JP6349955B2 - Method for producing thermoplastic resin composition - Google Patents

Description

  The present invention relates to a method for producing a thermoplastic resin composition.

  Currently, thermoplastic resins such as polycarbonate resins and polyester resins and resin compositions thereof are used in containers, from the viewpoints of excellent moldability, mechanical properties, heat resistance, weather resistance, appearance, hygiene, and economy. It is used in a wide range of fields as molding materials for packaging films, home appliances, OA equipment, AV equipment, electrical / electronic parts, and automotive parts.

  The resin molded product used for these uses is required to be flame retardant. In order to make a thermoplastic resin flame retardant, it is generally known to add a flame retardant to the resin (see, for example, Patent Document 1).

  In recent years, laws such as “Act on the Promotion of Separate Collection and Recycling Related to Containers and Packaging (Container and Packaging Recycling Law)” and “Act on Promotion of Procurement of Environmental Goods by the Countries (Green Purchasing Law)” With successive enforcement, interest in material recycling technology for molded products of such thermoplastic resins and resin compositions has increased. In particular, there is an urgent need to establish a material recycling technology for PET bottles using polyethylene terephthalate (hereinafter also referred to as “PET”) resin, whose usage is rapidly increasing. In addition, with the widespread use of optical recording medium products (optical discs) made of polycarbonate (hereinafter also referred to as “PC”) resin such as CD, CD-R, DVD, and MD, they are discharged during molding. Studies have been made on methods for reusing scrap materials and methods for reusing polycarbonate resin obtained after peeling off a reflective layer, a recording layer, and the like from an optical disc that has become waste.

  When re-molding a resin obtained by pulverizing a molded product of PC resin such as crystalline terephthalate-based polyester and optical disks such as used PET bottles collected from the market, especially by injection molding. In this case, in order to be applicable to various molded products, the resin is required to have high fluidity during molding as a characteristic of the resin.

  Furthermore, when the resin composition uses a polyester resin and a polycarbonate resin for constituent members such as home appliances and OA devices, high impact strength is required.

JP 2012-136558 A

  However, in a system in which a crystalline polyester resin such as PET and a polycarbonate resin are melt-mixed, it is difficult to achieve both the fluidity during molding and the impact resistance of the molded product.

  The present invention has been made in consideration of the above circumstances, and its purpose is to have high flame retardancy, high fluidity during injection molding, and high impact strength of the molded product. It is providing the manufacturing method of the thermoplastic resin composition containing crystalline polyester resin and polycarbonate resin from which a resin composition is obtained.

  The present inventors have conducted intensive research to solve the above problems. As a result, it was found that the above-mentioned problems were solved by the thermoplastic resin composition obtained by the following production method, and the present invention was completed; 100 parts by weight of a crystalline polyester resin, an organic compound and an inorganic compound A step (1) of obtaining a polyester resin mixture by melt-kneading 0.5 to 5 parts by weight of a nucleating agent comprising a mixture using an extruder, and the polyester resin mixture, polycarbonate resin, flame retardant, and toughening agent And a step (2) of mixing a thermoplastic resin composition.

  According to the present invention, a crystalline polyester resin and a nucleating agent composed of an organic compound and an inorganic compound are melt-kneaded in advance to obtain a resin composition that satisfies both flame retardancy and high fluidity. It is done. Moreover, the impact resistance of the molded article of the resin composition can be improved by previously melt-kneading the crystalline polyester resin and a nucleating agent comprising a mixture of an organic compound and an inorganic compound.

  In one embodiment of the present invention, 100 parts by weight of a crystalline polyester resin and 0.5 to 5 parts by weight of a nucleating agent composed of an organic compound and an inorganic compound are melt-kneaded using an extruder to obtain a polyester resin mixture. It is a manufacturing method of the thermoplastic resin composition which has a process (1) and the process (2) which mixes the said polyester resin mixture, a polycarbonate resin, a flame retardant, and a toughening agent.

  Hereinafter, embodiments of the present invention will be described.

  The present invention is characterized in that a crystalline polyester resin and a nucleating agent composed of an organic compound and an inorganic compound are previously melt-kneaded and then other components such as a flame retardant are added.

  As described above, if a crystalline polyester resin such as PET is to be molded again by recycling, it is difficult to achieve both the flow characteristics during molding and the impact resistance (toughness) of the molded product.

  The present inventors speculated that crystallization of the crystalline polyester resin had an adverse effect on the fluidity and impact resistance as a cause of the decrease in fluidity when the crystalline polyester resin was used.

  Therefore, as a result of diligent investigation, the crystalline polyester and a nucleating agent composed of an organic compound and an inorganic compound (hereinafter simply referred to as a nucleating agent) are previously melt-kneaded (primary kneading) and then other components are melt-mixed. It has been found that it is possible to achieve both fluidity and impact resistance.

  Although the detailed mechanism by which the thermoplastic resin composition obtained by the production method of the present invention has improved both fluidity and impact resistance is unknown, it is considered as follows. The mechanism below does not limit the present invention.

  Due to the presence of the inorganic compound in the nucleating agent, the number of nuclei of the polyester resin crystal increases, and a large number of small and fine crystals can be formed. The organic compound in the nucleating agent enters the molecular chain of the crystalline polyester resin and suppresses the folding (= crystallization) of the molecular chain of the crystalline resin, so that the crystal cannot grow to a certain size. Conceivable. Therefore, it is considered that the crystal of the polyester resin becomes small and uniform by previously melt-mixing the nucleating agent composed of an organic compound and an inorganic compound and the crystalline polyester.

  If the crystal size of the crystalline polyester resin is large, the resin becomes brittle and the toughness decreases. On the contrary, when the crystalline polyester resin has small and uniform crystals, the toughness increases. In addition, the smaller the crystal size, the more slowly the viscosity rises during the temperature lowering process. That is, when molding the resin by pouring it into the mold (corresponding to the temperature lowering process), the more slowly the viscosity rises, the more the resin is in the mold. Go around.

  For this reason, it is considered that the toughness and fluidity of the resin composition are improved by previously melt-mixing the nucleating agent and the crystalline polyester.

  Even if the crystalline polyester resin and the nucleating agent are melt-mixed together with other additive components (without primary kneading), it is not possible to achieve both improvement in resin fluidity and impact resistance (Comparative Example 2 described later). reference). This is due to the fact that even if it is added together and melt-mixed with polycarbonate resin, etc., the opportunity for reaction between the crystalline polyester and the nucleating agent is reduced, and crystallization is not effectively suppressed. Conceivable.

  Furthermore, by setting it as the structure of this invention, high flame retardance is also maintained with compatibility of the said impact resistance and high fluidity | liquidity.

  Therefore, the thermoplastic resin composition obtained by the production method of the present invention has a complicated structure and is used for parts for various applications such as office equipment, information / communication equipment, electrical / electronic equipment, and household appliances. can do. In addition, when using recycled resin such as polyester resin and polycarbonate resin obtained from recovered molded products and end materials at the time of molding, it has excellent flame retardancy, such as elastic modulus, bending strength, impact strength, etc. A resin composition excellent in mechanical strength and a molded product can be obtained.

