JP2011140587A - Method for producing raw material pellet for molding - Google Patents

Abstract

Disclosed is a method for producing a pellet of a polycarbonate resin-based thermoplastic resin composition, which is excellent in impact resistance and at the same time obtains a hollow molded article having a good surface appearance with few pinholes.
An aromatic polycarbonate resin (A1) and another thermoplastic resin (A2) are contained in a mass ratio of (A1) / (A2) at a ratio of 50 to 99/50 to 1, and a component (A1 ) And (A2) for a total of 100 parts by mass, the thermoplastic resin composition (C) containing 0.5 to 30 parts by mass of the rubbery polymer (B) is melt-kneaded with an extruder to produce pellets. In manufacturing,
The temperature is controlled so that the set temperature (Ta) of the supply zone (a) for feeding the resin composition forward is 10 ° C. or more lower than the set temperature (Tb) of the melt kneading zone (b) According to the manufacturing method of forming raw material pellets.
[Selection] Figure 1

Description

  The present invention relates to a method for producing raw material pellets for molding, and more specifically, a molded article having sufficient mechanical strength and good surface appearance is provided from a thermoplastic resin composition containing a polycarbonate resin and another thermoplastic resin. The present invention relates to a method for producing molding raw material pellets, a molding method using the pellets, and a molded product obtained thereby.

  Polycarbonate resin is a general-purpose engineering plastic that excels in transparency, impact resistance, heat resistance, dimensional stability, etc., and its excellent characteristics make it an excellent choice in a wide range of fields such as electrical / electronic / OA equipment parts, machine parts, and vehicle parts. in use. Furthermore, a resin composition comprising a polycarbonate resin and another thermoplastic resin, such as a thermoplastic polyester resin, improves the chemical resistance and molding processability, which are disadvantages of the polycarbonate resin, while taking advantage of the above-mentioned excellent features of the polycarbonate resin. Since it has excellent moldability, mechanical properties, chemical resistance and dimensional stability, it is widely used in various fields. In particular, in the field of vehicle interior parts and exterior parts such as automobiles, their excellent surface design and light weight have been evaluated and are widely used.

In recent years, in the automotive field and the electric / electronic field, a gas injection injection molding method that gives a hollow molded product has attracted attention for the purpose of reducing the cost by reducing the weight and shortening the molding cycle and applying it to a large molded product.
The gas injection injection molding method is also called a gas assist molding method and is a kind of injection molding method. First, a molten resin is injected into a mold cavity, and then compressed gas (mainly inert gas, for example, nitrogen gas). In the field of automotive parts, where there is a strong demand for weight reduction, the gas injection injection molding method is a method that can be made thin and highly rigid. Highly expected.

However, the holding pressure of gas in gas injection injection molding is usually about 8 to 12 MPa, which is considerably lower than the holding pressure in general injection molding of 30 to 80 MPa. Since the pressing pressure is small, the surface of the obtained molded product tends to have a noticeable roughness.
In particular, when the resin composition contains a rubber component or an inorganic filler, pinholes are likely to occur in areas where pressure is not easily applied during gas injection injection molding, and pinholes are generated when the shape of the molded product is complicated. Prominent and fatal.

Various proposals have been made for improving a thermoplastic resin composition containing a polycarbonate resin and other thermoplastic resins such as a polyester resin and an inorganic filler. Patent Document 1 discloses specific lengths and diameters of various resins. A composition using a needle-shaped fine particle inorganic filler, Patent Document 2 includes a polycarbonate resin, an aromatic polyester resin, a rubber-like elastic body, a composition containing an inorganic filler, and Patent Document 3 further includes a fluorinated olefin-based material. Proposals have been made for compositions containing polymers. Patent Document 4 describes an example in which a composition containing an inorganic filler is used in a gas injection injection molding method.
However, simply improving these thermoplastic resin compositions themselves does not solve the above-mentioned problems, and if molded by gas injection injection molding or the like, there are still problems such as pinholes, surface roughness and poor gloss on the molded product surface. Will occur.

Japanese Patent Laid-Open No. 7-149948 JP-A-5-222283 JP 2008-231440 A JP 2003-12912 A

  Under such circumstances, the development of materials, particularly raw material pellets, that can be obtained by molding a thermoplastic resin composition containing a polyester resin and other resins to obtain a molded product having excellent surface properties and mechanical strength is strongly desired. It was rare.

