elastomer (C). For example, it is preferably one or more selected from the following general formula (Z).

[0136] [Chemical] [In the general formula (Z), R A is an alkyl group having 1 to 5 carbon atoms, and m is an integer of 0 to 5. When m is 2 or more, a plurality of R A may be the same or different from each other. R B is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.] R A is preferably an alkyl group having 1 to 2 carbon atoms, more preferably a methyl group. m is preferably 0 or 1, more preferably 0. R B is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. As a preferable embodiment of the structural unit derived from the styrenic compound, a structural unit in which m = 0 and R B is a hydrogen atom can be mentioned. The styrenic elastomer (C) requires that the content of the styrenic segment is 10 to 40% by mass based on all the structural units of the styrenic elastomer (C), preferably 15 to 35% by mass, more preferably 20 to 30% by mass. When the content of the styrenic segment is at least the above lower limit value, the heat resistance is excellent, and when it is below the above lower limit value, the rubber properties are well exhibited, resulting in excellent impact strength and toughness, and the refractive index of the styrenic segment and the polycarbonate resin component is approximated, so the transparency is excellent.

[0137] The styrenic elastomer (C) preferably has a weight average molecular weight of 100,000 or more, more preferably 150,000 or more. When the weight average molecular weight of the styrenic elastomer (C) is at least the above lower limit, the physical properties such as the impact strength and toughness of the composition of the present invention are more excellent.

[0138] The structural units other than the structural units derived from styrenic compounds in the styrenic elastomer (C), that is, the structural units of the elastomeric segment which is the soft segment in the styrenic elastomer (C) include, for example, structural units derived from butadiene, structural units derived from isoprene, and structural units derived from isobutylene, and one or more selected from hydrogenated products thereof.

[0139] As the styrenic elastomer (C), for example, either an unmodified styrenic elastomer or a styrenic elastomer having a terminal group modified with a functional group can be used. From the viewpoint of compatibility with the polycarbonate resin component, the styrenic elastomer (C) preferably has a terminal group modified with a functional group. The functional group is preferably an amino group, an amide group, or a maleic anhydride group, and more preferably an amino group.

[0140] The styrenic elastomer (C) may be a hydrogenated type, that is, a hydrogenated styrenic elastomer (C). When the styrenic elastomer (C) is a hydrogenated type, the hydrogenation rate is preferably 90% by mass or more, and more preferably 98% by mass or more.

[0141] Specific examples of the styrenic elastomer (C) include one or more selected from styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-propylene block copolymer (SEP), styrene-ethylene-propylene block copolymer (SEP), hydrogenated product of styrene-isoprene·butadiene-styrene type triblock copolymer (SEEPS), etc.

[0142] A preferred embodiment of the styrenic elastomer (C) includes a styrene-ethylene-butylene-styrene copolymer having an amine-modified terminal group.

[0143] The styrenic elastomer (C) can be obtained by a known production method. For example, it can conform to the production method described in "Material Design and Molding Processing of Thermoplastic Elastomers" (published by Technical Information Association in 2007 under the supervision of Shinzo Yamashita). Also, commercially available products can be used. Examples of the styrenic elastomer (C) include Dynaron 6200 (manufactured by JSR Corporation), Clayton G1651 (manufactured by Clayton Polymer Japan Co., Ltd.), Septon series such as Septon 2104 (manufactured by Kuraray Co., Ltd.), and Tough Tech H series (manufactured by Asahi Kasei Corporation).

[0144] The content of the styrenic elastomer (C) in the polycarbonate resin composition (2) is preferably 2% by mass or more and 27% by mass or less, more preferably 5% by mass or more, still more preferably 10% by mass or more, and more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 15% by mass or less, based on 100% by mass of the polycarbonate resin composition (2). If the content of the styrenic elastomer (C) is 27% by mass or less, the polycarbonate resin composition (2) has excellent transparency, suppressed surface peeling, and excellent impact resistance. When the styrenic elastomer (C) is an unmodified styrenic elastomer, if the content of the styrenic elastomer (C) is less than 25% by mass, the polycarbonate resin composition (2) has even better transparency, more suppressed surface peeling, and better impact resistance. When the styrenic elastomer (C) is a styrenic elastomer having a terminal group modified with a functional group, if the content of the styrenic elastomer (C) is 27% by mass or less, the polycarbonate resin composition (2) has even better transparency, more suppressed surface peeling, and better impact resistance.