  Hereinafter, each step will be described.

<Step (1)>
In the step (1), 100 parts by weight of the crystalline polyester resin and 0.5 to 5 parts by weight of the nucleating agent are melt kneaded using an extruder to obtain a polyester resin mixture.

  Prior to the melting / kneading treatment, a premixing treatment in which the crystalline polyester resin and the nucleating agent are mixed in advance may be performed. Examples of the mixer used for the preliminary mixing include mixers such as a V-type mixer, a ribbon mixer, a nauter mixer, and a super mixer. In addition, after the premixing treatment, it is preferable to sufficiently dry the mixture from the viewpoint of suppressing the hydrolysis reaction of the thermoplastic polyester resin before the melt kneading treatment. Although it does not specifically limit as a drying temperature in this case, It is preferable that it is 70-100 degreeC. Moreover, although it does not specifically limit about drying time, It is preferable that it is 2 to 6 hours. Further, it is preferable to perform the drying under reduced pressure at the time of drying, because the drying is more likely to proceed.

  The melt kneading is performed using an extruder. Since high shearability can be imparted and the raw materials can be mixed uniformly, it is preferable to use a multi-screw kneading extruder and more preferably a bi-screw kneading extruder for melt kneading. The melt kneading means kneading at a temperature higher than the temperature at which the crystalline polyester resin melts.

  In melt kneading, the cylinder temperature of the extruder is preferably 250 to 280 ° C. If the cylinder temperature is 250 ° C. or higher, the raw materials can be mixed uniformly, so that the fluidity is maintained. If the cylinder temperature is 280 ° C. or lower, the polyester resin is less likely to decompose and the impact resistance is maintained. sell. The mixing pressure is not particularly limited, but is preferably 1 to 20 MPa.

  In addition, the cylinder temperature of an extruder here refers to the temperature of the highest cylinder part, when a some temperature setting is made in the cylinder of an extruder.

  The discharge amount from the extruder at the time of melt kneading is not particularly limited, but it is preferably 10 to 100 kg / hour because melt kneading is sufficiently performed and the raw materials can be mixed uniformly. More preferably, it is carried out at ˜70 kg / hour.

The heat release heat (ΔH _A ) in the DSC melting curve of the polyester resin mixture obtained in the step (1) is 70% or less with respect to the heat release heat (ΔH _B ) in the DSC melting curve of the crystalline polyester resin (ΔH _A / ΔH _B ≦ 0.7) is preferred. ΔH A _/ ΔH _B is an index indicating the uniformity of crystal size, it is ΔH A _/ ΔH _B ≦ 0.7, the effect of suppressing crystallinity of the polyester resin is exerted more remarkably, flowable And toughness can be improved. ΔH _A / ΔH _B is more preferably 0.5 or less. The lower limit of ΔH _A / ΔH _B is not particularly limited, but is usually 0 or more.

The method of [Delta] H _A is not particularly limited, for example, cylinder temperature, the kind of nucleating agent, by appropriately controlling the addition amount, it is possible to control the [Delta] H _A.

  Further, the half width (Δa) in the DSC melting curve of the polyester resin mixture obtained in the step (1) is 70% or less (Δa / Δb) with respect to the half width (Δb) in the DSC melting curve of the crystalline polyester resin. ≦ 0.7) is preferred. The full width at half maximum in the DSC melting curve is an index indicating the uniformity of crystal size. The smaller the full width at half maximum, the more uniform the crystal size. That is, as Δa / Δb is smaller, the crystal size of the mixture is more uniform than the crystal size of the crystalline polyester resin. When Δa / Δb ≦ 0.7, the crystallinity of the polyester resin is suppressed. The effect is exhibited more remarkably, and fluidity and toughness can be improved. The lower limit of Δa / Δb is not particularly limited, but is usually 0.4 or more.

  Although the control method of (DELTA) a is not specifically limited, For example, (DELTA) a can be controlled by controlling appropriately cylinder temperature, the kind of nucleating agent, addition amount, etc.

  The polyester resin mixture is obtained by melt-kneading 100 parts by weight of a crystalline polyester resin and 0.5 to 5 parts by weight of a nucleating agent. When the nucleating agent exceeds 5 parts by weight with respect to 100 parts by weight of the crystalline polyester resin, the toughness, fluidity and flame retardancy are lowered. This is because when the nucleating agent exceeds 5 parts by weight, a large amount of nuclei are united, resulting in a decrease in the number of nuclei and an increase in crystals, resulting in a decrease in fluidity and toughness. The nucleating agent itself becomes a crack point, which is considered to be due to a decrease in toughness. On the other hand, when the nucleating agent exceeds 5 parts by weight, the nucleating agent itself is likely to burn, so that it is considered that the flame retardancy also decreases. When the nucleating agent is less than 0.5 parts by weight, toughness and fluidity, particularly fluidity, are lowered. This is considered to be because when the nucleating agent is less than 0.5 parts by weight, the crystallization suppressing effect of the nucleating agent on the crystalline polyester resin cannot be obtained.

  The molten polyester resin kneaded material obtained by melt kneading as described above is preferably cooled after being injected. The cooling treatment is not particularly limited. For example, the polyester resin kneaded material is immersed in water at 0 to 60 ° C. and cooled with water, the method of cooling with a gas of −40 to 60 ° C., and the metal at −40 to 60 ° C. is contacted. Or the like can be used.

  Moreover, it is preferable to fully dry a mixture from a viewpoint of suppressing the hydrolysis reaction of a thermoplastic polyester resin before the below-mentioned process (2). Although it does not specifically limit as a drying temperature in this case, It is preferable that it is 70-100 degreeC. Moreover, although it does not specifically limit about drying time, It is preferable that it is 2 to 6 hours. Further, it is preferable to perform the drying under reduced pressure at the time of drying, because the drying is more likely to proceed.

(Crystalline polyester resin)
The crystalline polyester resin is not particularly limited, but is preferably an aromatic polyester having a structure in which an aromatic dicarboxylic acid or an ester derivative component thereof and a diol component such as an aliphatic diol or an alicyclic diol are linked by an ester reaction. is there. As the polyester resin, for example, those obtained by polycondensing an aromatic dicarboxylic acid or an ester derivative component thereof with an aliphatic diol or alicyclic diol by a known method can be used.

  Examples of aromatic dicarboxylic acids include, but are not limited to, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2 '-Biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid Acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4 '-P-terphenylenedicarboxylic acid and 2,5-pyridinedicarbo Such as acid, and the like.

  Examples of the aliphatic diol include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and triethylene glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol.

  Both of these aromatic dicarboxylic acids and aliphatic diols or alicyclic diols can be used alone or in combination of two or more. Furthermore, if the polyester resin which comprises the resin composition of this invention is 1 mol% or less based on all the structural units, for example, glycerol, a trimethylol propane, a pentaerythritol, trimellitic acid, pyromellitic acid, etc. 3 It may have a structural component derived from a functional or higher monomer.

  The crystalline polyester resin refers to a resin having a clear endothermic peak rather than a stepwise endothermic change in differential scanning calorimetry (DSC). Specifically, the clear endothermic peak means that the half-value width of the endothermic peak is within 15 ° C. when measured at a heating rate of 10 ° C./min in the differential scanning calorimetry (DSC) described in the examples. It means a peak.