  An object of the present invention is to provide a molded article having sufficient mechanical strength and good surface appearance from a thermoplastic resin composition containing a polycarbonate resin and another thermoplastic resin in view of the above-mentioned problems of the prior art. It is to provide a raw material pellet for molding.

  In order to achieve the above-mentioned problems, the present inventors have analyzed in detail the phenomenon during the melt-kneading of the thermoplastic resin composition, or the phenomenon from ejection to pelletizing, and as a result of intensive studies, the conventional method and On the other hand, it is effective to make the set temperature of the supply section lower than the set temperature of the compression section. When the raw material pellets obtained by this are used for molding such as gas injection injection molding, sufficient mechanical properties are achieved. The present inventors have found that a molded article having a good surface appearance with less strength and no pinholes can be obtained, and the present invention has been completed.

That is, according to the first invention of the present invention, the aromatic polycarbonate resin (A1) and the thermoplastic resin (A2) other than (A1) are mixed at a mass ratio of (A1) / (A2) to 50. Thermoplastic containing 0.5 to 30 parts by mass of rubbery polymer (B) with respect to 100 parts by mass of the total amount of components (A1) and (A2). When producing pellets by melting and kneading the resin composition (C) with an extruder,
In the heating barrel of the extruder having at least one melt kneading zone, the set temperature (Ta) of the supply zone (a) for feeding the resin composition forward is set to the first melting for melt kneading the resin composition. There is provided a method for producing forming raw material pellets, characterized in that the temperature is controlled to be lower by 10 ° C. or more than the set temperature (Tb) of the kneading zone (b).

According to the second invention of the present invention, in the first invention, the set temperature (Ta) of the supply zone part (a) is relative to the softening point Tm of the rubber polymer (C).
Formula: Tm-100 <Ta <Tm + 150 ° C.
The manufacturing method characterized by satisfy | filling is provided.

  According to a third aspect of the present invention, there is provided the production method according to the first or second aspect, wherein the temperature of the first melt-kneading zone (b) is 300 ° C. or lower.

  According to a fourth invention of the present invention, in any one of the first to third inventions, the other thermoplastic resin (A2) is polybutylene terephthalate or polyethylene terephthalate. Provided.

  According to the fifth invention of the present invention, in any one of the first to fourth inventions, the thermoplastic resin composition (C) has an average particle diameter measured by a laser diffraction particle size distribution measuring device of 0.00. The talc or wollastonite (D) having a particle diameter of 5 to 5.0 μm and substantially not containing particles having a particle diameter of 15 μm or more is based on 100 parts by mass of the total amount of (A1) and (A2). The manufacturing method characterized by containing 1-60 mass parts is provided.

  According to a sixth aspect of the present invention, in any one of the first to fifth aspects, the (D) component has a bulk density of 0.4 to 1.5 g / granulated using talc and a binder. A production process is provided which is characterized by ml of granular talc.

  According to a seventh invention of the present invention, in any one of the first to sixth inventions, at least one of the component (A1) or the component (A2) is in the form of a pellet. Is provided.

  According to the eighth invention of the present invention, in any one of the first to seventh inventions, the rubbery polymer (B) is masterbatched in advance by the component (A1) or the component (A2). A production method is provided which is supplied as a resin composition.

  Moreover, according to the ninth invention of the present invention, a molded article having a hollow portion is produced by a gas injection injection molding method using the raw material pellets produced by any one of the first to eighth inventions. A method for producing a molded product is provided.

  Further, according to the tenth aspect of the present invention, there is provided a molded product manufactured according to the ninth aspect.

  According to the production method of the present invention, it is possible to provide a raw material pellet for molding capable of providing a molded article having sufficient mechanical strength and good surface appearance. In particular, in the case of gas injection injection molding, it is possible to give a molded product having a hollow portion excellent in mechanical strength and surface appearance.

It is a schematic sectional drawing which shows one embodiment of the extruder and heating barrel which are used by this invention.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to

[1. Overview]
The present invention contains an aromatic polycarbonate resin (A1) and another thermoplastic resin (A2) in a ratio of (A1) / (A2) mass ratio of 50 to 99/50 to 1, and further a rubbery polymer. In producing pellets by melt-kneading the thermoplastic resin composition (C) containing 0.5 to 30 parts by mass of (B) with respect to a total of 100 parts by mass of components (A1) and (A2) in an extruder. ,
In a heating barrel of an extruder having at least one melting zone, the set temperature (Ta) of the supply zone (a) is 10 ° C. or more lower than the set temperature (Tb) of the melt kneading zone (b). It is characterized by temperature control.