[0145] [Production Method of Polycarbonate Resin Composition (2)] The polycarbonate resin composition (2) of the present invention can be produced using a known method. The method for producing the polycarbonate resin composition (2) is the same as the method for producing the polycarbonate resin composition (1) described above, except that a styrene-based elastomer (C) is further used.

[0146] [Molded article of polycarbonate resin composition (2)] In the same manner as the molded article of the polycarbonate resin composition (1), a molded article made of the polycarbonate resin composition (2) can be obtained. The resulting molded article can be used for members that require the same transparency, rigidity, and further scratch resistance and weather resistance as the molded article of the polycarbonate resin composition (1). The applications where it can be preferably used are the same.

Examples

[0147] Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited by these examples. Note that the characteristic values in each example were determined according to the following procedures. "wt%" in the table indicates "mass%".

[0148] 1. 1 1H-NMR measurement: Measurement of the molar ratio of each structural unit constituting the polycarbonate (co)polymer Using a nuclear magnetic resonance (NMR) measurement apparatus (manufactured by JEOL Ltd.; JNM-AL500), 1 1H-NMR measurement was performed, and the molar ratios of the structural unit (b1) represented by formula (1), the structural unit (b2) represented by formula (2), the structural unit (b3) represented by formula (3), and other carbonate structural units (X) were calculated.

[0149] 2. Measurement of viscosity average molecular weight Using an Ubbelohde viscometer, the viscosity of a methylene chloride solution (concentration: g / l) at 20 °C was measured, and the intrinsic viscosity [η] was determined therefrom. The viscosity average molecular weight (Mv) was calculated using the following formula (Schnell formula).

Equation

[0150] 3. Measurement of Refractive Index and Abbe Number of Polycarbonate (Co) Polymer, Polycarbonate Resin, and Styrene Elastomer The refractive index of the resin was measured as follows. Using a METRICON model 2010 / M PRISM COUPLER as the refractive index measuring device, the refractive indices at wavelengths of 785 nm, 594 nm, and 407 nm (H line) were measured. Based on these measured values, the refractive indices at 486.1 nm (nF), 589.3 nm (nD), and 656.3 (nC) were calculated from the regression curve according to Cauchy's dispersion formula. As the measurement sample, the resin was press-molded at 220 °C to produce a plate with a thickness of 1 mm, which was used as the measurement test piece.

[0151] 4. Measurement of Refractive Index and Abbe Number of Glass Filler The refractive index of the glass filler was measured in accordance with the immersion method of JIS K7142:2014, Method B. The Abbe number was calculated from the obtained refractive index.

[0152] 5. Measurement of Glass Transition Temperature Tg of Polycarbonate (Co) Polymer and Polycarbonate Resin Using a polycarbonate resin, differential scanning calorimetry (DSC) was performed using a DSC-2910 thermal analysis system manufactured by TA Instruments Co., Ltd. in accordance with JIS K 7121:2012 under a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) at a heating rate of 20 °C / min. As the glass transition temperature Tg, the midpoint glass transition temperature of the point where a straight line equidistant in the vertical axis direction from the straight lines extending the baseline on the high-temperature side and the baseline on the low-temperature side in the DSC curve intersects the curve of the stepwise change part of the glass transition was determined. As the number of glass transition temperatures, the number of stepwise changes in the DSC curve was determined. When one glass transition temperature was measured, the measured value was described in the table.

[0153] 6. Measurement of Haze Value The haze value was measured for a 1-mm thick sample in accordance with ASTM D1003 using an NDH sensor manufactured by Nippon Denshoku Industries Co., Ltd.

[0154] 7. Method for Measuring Charpy Impact Strength: Evaluation of Impact Resistance After drying the pellets of the produced resin composition at 100 °C for 5 hours, dumbbell test pieces for mechanical property evaluation (total length: 169 mm, length / width of narrow parallel part: 80 mm / 10 mm, length / width of wide parallel part: 35 mm / 20 mm, thickness: 3 mm) were injection molded at a cylinder temperature of 280 °C and a mold temperature of 80 °C. From the straight part of the dumbbell test piece, strip-shaped notchless test pieces with a length of 80 mm, a width of 10 mm, and a thickness of 3 mm were cut out. Further, notched test pieces with a notch (r = 0.25 mm ± 0.05 mm) applied by post-processing were also prepared. In accordance with ISO 179-1:2010, using the notched test pieces and notchless test pieces, the Charpy impact strength at 23 °C was measured with a Charpy impact tester (Charpy impact tester, model 611, manufactured by Toyo Seiki Seisaku-sho, Ltd.).