  The crystalline polyester resin is not particularly limited as long as it is defined above. For example, for a resin having a structure in which other components are copolymerized on the main chain of the crystalline polyester resin, the resin is clear as described above. If it shows an endothermic peak, it corresponds to the crystalline polyester resin referred to in the present invention.

  Specific examples of the crystalline polyester resin include polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate. The crystalline polyester resin is preferably at least one of polyethylene terephthalate and polybutylene terephthalate because it is widely used and is easy to recycle into a resin having high fluidity and high impact resistance by the method of the present invention. .

  The intrinsic viscosity of the crystalline polyester resin is not particularly limited, but is preferably 0.4 to 1.5 dl / g, more preferably 0.4 to 1.2 dl / g, considering impact resistance and fluidity. Preferably, it is the range of 0.7-1.0 dl / g. The intrinsic viscosity is a value when measured at 30 ° C. using a phenol / tetrachloroethane (mass ratio: 1/1) mixed solvent in accordance with JIS K7367-5 (2000).

  As the crystalline polyester resin, a resin piece obtained by pulverizing a discarded polyester resin product can be used. In particular, a pulverized product of a PET product such as a used waste PET bottle can be suitably used as the PET having an intrinsic viscosity in the above range. It is possible to use resin pieces obtained by pulverizing bottles, sheets, clothes, and molding wastes and fiber wastes produced when molding these molded products into appropriate sizes, which are PET products collected as waste. Among them, a crushed product of a beverage bottle that is large in quantity can be suitably used. In general, PET bottles are recycled into transparent clear flakes having a size of 5 to 10 mm after separating and collecting, through a process of removing different materials, crushing, and washing. Usually, the range of intrinsic viscosity of such clear flake is approximately 0.60 to 0.80 dl / g.

  The polyester resin piece of the discarded polyester resin product can be obtained by pulverizing, washing, drying, kneading at a temperature of 180 ° C. or higher and 260 ° C. or lower, cooling and pulverizing. Virgin (unused) polyester resins are commercially available in the form of pellets, but these are pressed at a temperature above the glass transition temperature, or once melted with an extruder or the like, and the molten strand is turned into a roller in cooling water. It can be used as a resin piece by crushing through and cutting with a normal pelletizer.

  By using the polyester resin as the resin piece, the supply to the kneader is facilitated during the production of the resin composition, and the load on the kneading apparatus is reduced in the kneading until melting. As a shape of the polyester resin piece, for example, a flake shape, a block shape, a powder shape and a pellet shape are preferable, and a particularly preferable shape is a flake shape. A preferable maximum length of the resin piece is 30 mm or less, more preferably 20 mm, and still more preferably 10 mm or less. Kneading is possible even if a resin piece having a maximum length exceeding 30 mm is contained, but it may be clogged in the supply process, which is not preferable. However, since it can be prevented by improving the supply device, there is no particular limitation as long as the object of the present invention is not impaired.

(Nuclear agent)
A nucleating agent consists of an inorganic compound and an organic compound. A nucleating agent refers to what accelerates | stimulates the crystal growth of crystalline polyester resin, and a solid thing is specifically preferable at normal temperature (25 degreeC). It is preferable that at least the inorganic compound has a function as a nucleating agent (an inorganic compound that can be a nucleating agent for a crystalline polyester resin alone), and both the organic compound and the inorganic compound are nucleating agents for a crystalline polyester resin. It is preferable.

  A mixture of an inorganic compound and an organic compound may be sufficient as a nucleating agent, and the form which surface-treated the inorganic compound with the organic compound may be sufficient as it. Preferably, the nucleating agent is a mixture of inorganic and organic compounds.

  When the organic compound and the inorganic compound coexist as the nucleating agent, the organic compound exists near the inorganic compound. As a result, as described above, it is considered that small and fine crystals formed by the presence of the inorganic compound in the nucleating agent suppress the crystal growth by the presence of the organic compound and improve the toughness and fluidity of the resin composition. It is done.

  The inorganic compound used for the nucleating agent is not particularly limited, but metal oxides such as tin oxide, magnesium oxide, zinc oxide, calcium oxide, aluminum oxide, titanium oxide, and silica; magnesium carbonate, magnesium hydroxide Group 2 element compounds such as calcium carbonate, calcium sulfide, calcium sulfate, barium sulfate; clay minerals such as talc, kaolinite, montmorillonite, mica, sepiolite, wollastonite, zonotolite; carbon such as graphite and carbon black Can be mentioned. Among them, the inorganic compound is composed of calcium carbonate, tin oxide, magnesium oxide, silica, talc, magnesium hydroxide, sepiolite, wollastonite, and zonotlite because of its high effectiveness as a nucleating agent for crystalline polyester resins. It is preferable that at least one selected from the group consisting of calcium carbonate, silica, talc, silica, and magnesium hydroxide as a main component. Here, including as a main component indicates that 80% by weight or more is contained in 100% by weight of the inorganic compound, preferably 90% by weight or more, and more preferably 100% by weight.

  An inorganic compound may be used individually by 1 type, and may be used together 2 or more types.

  The shape of the inorganic compound is not particularly limited, and examples thereof include particles, plates, and needles.

  The average particle size (D50) obtained by the laser diffraction / scattering particle size distribution measurement method of the inorganic compound is preferably 5 μm or less, more preferably 0.1 to 1 μm, since the effect as a nucleating agent is more exhibited. More preferably.

  Although it does not specifically limit as an organic compound used for a nucleating agent, Aromatic carboxylic acid or dicarboxylic acid, aliphatic carboxylic acid or dicarboxylic acid, or these metal salts (lithium salt, sodium salt, potassium salt, Calcium salts, magnesium salts, barium salts, etc., preferably sodium salts, calcium salts); phosphoric acid compounds; salicylates (sodium salts, potassium salts, zinc salts, etc.) and the like.

  As aromatic carboxylic acid, Preferably it is C7-30, More preferably, C7-11 aromatic carboxylic acid can be mentioned, For example, benzoic acid, toluic acid, etc. can be mentioned.

  As aromatic dicarboxylic acid, Preferably C8-30, More preferably, C8-12 aromatic dicarboxylic acid can be mentioned, For example, a terephthalic acid etc. can be mentioned.

  Examples of the aliphatic carboxylic acid include linear or branched aliphatic carboxylic acids having preferably 12 to 30 carbon atoms, such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, Examples include octacosanoic acid.

  Preferred examples of the aliphatic dicarboxylic acid include linear or branched aliphatic dicarboxylic acids having 2 to 30 carbon atoms, such as oxalic acid.

  Specific examples of metal salts of carboxylic acids include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, sodium toluate, lithium terephthalate, sodium terephthalate, terephthalate Potassium acid, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium palmitate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate, Examples include sodium montanate, calcium montanate, sodium octacosanoate, calcium octacosanoate, and calcium oxalate.

  Examples of the phosphoric acid compound include sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate, lithium-2,2′-methylenebis (4 Mention may be made of phosphate metal salts such as 6-ditert-butylphenyl) phosphate.