[2. Temperature control]
Hereinafter, the present invention will be specifically described with reference to the drawings.
FIG. 1 is a schematic sectional view showing an embodiment of an extruder and a heating barrel used in the present invention.

In general, raw material pellets are obtained from a polycarbonate resin-based thermoplastic resin composition by extrusion molding.
In extrusion molding, a screw 2 is rotatably disposed inside a heating barrel 1 of an extrusion molding machine, and a series of steps of supplying pellet-form or powder-form raw materials, melt-kneading, and melt-extrusion are performed. Yes. This series of steps can be classified according to the shape of the screw in the heating barrel, and the cylinder 1 has the supply zone (a), the melt-kneading zone (b), It is divided into melting zones (c), and band heaters 5, 6, 7 are arranged on the respective outer circumferences.

Explaining in the order of the steps, first, each raw material resin in the form of pellets or powders, usually pellets, was provided at the rear end of the heating barrel directly below the hopper from the hopper 3 disposed at the rear part on the extruder. Through the supply port 4, it is fed into the supply zone (a) in the heating barrel 1 heated by the heater.
In the supply zone (feed zone) (a), a screw 6 rotatably disposed in the barrel 1 is rotated so that polycarbonate resin, other thermoplastic resin, rubber polymer, etc. from the supply port 4 are rotated. While thoroughly kneading and heating the resin material, it is sent out to the melt-kneading zone (b) in front of the barrel.
The supply zone (a) is composed of a normal feed screw that does not include a screw segment for melting and kneading a resin such as a kneading disk or a rotary segment. There are 1 type and 2 type, but preferably 2 type is used.

In the melt-kneading zone (b), the unmelted or semi-molten resin composition conveyed from the supply zone (a) is sufficiently melt-kneaded with heat, pressure, and shearing force to melt forward. The resin composition melt-kneaded is sent out to the zone (c).
In the melt-kneading zone (b), using a kneading disk, a rotary segment, a special notch element or the like, from the heat generation between these screw segments or between the screw segment and the extruder barrel, from the band heater 6 attached to the barrel. This is the part where the resin is melted and kneaded by the heat of.
It is preferable that a vent port 8 and a gas seal portion such as a seal ring 9 are provided downstream of the melt kneading zone (b) (on the discharge die side). The seal ring 9 is a metal ring, which normally closes 70 to 80% of the flow path and prevents the gas from flowing by retaining the molten resin in this part, and this part is reduced in pressure (including the open state). By doing so, the volatile matter etc. in molten resin can be removed effectively.
In the case of adding other additives, it is preferable to provide an injection port 10 on the downstream side of the gas seal portion (seal ring 9) on the downstream side for injection. This can be said to prevent the injected additive from escaping from the vent.

  Further, in the melting zone (c), the molten resin composition is extruded from the discharge die 11 in front of the screw. The melting zone (c) is composed of a progressive screw, and feeds the molten resin composition forward of the cylinder. It is preferable to provide a vent port 8 in the melting zone (c) to remove the low volatile content in the resin material. In this case, it is preferable to use a vacuum vent that depressurizes the vent port 8 with a vacuum pump. More preferably, the degree of vacuum is -0.099 to -0.06 MPa.

The strand extruded from the discharge die 11 is usually provided with a cooling water tank. After cooling treatment, the strand is cut by a cutting means such as a pelletizer to obtain pellets having an average particle diameter of about 1 to 5 mm. When cutting with a pelletizer, if the strand is completely cooled (about room temperature), it will be difficult to cut and problems such as generation of fine powder will occur, so that it will be cut when the strand temperature is in the range of 90-150 ° C. It is desirable to make it.
The temperature at the time of strand cutting is the temperature measured with a non-contact type thermometer just before entering the pelletizer, but simply measure the amount of the cut pellets by inserting a thermometer. But it ’s enough.