[0155] [Manufacture of Aliphatic Polycarbonate Copolymer (B n ) <Production Example 1: Production of PC1> Into a reaction vessel equipped with a stirring device, a distillation apparatus, and a decompression device, 87.69 g (0.60 mol) of isosorbide (ISB) and 86.53 g (0.60 mol) of 1,4-cyclohexanedimethanol (CHDM) as monomer raw materials, 269.64 g (1.26 mol) of diphenyl carbonate as a carbonic acid diester, 1.44 mL of a 15 wt% aqueous solution of tetramethylammonium hydroxide, and 24 μL of a 0.1 mol / L aqueous solution of sodium hydroxide were charged. After purging the system with nitrogen, the contents were melted at 140 °C. After stirring for 30 minutes, while gradually reducing the pressure, the internal temperature was raised to 180 °C, and the reaction was carried out at 13.3 kPa for 30 minutes to distill off the generated phenol. Subsequently, while maintaining the same pressure, the temperature was continuously raised, and the reaction was carried out at 190 °C for 30 minutes, 200 °C for 30 minutes, 210 °C for 30 minutes, and 220 °C for 60 minutes to distill off the phenol. The pressure was slowly reduced to 133 Pa or less at 220 °C, and this state was maintained for 30 minutes. Then, the degree of vacuum was further increased. After reaching 1 mmHg or less, the reaction was carried out with stirring for 4 hours. Thereafter, 16 μL of a toluene solution containing 10 volume% of butyl p-toluenesulfonate as a deactivator was added, and then stirred at 240 °C and 13.3 kPa for 20 minutes to obtain the target aliphatic polycarbonate copolymer (PC1). The physical properties and characteristics shown in Table 1 for PC1 were measured. Based on the measured haze value, the transparency was evaluated according to the following criteria. Transparent: The haze value at a thickness of 1 mm is less than 1.5 Cloudy: The haze value at a thickness of 1 mm is 1.5 or more The results are shown in Table 1.

[0156] <Production Examples 2 to 10: Production of PC2 to PC10> Polymerization was carried out under the same conditions as for PC1 except that the monomer raw materials and their molar ratios were as shown in Table 1, and the physical properties and characteristics were measured. The results are shown in Table 1.

[0157]

Table 1

[0158] The abbreviations in the table are as follows. *1 ISB: Isosorbide *2 CHDM: 1,4-Cyclohexanedimethanol *3 TCDDM: Tricyclodecane dimethanol *4 BPA: Bisphenol A

[0159] [Reference Examples 1-1 to 1-10, Comparative Reference Examples 1-1 to 1-3] The polycarbonate resins (PC1 to PC10) obtained in Production Examples 1 to 10 were blended in the composition shown in Table 2, supplied to an extruder [Model name: Micro Twin Screw compounder (manufactured by DSM)], and melt-kneaded under the condition of a resin temperature of 250°C. No transesterification catalyst was used during the melt-kneading. Using the obtained composition, dumbbell pieces were obtained by injection molding with an injection molding machine [Model name: Injection Molding Machine (manufactured by Explore)] under the conditions of a resin temperature of 250°C and a mold temperature of 100°C. The obtained dumbbell pieces were press-molded again at 220°C to produce a plate with a thickness of 1 mm, which was used as a measurement test piece. For the obtained molded products, the physical properties shown in Table 2 were measured. Based on the measured haze value, the transparency was evaluated according to the following criteria. Transparent: Haze value at 1 mm thickness is less than 1.5 Cloudy: Haze value at 1 mm thickness is 1.5 or more Regarding compatibility, when one glass transition temperature was measured, it was evaluated as compatible. When two or more glass transition temperatures were measured, it was evaluated as incompatible. The results are shown in Table 2.

[0160]

Table 2

[0161] Generally, different types of polymers tend to have low compatibility. Surprisingly, the ISB-CHDM copolymer and the ISB-TCDDM copolymer showed complete compatibility with a single glass transition temperature and transparency over a wide range of copolymer composition ratios and mixing ratios. In addition, the ISB-CHDM-TCDDM copolymer also showed complete compatibility with the ISB-CHDM copolymer and the ISB-TCDDM copolymer. By adjusting the copolymer composition ratio and / or the mixing ratio, it was also possible to set the refractive index of the copolymer mixture over a wide range.