  Among them, since the effectiveness as a nucleating agent for the crystalline polyester resin is high, the organic compound is a metal salt of a carboxylic acid (aromatic carboxylic acid, aromatic dicarboxylic acid, aliphatic carboxylic acid, aliphatic dicarboxylic acid), And at least one selected from the group consisting of phosphate compounds as a main component, sodium benzoate, sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate, sodium bis ( It is more preferable that at least one selected from the group consisting of 4-tert-butylphenyl) phosphate, sodium palmitate, and sodium stearate as a main component. Here, including as a main component means that 80% by weight or more is contained in 100% by weight of the organic compound, preferably 90% by weight or more, and more preferably 100% by weight.

  An organic compound may be used individually by 1 type, and may be used together 2 or more types.

  The mixing weight ratio of the inorganic compound and the organic compound in the nucleating agent is not particularly limited, but since the inorganic compound has a function as a main nucleating agent, the inorganic compound: organic compound = 2-50. : 1 is preferable, and 5 to 20: 1 is more preferable.

  Although mixing of an inorganic compound and an organic compound is not specifically limited, Both can be mixed using a ball mill, a Henschel mixer, a bead mill, spray drying, etc. Moreover, you may mix an organic compound simultaneously at the time of the grinding | pulverization of an inorganic compound.

  A commercially available product may be used as the nucleating agent, and examples of the commercially available product include BRUGGOLEN (registered trademark) P250 (manufactured by Bruggemann Chemical).

  The amount of the nucleating agent added in 100 parts by weight of the crystalline polyester resin in the step (1) is 0.5 to 5 parts by weight. When the addition amount of the nucleating agent is less than 0.5 parts by weight, the effect of suppressing crystallization cannot be obtained. Moreover, when the addition amount of the nucleating agent is more than 5.0 parts by weight, a large amount of nuclei are united, and as a result, the number of nuclei is reduced and the crystal becomes larger, Since it becomes a crack point, toughness decreases. Moreover, since the nucleating agent itself contains a flammable substance, the flame retardancy also decreases. The addition amount of the nucleating agent is preferably 3 parts by weight or less with respect to 100 parts by weight of the crystalline polyester resin from the viewpoint of improving toughness.

<Step (2)>
In step (2), the polyester resin mixture obtained in step (1) (hereinafter also simply referred to as a polyester resin mixture), polycarbonate resin, flame retardant and toughening agent are mixed. The mixing is preferably performed by melt kneading.

  Prior to the melting / kneading process, a premixing process in which the mixed components are mixed in advance may be performed. Examples of the mixer used for the preliminary mixing include mixers such as a V-type mixer, a ribbon mixer, a nauter mixer, and a super mixer.

  Melt-kneading can be performed with a Banbury mixer, a roll, a single-screw or multi-screw extruder, and preferably with a twin-screw extruder. The melt-kneading conditions are not particularly limited. For example, the cylinder temperature during melt-kneading is preferably in the range of 240 to 300 ° C, and more preferably in the range of 250 to 280 ° C. The kneading pressure is not particularly limited, but is preferably 1 to 20 MPa.

  The amount of discharge from the extruder at the time of melt-kneading is not particularly limited, but it is preferably 10 to 100 kg / hour because melt-kneading is sufficiently performed, and 20 to 70 kg / hour. Is more preferable.

  The kneading weight ratio of the polycarbonate resin and the polyester resin mixture is not particularly limited, but from the viewpoint of impact resistance and fluidity, the polycarbonate resin: polyester resin mixture (weight ratio) = 10: 90 to 98: 2 It is preferably 10:90 to 90:10, more preferably 30:70 to 90:10.

  The kneading weight ratio of the flame retardant is not particularly limited, but from the viewpoint of improving the flame retardancy, it may be 1 to 40 parts by weight of the flame retardant with respect to 100 parts by weight of the total of the polyester resin mixture and the polycarbonate resin. The amount is preferably 10 to 40 parts by weight.

  The kneading weight ratio of the toughening agent is not particularly limited, but from the viewpoint of improving toughness, it is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the total of the polyester resin mixture and the polycarbonate resin, More preferably, it is 5 to 25 parts by weight.

  The molten resin kneaded material obtained by melt kneading as described above is preferably cooled after being injected. The cooling treatment is not particularly limited. For example, the resin kneaded product is immersed in water at 0 to 60 ° C. and cooled with water, the method of cooling with a gas of −40 to 60 ° C., and the metal at −40 to 60 ° C. is contacted. A method or the like can be used.

  The resin composition thus obtained is preferably cut into pellets by, for example, a pelletizer in order to facilitate the processing during injection molding by the injection molding method.

(Polycarbonate resin)
The polycarbonate resin may be an aromatic homo or copolycarbonate resin obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. A method for producing such a polycarbonate resin is not particularly limited, and a known method can be adopted. For example, a method in which phosgene is directly reacted with an aromatic dihydric phenol compound (an interfacial polymerization method), an aromatic And a method (solution method) in which a transesterification reaction of an aliphatic dihydric phenol compound and a carbonic acid diester such as diphenyl carbonate is performed in a molten state.

  The weight average molecular weight of the polycarbonate resin is preferably 20,000 to 70,000. When the weight average molecular weight of the polycarbonate resin is 20,000 or more, high fluidity is obtained, and since it is difficult to vaporize the combustible gas, the flame retardancy is improved, and by setting the weight to 70,000 or less, the toughness is reduced. It is preferable because it improves. More preferably, the polycarbonate resin has a weight average molecular weight of 20,000 to 55,000. A weight average molecular weight is measured by the measuring method as described in the following Example. According to the production method of the present invention, since the crystallinity of the crystalline polyester resin is suppressed, a relatively low molecular weight (impact resistance has been reduced in a combined system of a normal crystalline polyester resin and a polycarbonate resin ( For example, even when a polycarbonate resin having a weight average molecular weight of about 20,000 to 45,000 is used, the impact resistance is ensured. In addition, according to the production method of the present invention, since the crystallinity of the crystalline polyester resin is suppressed, the flowability is lowered in the combined system of the normal crystalline polyester resin and the polycarbonate resin. Even if a polycarbonate resin having a weight average molecular weight of about 40,000 to 70,000 is used, high fluidity is ensured.

  Examples of aromatic dihydric phenol compounds include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4-hydroxyphenyl). ) Methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2 -Bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1 -Phenyl-1,1-bis (4-hydroxyphenyl) ethane and the like can be mentioned, and these can be used alone or as a mixture.

  Examples of the carbonic acid diester include diaryl carbonates such as diphenyl carbonate, ditoluyl carbonate and bis (chlorophenyl) carbonate, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, carbonyl halides such as phosgene, and haloformates such as dihaloformates of dihydric phenols. Although it can be used, it is not limited to these. Of these, diphenyl carbonate is preferred. These carbonic acid diesters can also be used alone or in combination of two or more.

  Examples of the polycarbonate resin include trifunctional or more polyfunctional compounds such as 1,1,1-tris (4-hydroxyphenyl) ethane or 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. It may be a branched polycarbonate resin copolymerized with a functional aromatic compound or a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid. Moreover, the mixture obtained by mixing 2 or more types of obtained polycarbonate resin may be sufficient.