As described above, the band heaters 5, 6, and 7 are disposed on the outer circumferences of the supply zone (a), the melt-kneading zone (b), and the melt zone (c) of the cylinder 1, respectively. Is provided with a temperature sensor (not shown), and the band heaters 5, 6 and 7 are ON / OFF controlled or energized for each zone, and the temperature is controlled independently for each zone.
The temperature control is usually performed by computer control, but during operation of the extruder, the set temperature stored for each zone is read and each supply zone (a) measured by the temperature sensor is melted and kneaded. Compared with the temperature of zone (b) and melting zone (c), if the measured temperature is lower than the set temperature, the supply current of the corresponding band heater 5, 6 or 7 is set to “ON” and the temperature is raised to the set temperature. If the measured temperature is higher than the set temperature, the supply current of the corresponding band heater 5, 6 or 7 is turned “OFF” and the temperature is lowered to the set temperature.

In the present invention, the set temperature (Ta) of the supply zone (a) is set to be 10 ° C. or lower than the set temperature (Tb) of the first melt-kneading zone (b) for melt-kneading the resin composition. It is characterized by controlling.
The thermoplastic resin composition raw material pellets obtained by setting the temperature in this way can be used for molding, for example, gas injection injection molding, molding at a low molding pressure unique to gas injection molding, and molded products. Pinholes are unlikely to occur on the surface. On the other hand, in the case of pellets in which the barrel temperature was lowered overall and the discharge temperature was lowered, the number of pinholes generated was reduced, but it was still insufficient.

The specific setting of the set temperature Ta of the supply zone (a) is determined by referring to the glass transition temperature and melting point of the raw material polycarbonate resin (A1) and the other thermoplastic resin (A2) other than polycarbonate. The ratio is preferably determined in consideration of the softening point Tm of the rubber polymer (B) blended together with the ratio being taken into consideration.
The glass transition temperature of the polycarbonate resin preferably used in the present invention as described later is usually about 140 to 160 ° C. and does not show a clear melting point. On the other hand, the glass transition temperature of polybutylene terephthalate, which is a typical example of the polyester resin preferably used in the present invention, is usually 40 to 50 ° C., the melting point is about 230 ° C., and the glass transition temperature of polyethylene terephthalate is usually 80 to 90. The melting point is about 250 ° C. Moreover, the softening point of the methyl methacrylate-butadiene core-shell type elastomer which is a typical example of the rubber polymer preferably used in the present invention is about 100 to 105 ° C.

The set temperature (Ta) of the supply zone zone (a) is relative to the softening point Tm of the rubber polymer (C).
Formula: Tm-100 <Ta <Tm + 150 ° C.
Preferably, Tm−70 <Ta <Tm + 120 ° C., more preferably Tm−50 <Ta <Tm + 100 ° C.
By doing in this way, pinhole generation | occurrence | production of a molded article can be suppressed.

The set temperature Ta of the specific preferable supply zone (a) is in the range of −70 ° C. to + 150 ° C. of the glass transition temperature of the polycarbonate resin, more preferably in the range of −50 to + 100 ° C., and melt kneading. It is preferable that the temperature is not higher than the set temperature of the zone (b), but if it exceeds 310 ° C, there is a high possibility that the polycarbonate resin or the polyester resin will be decomposed. Therefore, the preferable range of the set temperature Ta in the specific supply zone (a) is 80 to 300 ° C, more preferably 90 to 280 ° C, and particularly 95 to 260 ° C. When the temperature is lower than 80 ° C., appearance defects of the molded product are likely to occur.
In the present invention, the set temperature (Ta) of the supply zone (a) is required to be controlled to be 10 ° C. or lower than the set temperature (Tb) of the melt kneading zone (b). Even if only a part of the supply zone (a) is partially or for a short time, the set temperature (Ta) can be increased as long as the effect of the present invention is not impaired. Of course, the present invention is included in the present invention as long as the temperature is controlled to be lower by 10 ° C. or more.

The set temperature Tb of the melt kneading zone (b) is set higher than the set temperature Ta of the supply zone (a).
It is preferable to set so as to satisfy the formula: Ta-5 <Tb <Ta + 50.
Specifically, the temperature of the first melt-kneading zone (b) is preferably 300 ° C. or lower, more preferably 250 to 295 ° C. and higher than the set temperature Ta of the supply zone (a). Is preferred.
If the set temperature Tb of the melt-kneading zone (b) is too high, the resin will be deteriorated so severely that the physical properties necessary for the molded product cannot be obtained and stable molding tends to be difficult.