[0162] [Production Examples 11-12: Production of Glass Fibers] Glass fibers GF1 and GF2 were produced from a raw material glass having the composition (mass %) shown in Table 3. Specifically, a raw material mixture (raw material batch) prepared and mixed to have the target composition was charged into a melting furnace and heated to form a glass melt. The glass melt was supplied to a bushing, and continuously drawn from the tip of the bushing nozzle and rapidly cooled to be formed into filaments. An aminosilane and urethane adjusted to a total amount of 0.5 mass% with respect to the glass filament were attached to the filaments as a binder, and glass fibers having an average fiber diameter of 10 μm with filaments bundled every predetermined number were produced. For the obtained glass fibers GF1 and GF2, the characteristics shown in Table 3 were measured. The results are shown in Table 3.

[0163]

Table 3

[0164] [Production Examples 13-14: Production of Glass Cloth] The glass fiber GF1 obtained in Production Example 11 was woven into a cloth by a plain weave method to produce a glass cloth GC1 (Production Example 13). A glass cloth GC2 was produced (Production Example 14) in the same manner as in Production Example 13, except that the glass fiber GF2 obtained in Production Example 12 was used instead of the glass fiber GF1. The refractive indices (nF) of the obtained glass cloths GC1 and GF2 for light with a wavelength of 486.1 nm, the refractive indices (nD) for light with a wavelength of 589.3 nm, the refractive indices (nC) for light with a wavelength of 656.3 nm, the details of each refractive index, and the results of measuring the Abbe number are shown in Table 4.

[0165]

Table 4

[0166] Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-4 [Manufacture of Glass Fiber Reinforced Polycarbonate Resin Molded Product] Using the polycarbonate resin obtained in Production Examples 1 to 10 and the glass filler (glass fiber) obtained in Production Examples 11 to 12, compounds were prepared under the composition (parts by mass) shown in Table 5 and the following conditions to produce polycarbonate resin composition molded articles of Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-4. The glass fiber used at this time was used as chopped strands obtained by cutting the glass long fibers obtained by the production of glass fiber to a length of 3 to 5 mm. Each polycarbonate resin and each glass fiber were blended at the ratios shown in Table 5, supplied to an extruder [Model name: Micro Twin Screw compounder (manufactured by DSM)], melt-kneaded at an extrusion temperature of 170°C to 250°C, and injection molded under the conditions of a cylinder temperature of 170°C to 250°C and a mold temperature of 30 to 120°C using an injection molding machine [Model name: Injection Molding Machine (manufactured by Explore)] to obtain dumbbell pieces. The obtained dumbbell pieces were press-molded again at 150 to 220°C to produce a plate with a thickness of 1 mm, which was used as a measurement test piece. For the obtained molded products, the characteristics shown in Table 5 were measured. Based on the measured haze values, the transparency was evaluated according to the following criteria. Transparent: The haze value at a thickness of 1 mm is less than 15.0 Cloudy: The haze value at a thickness of 1 mm is 15.0 or more The results are shown in Table 5.

[0167]

Table 5

[0168] Examples 1-15 to 1-17, and Comparative Examples 1-5 to 1-6 [Manufacture of Glass Cloth Reinforced Polycarbonate Resin Molded Body] Using the polycarbonate resin obtained in Production Examples 1 to 10, a polycarbonate resin sheet was obtained by press molding. A melt kneaded product of the polycarbonate resin having the composition shown in Table 6 was pressurized at 250 ° C. and 5 MPa for 5 minutes using a vacuum press machine (Model 11FD, Imoto Seisakusho Co., Ltd.) and using a 1 mm aluminum spacer. Then, it was cooled to obtain a sheet having a thickness of 1 mm. The obtained polycarbonate resin sheet (hereinafter also referred to as PC sheet) and the glass cloth GC1 obtained in Production Example 13 or the glass cloth GC2 obtained in Production Example 14 in the number shown in Table 6 were alternately laminated and heat pressed at 250 ° C. using a vacuum press machine (Model 11FD, Imoto Seisakusho Co., Ltd.) to produce a glass cloth reinforced polycarbonate resin molded product. In the case of one glass cloth, it was laminated in the configuration of PC sheet / GC / PC sheet, and the thickness of the glass cloth reinforced polycarbonate resin molded product was 0.2 mm. In the case of three glass cloths, it was laminated in the configuration of PC sheet / GC / PC sheet / GC / PC sheet / GC / PC sheet, and the thickness of the glass cloth reinforced polycarbonate resin molded product was 0.6 mm. For the obtained molded product, the physical properties shown in Table 6 were measured. Based on the measured haze value, the transparency was evaluated according to the following criteria. Transparent: Haze value at 1 mm thickness is less than 15.0 Cloudy: Haze value at 1 mm thickness is 15.0 or more The results are shown in Table 6.