  A commercially available product may be used as the polycarbonate resin.

  As the polycarbonate resin, a resin piece obtained by pulverizing a discarded polycarbonate resin product may be used. In particular, as the polycarbonate having the above molecular weight range, a discarded pulverized product such as an optical disk can be suitably used. CDs, CD-Rs, DVDs, MDs, etc. Optical discs such as CDs, CD-Rs, DVDs, MDs, and the like that are produced by molding and cutting off the reflective layer, recording layer, etc. If it is the resin piece grind | pulverized to the inside, it will not specifically limit, It can use in this invention. The discarded polycarbonate resin product of the polycarbonate resin product can be obtained by kneading at a temperature of 180 ° C. or higher and 260 ° C. or lower once after pulverizing and washing, cooling and pulverizing.

  Virgin (unused) polycarbonate resins are commercially available in the form of pellets, but these are pressed at a temperature above the glass transition temperature, or once melted with an extruder or the like, and the molten strand is turned into a roller in cooling water. It can be used as a resin piece by crushing through and cutting with a normal pelletizer.

  By using the polycarbonate resin as the resin piece, the supply to the kneader is facilitated during the production of the resin composition, and the load on the kneading apparatus is reduced in the kneading until melting. As the shape of the polycarbonate resin piece, for example, a flake shape, a block shape, a powder shape, and a pellet shape are preferable, and a particularly preferable shape is a flake shape. A preferable maximum length of the resin piece is 30 mm or less, more preferably 20 mm or less, and still more preferably 10 mm or less. Kneading is possible even if a resin piece having a maximum length exceeding 30 mm is contained, but it may be clogged in the supply process, which is not preferable. However, since it can be prevented by improving the supply device, there is no particular limitation as long as the object of the present invention is not impaired.

(Flame retardants)
The flame retardant may be an organic flame retardant or an inorganic flame retardant. Examples of organic flame retardants include bromo compounds and phosphorus compounds. Examples of inorganic flame retardants include antimony compounds and metal hydroxides.

  At least a part of the flame retardant is preferably a phosphorus compound. This is because the phosphorus compound easily imparts high flame retardancy to the resin composition and has no environmental toxicity. The phosphorus compound is typically a phosphate ester compound, and examples of the phosphate ester compound include phosphite ester, phosphate ester and phosphonate esterified product. Particularly preferred are phosphoric esters.

  Specific examples of phosphites include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2 , 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, and the like.

  Specific examples of phosphate esters include triphenyl phosphate, tris (nonylphenyl) phosphate, tris (2,4-di-t-butylphenyl) phosphate, distearyl pentaerythritol diphosphate, bis (2,6-di-). t-butyl-4-methylphenyl) pentaerythritol diphosphate, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphate, tributyl phosphate, bisphenol A bis-diphenyl phosphate, aromatic condensed phosphate, etc. Can be mentioned. Examples of the condensed phosphate ester include 1,3-phenylene bis (di2,6xylenyl phosphate), bisphenol A bis (diphenyl phosphate), 1,3-phenylene bis (diphenyl phosphate), and the like.

  Specific examples of the phosphonic acid ester include dimethyl benzenephosphonate, benzenephosphonic acid ester, and the like.

  Examples of the bromo compound include polybromodiphenyl ether, tetrabromobisphenol-A, brominated epoxy oligomer, brominated polycarbonate oligomer.

  Commercially available flame retardants may be used, and commercially available phosphorus compounds include, for example, “CR-733S” and “CR-741” manufactured by Daihachi Chemical Industry Co., Ltd. (both condensed phosphoric acid ester and liquid). , “PX-200” (condensed phosphate ester, solid), “SPS-100” (phosphazene compound, solid) manufactured by Otsuka Chemical Co., Ltd., and the like.

(Thickener)
The toughening agent improves the flexibility, workability, impact resistance and the like of the resin composition. One or more toughening agents may be used. The toughening agent is, for example, a resin having rubber elasticity. The toughening agent is preferably a thermoplastic elastomer including a soft segment composed of a polymer of a monomer containing butadiene and a hard segment composed of a polymer of a monomer having an aromatic group such as styrene. . For example, if the molecular size of the thermoplastic elastomer is too small, the impact resistance of the resin composition may be reduced. If it is too large, the processability of the thermoplastic resin composition may be reduced. . From such a viewpoint, for example, the weight average molecular weight of the thermoplastic elastomer is preferably 10,000 to 500,000. The weight average molecular weight of the thermoplastic elastomer is also determined using a known method such as gel permeation chromatography.

  As the structure of the thermoplastic elastomer, for example, a core-shell structure, a graft structure, a straight chain structure, and a sea-island structure (so-called “polymer alloy”) are known. Any of the structures of the thermoplastic elastomer may be used. The core-shell structure includes, for example, a core of crosslinked rubber particles and a shell formed by graft polymerization of a vinyl monomer in the presence of the core. The core is mainly composed of soft segments, and the shell is mainly composed of hard segments. The graft structure is composed of, for example, a trunk polymer that is one of a soft segment and a hard segment and a branch polymer that is the other. The linear structure is composed of, for example, a block copolymer of a soft segment and a hard segment. The sea-island structure is composed of, for example, an island mainly composed of soft segments (dispersed phase) and a sea mainly composed of hard segments (continuous phase).

  Examples of the thermoplastic elastomer include methyl methacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS), styrene butadiene styrene copolymer (SBS), and butyl acrylate- Examples include methyl methacrylate copolymer. These may be used alone or in combination of two or more. Among them, the toughening agent is at least one selected from the group consisting of MBS, ABS, and SBS. The compatibility and flame retardancy of the thermoplastic resin composition, and the dispersion of the thermoplastic elastomer in the thermoplastic resin composition From the viewpoint of sex.

  Further, the MBS structure is a core-shell structure, and the rubber amount of MBS is 50 to 80% by weight, so that the impact resistance of the thermoplastic resin composition, the dispersibility of MBS in the thermoplastic resin composition, etc. To preferred. Further, the ABS structure is preferably a graft structure, and the rubber amount of ABS is preferably 10 to 55% by weight from the viewpoint of the compatibilizing property and processability of the thermoplastic resin composition. Moreover, it is preferable from a viewpoint of the softness | flexibility of a thermoplastic resin composition, and impact resistance that the structure of SBS is a linear structure and the rubber amount of SBS is 50 to 80 weight%. The “rubber amount” means the content of the soft segment in the thermoplastic elastomer.

  An example of MBS is EM500 (LG Chemical, Ltd.). An example of ABS includes TFX-610 (Mitsubishi Chemical Corporation). Examples of SBS include Califlex TRKX65S (Shell Corporation).

  In step (2), an anti-drip agent and a compatibilizing agent may be added and mixed in addition to the above components.

(Anti-drip agent)
Anti-drip agent is added for the purpose of preventing dripping (drip) of resin material during combustion and improving flame retardancy. Fluorine-based anti-drip agent, silicone rubber, layered silicate, etc. Can be mentioned.