Furthermore, the set temperature Tc of the melting zone (c) may be higher than the set temperature Tb of the melt-kneading zone (b), but it is equal to or lower than 0 to 30 ° C., that is,
It is preferable to set so as to satisfy the formula: Tb-30 <Tc <Tb + 5. Specifically, the set temperature Tc of the melting zone (c) is preferably about 230 to 290 ° C. and equal to or lower than the set temperature Tb of the melt kneading zone (b).

  If the temperature of the melting zone (c) is too high, the resin material is likely to deteriorate, the resin leaks from the tip of the nozzle 2 and it becomes difficult to perform stable molding, and if it is too low, the viscosity of the resin increases too much and stable molding is possible. It tends to be difficult.

  In addition, the zone ratio of the supply zone (a), the melt kneading zone (b), and the melting zone (c) is usually 40 to 70% / melt of the supply zone / melt kneading zone / the total length of the melting zone 100. The kneading zone is about 5 to 20% / melting zone about 15 to 35%. If the length of the supply zone is shorter than this, the bite will be poor and the amount of plasticization will be insufficient, the amount of heat supplied to the raw resin will be insufficient, and the measurement will be liable to occur. Deaeration and melt-kneading tend to be insufficient.

A known apparatus can be used as the melt extruder used in the present invention, and a vented extruder is preferably used. Specifically, for example, the same direction meshing type twin screw extruders such as TEX series manufactured by Nippon Steel Works, TEM series manufactured by Toshiba Machine Co., Ltd., KTX series manufactured by Kobe Steel, and ZSK series manufactured by Warner are preferably used.
Moreover, as a material of the resin contact part of the barrel and screw of an extruder used by this invention, it is preferable to use the metal excellent in corrosion resistance and abrasion resistance, such as stellite, hastelloy, and Kolmonoy. When a material having high corrosion resistance and high wear resistance is used, it is more preferable because the barrel and the screw surface are not easily eroded, and the number of foreign matters in the pellet can be further reduced. Further, the effect is increased by applying titanium coating such as titanium carbide or titanium nitride, hard chrome plating or nickel plating on the surface material of the barrel and screw resin contact portion of the extruder.
The ratio (L / D) of the screw length (L) to the diameter (D) in the twin-screw extruder is preferably 20 to 50, more preferably 30 to 42. When the L / D is 20 or less, it is difficult to melt and knead the resin composition sufficiently. When the L / D is 50 or more, the thermal load applied to the resin composition becomes too high, so that the mechanical properties are deteriorated.
It is preferable to install at least one kneading zone in the twin screw extruder. The length of the kneading zone is preferably 1 to 15 in L / D, more preferably 2 to 10 in L / D. When the length of the kneading zone is less than 1 in L / D, the resin composition cannot be sufficiently melt-kneaded, and an unmelted product is generated. On the other hand, when the ratio is 15 or more, the shearing force and thermal load applied to the resin composition become excessively high, so that deterioration and burns occur, and the mechanical properties are lowered.

[3. Raw material resin 1: Polycarbonate resin (A1)]
[2. Raw material resin 1: aromatic polycarbonate resin (A1)]
As is well known, the aromatic polycarbonate resin (A1) is produced by an interfacial polymerization method in which an aromatic dihydroxy compound is reacted with phosgene or a transesterification method in which it is reacted with a carbonic acid diester. Can also be used. In the transesterification method, the terminal OH group concentration may be adjusted by reacting the terminal blocking agent, but those subjected to this treatment can also be used.

  As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) is mainly used, but as is well known, other aromatic dihydroxy compounds such as tetramethylbisphenol A are used. Bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, and the like can also be used. In addition, in order to impart flame retardancy to the resulting resin, a compound in which tetraalkylphosphonium sulfonate is bonded to the above aromatic dihydroxy compound, a polymer or oligomer having a siloxane structure and having a phenolic OH group at both ends are used. It can also be used together.

  In the present invention, a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, which is usually easily available on the market, is used, but other polycarbonate resins such as 2,2-bis (4-hydroxy) are used. Copolymeric polycarbonate resins derived from (phenyl) propane and other aromatic dihydroxy compounds can also be used. Two or more polycarbonate resins may be used in combination.

  In the present invention, it is preferable to use an aromatic polycarbonate resin (A1) having a viscosity average molecular weight (MV) of 14,000 to 30,000. If the viscosity average molecular weight is too low, the mechanical strength of the resin composition is remarkably reduced. Conversely, if the viscosity average molecular weight is too high, the fluidity is remarkably reduced. The viscosity average molecular weight is preferably 15,000 to 29,000, and most preferably 16,000 to 28,000. The viscosity average molecular weight is calculated based on the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent.