[0169]

Table 6

[0170] Reference Examples 2-1 to 2-10, Comparative Reference Examples 2-1 to 2-5 [Manufacture of Polycarbonate Resin Molded Products] A polycarbonate resin molded product was produced in the same manner as in Reference Example 1-1, except that a styrene-based elastomer was further blended with the composition shown in Table 8. (Styrene-based Elastomer) As the styrene-based elastomer, the following hydrogenated styrene-based thermoplastic elastomer (SEBS) was used. TPE-1: Tough Tech H1221 (manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene mass ratio = 12 / 88, unmodified) TPE-2: Tough Tech H1052 (manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene mass ratio = 20 / 80, unmodified) TPE-3: A mixture of 53% by mass of Tough Tech H1052 (manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene mass ratio = 20 / 80, unmodified) and 47% by mass of Tough Tech H1041 (manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene mass ratio = 30 / 70, unmodified), melt-kneaded at 280°C TPE-4: Tough Tech H1041 (manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene mass ratio = 30 / 70, unmodified) TPE-5: Tough Tech H1051 (manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene mass ratio = 42 / 58, unmodified) TPE-6: Tough Tech MP10 (manufactured by Asahi Kasei Corporation, styrene / ethylene-butylene mass ratio = 30 / 70, amine-modified) The physical properties and characteristics of the styrene-based elastomers used are shown in Table 7.

[0171]

Table 7

[0172] The transparency of the obtained molded products was evaluated. The results are shown in Table 8.

[0173]

Table 8

[0174] Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-4 [Manufacture of Glass Fiber Reinforced Polycarbonate Resin Molded Products] A glass fiber reinforced polycarbonate resin molded product was produced in the same manner as in Example 1-1, except that a styrene-based elastomer was further blended with the composition shown in Table 9. The results are shown in Table 9.

[0175] Examples 2-5 to 2-6 [Manufacture of Glass Cloth Reinforced Polycarbonate Resin Molded Products] A glass cloth reinforced polycarbonate resin molded product was produced in the same manner as in Example 1-15, except that a styrene-based elastomer was further blended with the composition shown in Table 9. The results are shown in Table 9.

[0176]

Table 9

Claims

1. A glass filler (A), and An aliphatic polycarbonate copolymer (B) containing a structural unit (b1) represented by the following formula (1) and one or more selected from a structural unit (b2) represented by the following formula (2) and a structural unit (b3) represented by the following formula (3) ｎ ), and containing a polycarbonate resin component (B) containing two or more kinds thereof A polycarbonate resin composition (1) in which the difference in refractive index with respect to light having a wavelength of 589.3 nm between the glass filler (A) and the polycarbonate resin component (B) is 0.0150 or less. 【Chemical 1】

2. The polycarbonate resin composition (1) according to claim 1, wherein the polycarbonate resin component (B) satisfies one or more of the following conditions (i) and (ii). (i) The haze value is less than 1.5 at a thickness of 1 mm (ii) It has one glass transition temperature

3. The polycarbonate resin composition (1) according to claim 1 or 2, obtained by melt-kneading under conditions that do not promote transesterification.

4. The glass filler (A) is Silicon dioxide (SiO 2 ) having a content of 50% by mass or more and 70% by mass or less Aluminum oxide (Al 2 O 3 ) having a content of more than 0% by mass and 25% by mass or less 8 mass% or more and 25 mass% or less of boron oxide (B 2 O 3 ), Magnesium oxide (MgO) in an amount of more than 0% by mass and 10% by mass or less Calcium oxide (CaO) in an amount of more than 0% by mass and 20% by mass or less Sodium oxide (Na 2 O) in an amount of more than 0% by mass and 5% by mass or less Potassium oxide (K 2 O) in an amount of more than 0% by mass and not more than 5% by mass, and Titanium oxide (TiO with more than 0% by mass and 10% by mass or less 2 ) is included, and The total content of the silicon dioxide (SiO ２ ) and the aluminum oxide (Al ２ O ３ ) in the glass filler (A) is more than 50% by mass and 90% by mass or less, and the total content of the sodium oxide (Na ２ O), the potassium oxide (K ２ O) and the lithium oxide (Li ２ O) is more than 0% by mass and 15% by mass or less. The polycarbonate resin composition (1) according to any one of claims 1 to 3.