  Examples of the layered silicate include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, swellable mica, talc, etc. A cation, a quaternary ammonium cation, or a phosphonium cation may be intercalated.

  Among the anti-drip agents, a fluorine-based anti-drip agent is particularly preferable. Specific examples of the fluorine-based anti-drip agent include fluorine resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene. Perfluoromethanesulfonic acid sodium salt, perfluoro-n-butanesulfonic acid potassium salt, perfluoro-t-butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, perfluoro-2-ethylhexanesulfonic acid calcium salt, etc. Perfluoroalkanesulfonic acid alkali metal salt compounds or perfluoroalkanesulfonic acid alkaline earth metal salts. Among the fluorine-based anti-drip agents, polytetrafluoroethylene is most preferable from the viewpoint of anti-drip properties.

  The addition amount of the anti-drip agent is preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total of the polyester resin composition and the polycarbonate resin.

(Compatibilizer)
The compatibilizer is a compound (low molecular compound or polymer) having a double bond, a carboxyl group, an epoxy group, an isocyanate group, etc., and reacts with one or both of the polymers to be compatibilized in the molding process. It functions as a compatibilizer by acting as a surfactant based on the graft or block structure (reference: “Polymer Alloy” Fundamentals and Applications, edited by the Society of Polymer Science, published in 1993), JP2013 Examples thereof include resins having a reactive functional group disclosed in JP-A-133369. Examples of the compatibilizer include ethylene glycidyl methacrylate copolymer (E-GMA; copolymer weight composition, for example, E / GMA = 100/6 to 12), ethylene glycidyl methacrylate-vinyl alcohol copolymer (E-GMA- VA; copolymer weight composition, for example, E / GMA / VA = 100/3 to 12 / 8-5, ethylene glycidyl methacrylate-methacrylate copolymer (E-GMA-MA; copolymer weight composition, for example, E / GMA / Copolymer having structural units derived from glycidyl methacrylate (GMA) such as MA = 100/3 to 12/30); ethylene glycidyl methacrylate-acrylonitrile styrene (EGMA-AS; copolymer weight composition such as EGMA / AS = 70 / 30), ethylene glycidyl methacrylate-polystyrene EGMA-PS; copolymer weight composition, eg EGMA / PS = 70/30), ethylene glycidyl methacrylate-polymethyl methacrylate (EGMA-PMMA, eg EGMA / PMMA = 70/30), styrene-acrylonitrile-glycidyl methacrylate (SAN-) GMA, for example, a resin in which glycidyl methacrylate such as SAN / GMA = styrene / acrylonitrile / glycidyl methacrylate = 70/50/10 to 75/23/2) is introduced; ethylene maleic anhydride ethyl acrylate copolymer (E-MAH -EA); acid-modified polyethylene wax; COOH-modified polyethylene graft polymer, COOH-modified polypropylene graft polymer; polyisocyanate containing 5 to 30% by weight of isocyanate groups That.

  A commercially available product may be used as the compatibilizer. Specifically, Bond First E, Bond First 2C (manufactured by Sumitomo Chemical Co., Ltd.); Lexpearl RA, Lexpearl ET, Lexpearl RC (manufactured by Nippon Polyolefin Co., Ltd.); Bondine (Manufactured by Sumitomo Chemical Co., Ltd.); Modiper (manufactured by NOF Corporation); high wax (APEW; manufactured by Mitsui Chemicals); VESTANAT T1890 (manufactured by Degussa).

  Only 1 type of these compatibilizers may be used, and 2 or more types may be mixed and used as needed.

  Among these, from the viewpoint of easy reaction with the polyester resin, the compatibilizer is preferably a copolymer having a structural unit derived from glycidyl methacrylate (GMA) or a resin into which glycidyl methacrylate is introduced.

  As the addition amount of the compatibilizing agent, the total amount of the polyester resin composition and the polycarbonate resin is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight.

(Other resin components, optional components)
In the step (2), other resin components and optional additive components can be added as necessary within the range in which the object of the present invention is achieved.

  As other resin components, for example, polyolefins such as polyethylene and polypropylene, polyamides such as nylon 6 and nylon 66, and the like can be added to improve the performance as a molding resin. The content of the other resin components is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, with respect to 100% by weight of the total weight of the polycarbonate resin and the polyester resin.

  In addition, as other optional components, for example, a crosslinking agent (for example, phenol resin), an antioxidant (hindered phenol-based, sulfur-containing organic compound-based, phosphorus-containing organic compound-based, etc.), heat stabilizer (phenol-based, Acrylates), transesterification inhibitors (such as mixtures of monostearyl acid phosphate and distearyl acid phosphate), UV absorbers (benzotriazoles, benzophenones, salicylates, etc.), light stabilizers (such as Organic nickel-based, hindered amine-based, etc.), lubricants (metal salts of higher fatty acids, higher fatty acid amides, etc.), pigments (carbon black, titanium oxide), dyes, antistatic agents, foaming agents and the like.

  Still other examples of optional ingredients include metal fibers, aramid fibers, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide and aluminum oxide. Of filler. Of these, glass fiber, carbon fiber and metal fiber are preferable, and carbon fiber is most preferable. The type of the fibrous filler is not particularly limited as long as it is generally used for reinforcing a resin. For example, the fibrous filler is selected from a long fiber type or a short fiber type chopped strand, a milled fiber, or the like. be able to. Moreover, it is preferable that content of an arbitrary component is 0.01 to 10 weight% with respect to the total weight of 100 weight% of polycarbonate resin and polyester resin, More preferably, it is 0.1 to 5 weight% .

(Thermoplastic resin composition)
The thermoplastic resin composition obtained by the above production method has high flame retardancy.

  Flame retardancy is one of flame resistance, and refers to the property of burning slowly but burning to some extent. Regarding the evaluation of flame resistance, there are JIS, ASTM, etc., but in general, the UL standard is particularly emphasized. The UL standard is a standard established by “Underwriters Laboratories” in the United States and evaluated by the company. Generally, a test method is used to confirm the burning time and the presence or absence of dripping material by applying flame to a test piece specified in UL94. The retarding substance is “UL94-HB”, and the self-extinguishing substance is “ It is classified into one of the classifications “UL94-V2”, “UL94-V1”, “UL94-V0”, and “UL94-5V”. Self-extinguishing is a flame-retardant property that continues to burn if there is a fire source, but extinguishes itself if the fire source is removed.

  In general, in various fields such as office equipment, information / communication equipment, electrical / electronic equipment, household appliances, automobile field, construction field, etc., the flame retardant specified in UL-94 for parts used It is required to have sex. The flame retardancy of the thermoplastic resin composition obtained is preferably UL94-V1 or more, and more preferably V0 or more.

(Resin molding)
The thermoplastic resin composition obtained by the above production method can be molded into a resin molded body by any method. Examples of molding methods include injection molding, extrusion molding, blow molding, vacuum molding, profile extrusion molding, compression molding, gas assist molding, and the like. As described above, since the resin composition of the present invention has high fluidity and is suitable for injection molding, it is preferably a resin composition for injection molding.