  In the present invention, as the aromatic polycarbonate resin (A1), not only a virgin product but also a product regenerated from a used product, a so-called material recycled product can be used. For example, optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, spectacle lenses, soundproof walls, glass windows, and building materials such as corrugated plates It is possible to use those reproduced from the above. Moreover, what was regenerated from defective products, sprues, runners, etc. at the time of molding can also be used.

[4. Raw material resin 2: Other thermoplastic resin (A2) other than (A1)]
Examples of the thermoplastic resin (A2) other than the aromatic polycarbonate resin (A1) used in the present invention include, for example, polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), polybutylene terephthalate resin ( Thermoplastic polyester resins such as PBT resin);
Polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA) Resin), styrene resin such as acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin);

Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin;
Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU) Resin); polymethacrylate resin (PMMA resin); and the like.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

Of the other thermoplastic resins (A2), the most preferable is a polyester resin.
As the polyester resin, a thermoplastic polyester resin obtained by subjecting an aromatic dicarboxylic acid as a main acid component to a polycondensation reaction with an alcohol mainly containing an aliphatic glycol is used. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and diphenyldicarboxylic acid. Examples of the aliphatic glycol include alkylene glycols having 2 to 10 carbon atoms such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or neo Examples include pentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Furthermore, bisphenol A polyoxyethylene glycol, polyoxytetramethylene glycol, and the like are also included.

  Polyester resins can be copolymerized with hydroxycarboxylic acids such as parahydroxybenzoic acid, carboxylic acids other than aromatic dicarboxylic acids, and alcohols other than aliphatic diols. In the present invention, such copolymer resins are used. You can also However, such a copolymer component is preferably a small amount, and 80% by mass or more, more preferably 90% by mass or more of the polyester resin is preferably a component from an aromatic dicarboxylic acid and an aliphatic diol. The aromatic dicarboxylic acid and the aliphatic diol each preferably occupy 80 mol% or more, more preferably 90 mol% or more, with one compound.

  Specific examples of such a polyester resin include polybutylene terephthalate, polybutylene naphthalate, polycyclohexanedimethanol terephthalate, polyethylene terephthalate, and polyethylene naphthalate. These may contain a copolymerization component. In the present invention, among these, it is preferable to use polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), and it is also preferable to use both in combination. When used in combination, the ratio is preferably PET: PBT = 1: 1 to 1: 8 (mass ratio).

  As the polymerization catalyst for producing the polyethylene terephthalate resin, germanium compounds, antimony compounds, tin compounds, titanium compounds and the like are known. In the present invention, it is preferable to use a polymer obtained by polymerizing a germanium compound as a catalyst. When a polymer obtained by polymerization with another catalyst is used, the thermal stability and recyclability of the composition with the finally obtained polycarbonate resin tends to be lowered. Germanium compounds used as catalysts include germanium oxides such as germanium dioxide, germanium alkoxides such as germanium tetraethoxide, germanium tetraisopropoxide, germanium hydroxide and its alkali metal salts, germanium glycolate, germanium chloride, germanium acetate, etc. Is mentioned. These may be used alone or in combination of two or more. Among these, it is preferable to use germanium dioxide from the viewpoints of solvent resistance and thermal stability of the obtained polyethylene terephthalate resin.

  The germanium catalyst is preferably used in a polyethylene terephthalate resin to be produced so that the germanium atom is 15 PPM to 40 PPM. If it is less than 15 PPM, the progress of the polymerization reaction is slow, and if it exceeds 40 PPM, a side reaction may occur due to the germanium compound remaining in the resin.

  As the polybutylene terephthalate resin, a polymer obtained by polymerizing a titanium compound as a main catalyst and a Group 1 metal compound or Group 2 metal compound as a cocatalyst is preferably used. Examples of the titanium compound include inorganic titanium compounds such as titanium oxide and titanium tetrachloride; titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate; titanium phenolates such as tetraphenyl titanate and the like. . Of these, titanium alcoholates are preferably used. Most preferred are tetraalkyl titanates, especially tetrabutyl titanate.