5. The polycarbonate resin composition (1) according to any one of claims 1 to 4, having a haze value at a thickness of 1 mm of 15.0 or less.

6. A molded article of the polycarbonate resin composition (1) according to any one of claims 1 to 5.

7. The molded article according to claim 6, which is a sheet.

8. A method for producing the polycarbonate resin composition (1) according to any one of claims 1 to 5, including a step (step A) of mixing the glass filler (A) and the polycarbonate resin component (B).

9. In the step A, at least one of the types of the structural unit (b1) represented by the formula (1), the structural unit (b2) represented by the formula (2), and the structural unit (b3) represented by the formula (3), the composition ratio of the structural units, and the blending ratio of two or more of the aliphatic polycarbonate copolymers (B ｎ ), is adjusted so that the difference in refractive index with respect to light having a wavelength of 589.3 nm between the glass filler (A) and the polycarbonate resin component (B) is 0.0150 or less. A method for producing the polycarbonate resin composition (1) according to claim 8.

10. A glass cloth (A'), and An aliphatic polycarbonate copolymer (B) containing a structural unit (b1) represented by the following formula (1) and at least one selected from a structural unit (b2) represented by the following formula (2) and a structural unit (b3) represented by the following formula (3) ｎ ), which is formed by laminating a polycarbonate resin component layer (B') containing two or more of them. A laminate in which the difference in refractive index with respect to light having a wavelength of 589.3 nm between the glass cloth (A') and the polycarbonate resin component layer (B') is 0.0150 or less. [Chemical 2]

11. The laminate according to claim 10, having a thickness of 0.05 mm or more and 5 mm or less.

12. A glass filler (A), A polycarbonate resin component (B'') containing two or more selected from the group consisting of a structural unit (b1) represented by the following formula (1), a structural unit (b2) represented by the following formula (2), and a structural unit (b3) represented by the following formula (3), and A styrene-based elastomer (C) The polycarbonate resin composition (2) in which the differences in refractive index with respect to light having a wavelength of 589.3 nm between the glass filler (A), the polycarbonate resin component (B''), and the styrene-based elastomer (C) are each 0.0150 or less. [Chemical Formula 3]

13. The glass filler (A) is Silicon dioxide (SiO with 50% to 70% by mass 2 ) Aluminum oxide (Al 2 O 3 ) with a content of more than 0% by mass and 25% by mass or less 8 mass% or more and 25 mass% or less of boron oxide (B 2 O 3 ), magnesium oxide (MgO) in an amount exceeding 0% by mass and 10% by mass or less, calcium oxide (CaO) in an amount exceeding 0% by mass and 20% by mass or less, Sodium oxide (Na 2 O) in an amount greater than 0% by mass and not exceeding 5% by mass Potassium oxide (K 2 O) in an amount of more than 0% by mass and 5% by mass or less, and Titanium oxide (TiO 2 ) containing more than 0% by mass and up to 10% by mass, and The total content of the silicon dioxide (SiO ２ ) and the aluminum oxide (Al ２ O ３ ) in the glass filler (A) is more than 50% by mass and 90% by mass or less, and the total content of the sodium oxide (Na ２ O), the potassium oxide (K ２ O) and the lithium oxide (Li ２ O) is more than 0% by mass and 15% by mass or less. The polycarbonate resin composition (2) according to claim 12.

14. The styrene-based elastomer (C) is composed of a hard segment composed of repeating constitutional units derived from a styrene-based compound and a soft segment composed of an elastomer segment, and has an amine-modified terminal group. The polycarbonate resin composition (2) according to claim 12 or 13.

15. The styrene-based elastomer (C) is a styrene-ethylene-butylene-styrene copolymer having an amine-modified terminal group. The polycarbonate resin composition (2) according to claim 14.

16. The polycarbonate resin component (B'') is An aliphatic polycarbonate copolymer (B) containing at least one selected from the structural unit (b1) represented by the formula (1), the structural unit (b2) represented by the formula (2), and the structural unit (b3) represented by the formula (3) ｎ The polycarbonate resin composition (2) according to any one of claims 12 to 15, containing two or more of them.

17. A method for producing the polycarbonate resin composition (2) according to any one of claims 12 to 16, the method including a step of mixing the glass filler (A), the polycarbonate resin component (B''), and the styrene-based elastomer (C).

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