  The resin molded product of the thermoplastic resin composition obtained by the above production method can be used for electrical / electronic parts, automobile parts, mechanical mechanism parts, OA equipment, or housing parts of home appliances. In particular, it is preferably used for a housing of an OA device such as a printer.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples.

<Measurement method>
(Measurement of weight average molecular weight ( _Mw ))
A sample was weighed in the range of 4 to 7 μg and added to THF, and then ultrasonic waves were applied for 30 minutes, and the dissolved portion was used for measurement by a GPC apparatus. The weight average molecular weight _(M W) (in terms of polystyrene), as GPC device, manufactured by Tosoh Corporation HLC-8120GPC, using SC-8020 apparatus, column TSKgel, Super HM-H a (6.0 mm ID × 15cm × 2) The chromatograph THF (tetrahydrofuran) manufactured by Wako Pure Chemical Industries, Ltd. was used as the eluent. As experimental conditions, a flow rate of 0.6 ml / min. The experiment was conducted using a 10 μl sample injection volume, a measurement temperature of 40 ° C., and an RI detector. The calibration curve is "polystylen standard sample TSK standard" manufactured by Tosoh Corporation: A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F- It produced from 10 samples of 128 and F-700. The data collection interval in sample analysis was 300 ms.

(Differential scanning calorimetry (DSC))
The endothermic peak temperature of the crystalline polyester resin and the heat release amount and half-value width in the melting curve of the polyester resin were obtained using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60A) in accordance with ASTM D3418. The temperature correction of the detection part of this apparatus (DSC-60A) was performed using the melting point of indium and zinc, and the heat of fusion of indium was used to correct the amount of heat. For the sample, an aluminum pan was used, an empty pan was set as a control, the temperature was raised from 30 ° C. to 270 ° C. at a heating rate of 10 ° C./min, held at 270 ° C. for 5 minutes, and from 270 ° C. to 30 ° C. The temperature was lowered at −10 ° C./min using liquid nitrogen. The heat release and half-value width in the melting curve of the polyester resin were analyzed from the endothermic curve at the time of temperature drop. The amount of heat dissipated is the area of the heat dissipating peak, and the half width is the width of the wavelength where the intensity ratio of the heat dissipating peak is 50%.

[Example 1]
(1) Preparation of nucleating agent 100 parts by weight of NANO ACE D-600 (talc; Nippon Talc Co., Ltd.) and 10 parts by weight of sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate (Chem Special) was stirred at room temperature for 15 minutes at a peripheral speed of a stirring blade of a Henschel mixer at a stirring speed of 25 m / sec or more to obtain a mixture 1.

(1) Step (1)
100 parts by weight of polyethylene terephthalate resin (inherent viscosity [η] = 0.780 dl / g, trade name: Dianite MA521H-D25, manufactured by Mitsubishi Rayon Co., Ltd.) and 1 part by weight of the nucleating agent of mixture 1 are dried using a V-type mixer. After blending, the mixture was dried under reduced pressure at 80 ° C. for 4 hours using a vacuum dryer.

  The dried mixture was charged from the raw material supply port of the twin-screw kneading extruder, and melt kneaded under the conditions of a cylinder temperature of 260 ° C. and a discharge rate of 30 kg / hour. The kneaded product discharged from the biaxial kneader-extruder was quenched by immersing in water at 30 ° C. and pulverized into pellets by a pelletizer to obtain a polyester resin mixture. The obtained polyester resin mixture was dried at 80 ° C. for 4 hours under reduced pressure using a vacuum dryer.

(2) Step (2)
10 parts by weight of the polyester resin mixture obtained in the step (1), 55 parts by weight of a polycarbonate resin (weight average molecular weight 50,000, trade name Toughlon A-1900, manufactured by Idemitsu Kosan Co., Ltd.), flame retardant (condensed phosphate compound; Trade name PX-200, manufactured by Daihachi Chemical Co., Ltd. 20 parts by weight and a toughener (MBS; trade name EM500, manufactured by LG Chemical, and ABS; trade name TFX-610, manufactured by Mitsubishi Chemical Co., Ltd., 1: 1 (weight ratio) ) Mixture) 15 parts by weight were dry blended using a V-type mixer.

  The mixture was introduced from the raw material supply port of the twin-screw kneading extruder, and melt kneaded at 250 ° C. and a kneading pressure of 1.0 MPa under the condition of a discharge rate of 30 kg / hour. The kneaded product discharged from the biaxial kneader / extruder was quenched by immersing in water at 30 ° C., and pulverized into pellets by a pelletizer to obtain a thermoplastic resin composition.

[Example 2]
In Example (2), a polycarbonate resin having a weight average molecular weight of 20,000 (trade name novarex 7020R, manufactured by Idemitsu Kosan Co., Ltd.) was used instead of a polycarbonate resin having a weight average molecular weight of 50,000. 1 to obtain a thermoplastic resin composition.

[Example 3]
In Example (2), a polycarbonate resin having a weight average molecular weight of 70,000 (trade name novarex 7027U, manufactured by Idemitsu Kosan Co., Ltd.) was used instead of the polycarbonate resin having a weight average molecular weight of 50,000. 1 to obtain a thermoplastic resin composition.

[Example 4]
In step (1), a thermoplastic resin composition was obtained in the same manner as in Example 1 except that 0.5 part by weight of the nucleating agent was added instead of 1 part by weight of the nucleating agent.

[Example 5]
In step (1), a thermoplastic resin composition was obtained in the same manner as in Example 1, except that 5 parts by weight of the nucleating agent was added instead of 1 part by weight of the nucleating agent.

[Example 6]
In step (1), a thermoplastic resin composition was obtained in the same manner as in Example 1 except that instead of the mixture 1, the following mixture 2 was used as a nucleating agent.

(1) Preparation of nucleating agent 100 parts by weight of Brilliant-1500 (calcium carbonate; Shiraishi Kogyo Co., Ltd.) and 10 parts by weight of sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate ( Chemspecial Co., Ltd.) was stirred at room temperature for 15 minutes at a stirring speed of 25 m / sec or more at the peripheral speed of the stirring blade of the Henschel mixer.

[Example 7]
In step (1), a thermoplastic resin composition was obtained in the same manner as in Example 1 except that the following mixture 3 was used as a nucleating agent instead of the mixture 1.

(1) Preparation of nucleating agent 100 parts by weight of sicastar 43-00-102 (silica; Corefront Corporation) and 10 parts by weight of sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) Phosphate (manufactured by ChemSpecial) was stirred at room temperature for 15 minutes at a stirring speed of 25 m / sec or more at the peripheral speed of the stirring blade of the Henschel mixer to obtain a mixture 3.

[Example 8]
In step (1), a thermoplastic resin composition was obtained in the same manner as in Example 1 except that instead of the mixture 1, the following mixture 4 was used as a nucleating agent.

(1) Preparation of nucleating agent 100 parts by weight of NANO ACE D-600 (manufactured by Nippon Talc Co., Ltd.) and 10 parts by weight of sodium benzoate (Tokyo Kasei Kogyo Co., Ltd.) for 15 minutes at room temperature Stirring was performed at a stirring speed of 25 m / sec or more with the peripheral speed of the stirring blade, whereby a mixture 4 was obtained.

[Example 9]
In step (1), a thermoplastic resin composition was obtained in the same manner as in Example 1, except that the product name BRUGGOLEN (registered trademark) P250, manufactured by Bruggemann Chemical Co.) was used as the nucleating agent instead of the mixture 1. .

[Example 10]
Except for changing from polyethylene naphthalate resin to polybutylene naphthalate resin (inherent viscosity [η] = 0.5 to 1.5 dl / g, trade name PBN resin, manufactured by Teijin Chemicals Limited) in step (1). In the same manner as in Example 1, a thermoplastic resin composition was obtained.

[Comparative Example 1]
10 parts by weight of polyethylene terephthalate resin (trade name: Dianite MA521H-D25, manufactured by Mitsubishi Rayon Co., Ltd.), 55 parts by weight of polycarbonate resin (weight average molecular weight: 50,000, trade name: Toughlon A-1900, manufactured by Idemitsu Kosan Co., Ltd.), flame retardant ( 20 parts by weight of a condensed phosphoric acid compound; trade name PX-200, manufactured by Daihachi Chemical Co., Ltd. and a toughening agent (MBS; trade name EM500, manufactured by LG Chemical, and ABS; trade name TFX-610, manufactured by Mitsubishi Chemical Corporation) 15 parts by weight of a 1: 1 (mass ratio) mixture was dry blended using a V-type mixer.

  The mixture was charged from the raw material supply port of the twin-screw kneading extruder and melt-kneaded under the condition of a discharge rate of 30 kg / hour. The kneaded product discharged from the biaxial kneader / extruder was quenched by immersing in water at 30 ° C., and pulverized into pellets by a pelletizer to obtain a thermoplastic resin composition.

[Comparative Example 2]
10 parts by weight of a polyethylene terephthalate resin (trade name: Dianite MA521H-D25, manufactured by Mitsubishi Rayon Co., Ltd.), 0.5 parts by weight of a trade name: BRUGGOLEN (registered trademark) P250, manufactured by Bruggemann Chemical Co., as a nucleating agent, and a polycarbonate resin (weight average molecular weight: 50) , 000, trade name Toughlon A-1900, manufactured by Idemitsu Kosan Co., Ltd.) 55 parts by weight, flame retardant (condensed phosphoric acid compound; trade name PX-200, manufactured by Daihachi Chemical Co., Ltd.) 20 parts by weight and thickener (MBS; 15 parts by weight of a trade name EM500, LG Chemical, and ABS; a trade name TFX-610, a 1: 1 (weight ratio) mixture made by Mitsubishi Chemical Co., Ltd. were dry-blended using a V-type mixer.

  The mixture was charged from the raw material supply port of the twin-screw kneading extruder and melt-kneaded under the condition of a discharge rate of 30 kg / hour. The kneaded product discharged from the biaxial kneader / extruder was quenched by immersing in water at 30 ° C., and pulverized into pellets by a pelletizer to obtain a thermoplastic resin composition.

[Comparative Example 3]
In step (1), a thermoplastic resin composition was obtained in the same manner as in Example 1 except that 10 parts by weight of the nucleating agent was added instead of 1 part by weight of the nucleating agent.

  The following evaluation was performed about the thermoplastic resin composition obtained by each Example and the comparative example.

<Evaluation method>
(1) Flowability After the resin composition is dried at 80 ° C. for 4 hours, an Archimedes spiral flow test piece (flow path thickness: 2 mm, flow path) using an injection molding machine “ROBOSHOT_S-2000i 50BP” (manufactured by FANUC) The flow length was evaluated according to the following evaluation criteria at a width of 10 mm). The conditions were an injection speed of 60 mm / s, a cylinder temperature of 250 ° C., a mold temperature of 50 ° C., and an injection pressure of 860 MPa. The longer the flow length, the better the fluidity.

◎: 350 mm or more ○: 330 mm or more and less than 350 mm △: 300 mm or more and less than 330 mm (no problem in practical use)
×: Less than 300 mm (practical problem)
(2) Charpy impact strength Using specimen A, a Charpy impact test (U notch, R = 1 mm) was performed in accordance with "JIS-K7111", the impact strength was measured, and evaluated according to the following evaluation criteria.

◎: 42 kJ / m ² or more ○: 32 kJ / m ² or more and less than 42 kJ / m ² Δ: 6 kJ / m ² or more and less than 32 kJ / m ² ×: less than 6 kJ / m ² (practical problem)
(3) Flame retardancy Test piece B was evaluated by a technique based on UL-94. The criteria are 5VA, 5VB, V-0, V-1, V-2 and HB in descending order of flame retardancy. In addition, the case where flame retardance was so low that it did not correspond also to HB was evaluated as "non-standard". “Non-standard” means that there is a practical problem in the above-mentioned use.

A: 5VA, 5VB
○: V0
Δ: V1, V2, HB
×: Non-standard (practical problem)
The manufacturing conditions and evaluation results of each example are shown in Table 1, and the manufacturing conditions and evaluation results of each comparative example are shown in Table 2.

  The thermoplastic resin compositions of Examples 1 to 10 of the present invention have an evaluation of Δ or more in all items of impact resistance, fluidity and flame retardancy, and the physical properties of all items are good. Indicated.

  On the other hand, in the step (1), the crystalline polyester resin and the nucleating agent are not melt-kneaded (Comparative Example 1). In the step (1), the crystalline polyester resin and the nucleating agent are not melt-kneaded, but in the step (2). When the nucleating agent was added together with other additives (Comparative Example 2), the fluidity deteriorated. Moreover, when the compounding quantity of the nucleating agent in process (1) was high (comparative example 3), toughness, fluidity | liquidity, and the flame retardance fell.

Claims (5)

(1) a step of obtaining a polyester resin mixture by melt-kneading 100 parts by weight of a crystalline polyester resin and 0.5 to 5 parts by weight of a nucleating agent comprising a mixture of an organic compound and an inorganic compound using an extruder;
Mixing the polyester resin mixture, polycarbonate resin, flame retardant and toughening agent (2);
A method for producing a thermoplastic resin composition, comprising:   The heat of fusion (ΔHA) in the DSC melting curve of the polyester resin mixture is 70% or less (ΔHA / ΔHB ≦ 0.7) with respect to the heat of fusion (ΔHB) in the DSC melting curve of the crystalline polyester resin. The manufacturing method according to claim 1.   The half width (Δa) in the DSC melting curve of the polyester resin mixture is 70% or less (Δa / Δb ≦ 0.7) with respect to the half width (Δb) in the DSC melting curve of the crystalline polyester resin. Item 3. The method according to Item 1 or 2. In the step (2), 10 to 90 parts by weight of the polyester resin mixture, 10 to 90 parts by weight of the polycarbonate resin (here, the total of the polyester resin mixture and the polycarbonate resin is 100 parts by weight), 1 to 40 parts by weight of the flame retardant, and The manufacturing method of any one of Claims 1-3 which mixes 1-30 weight part of thickeners.   The manufacturing method of any one of Claims 1-4 whose molecular weight (Mw) of the said polycarbonate resin is 20,000-70,000.