  The titanium compound is preferably used in the resulting polybutylene terephthalate resin so as to be 20 PPM to 50 PPM, particularly 30 to 40 PPM in terms of titanium atoms. If the amount of the titanium compound used is too large, the color tone and hydrolysis resistance of the resulting polybutylene terephthalate resin may decrease, or solution haze and foreign matter increase may occur due to deactivation of the titanium catalyst. Conversely, if the amount is too small, the polymerizability of the polybutylene terephthalate resin tends to decrease.

  The molecular weight of the polyester resin is preferably such that the intrinsic viscosity measured at 30 ° C. in a mixed solvent of phenol and tetrachloroethane (mass ratio = 50/50) is 0.4 to 2.0. If a material having an intrinsic viscosity of less than 0.4 is used, the mechanical strength of the resin composition is inferior. Conversely, if it has a viscosity exceeding 2.0, the moldability tends to decrease. The preferable intrinsic viscosity of the polyester resin is 0.6 to 1.2.

The blending ratio of the aromatic polycarbonate resin (A1) and the other thermoplastic resin (A2) is a mass ratio of (A1) / (A2) and is a ratio of 50 to 99 / 50-1.
When the other thermoplastic resin (A2) is a polyester resin, the blending ratio is 50 to 99/50 to 1 in terms of mass ratio of polycarbonate resin (A1) / polyester resin (A2). The chemical resistance of the resin composition is insufficient, and if it exceeds 99, the heat resistance and impact resistance may decrease. A more preferable blending ratio is polycarbonate resin 51 to 90 / polyester resin 49 to 10, particularly polycarbonate resin 60 to 80 / polyester resin 40 to 20.

[5. Other components of thermoplastic resin composition 1: rubber polymer (B)]
The thermoplastic composition used in the present invention contains a rubbery polymer.
What is necessary is just to use what is mix | blended with a polyester resin or a polycarbonate resin, and is generally used for improving the impact resistance as a rubber polymer. For example, so-called rubber or rubber obtained by graft polymerization of a compound that reacts with rubber is used. The glass transition temperature of the rubbery polymer is preferably 0 ° C. or less, particularly preferably −20 ° C. or less.

  Specific examples of rubbery polymers include, for example, polybutadiene, polyisoprene, diene copolymers (styrene / butadiene copolymers, acrylonitrile / butadiene copolymers, acrylic / butadiene rubbers, etc.), ethylene and 3 or more carbon atoms. Copolymers of Α-olefins (ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / octene copolymers, etc.), copolymers of ethylene and unsaturated carboxylic acid esters (ethylene / methyl methacrylate) Copolymers, ethylene / butyl acrylate copolymers, etc., copolymers of ethylene and aliphatic vinyl compounds, terpolymers of ethylene, propylene and non-conjugated dienes, acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl) Acrylate), butyl acrylate, 2-ethylhexyl Acrylate copolymers), silicone rubber (a polyorganosiloxane rubber, a polyorganosiloxane rubber and a polyalkyl (meth) IPN type composite rubber consisting of acrylate rubber), and the like. These may be used alone or in combination of two or more.

  Another example of the rubber polymer is a copolymer obtained by graft polymerization of a monomer component to the above rubber polymer. Examples of this monomer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and the like. In addition, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide; and soot such as maleic acid, phthalic acid, and itaconic acid Examples thereof also include unsaturated carboxylic acid compounds and anhydrides thereof (for example, maleic anhydride). These monomers can be used alone or in combination of two or more.

  The rubbery polymer is preferably of the core / shell type graft copolymer type from the viewpoint of improving the impact resistance of the resin composition. Above all, rubber selected from butadiene component-containing rubber, butyl acrylate component-containing rubber and silicone rubber is used as a core layer, and a monomer selected from acrylic acid ester, methacrylic acid ester and aromatic vinyl compound is grafted around it. A core / shell type graft copolymer comprising a shell layer formed in this manner is particularly preferred.

  Examples of core / shell type graft copolymers include methyl methacrylate-butadiene-styrene polymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS), methyl methacrylate-butadiene polymer (MB), methyl Methacrylate-acrylic rubber polymer (MA), methyl methacrylate-acrylic rubber-styrene polymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, methyl methacrylate- (Acrylic / Silicone IPN (INTERPRANETRATING POLYMER NETWORK) rubber) polymer and the like. These rubbery polymers may be used alone or in combination of two or more.

  A preferable blending amount of the rubber polymer is 0.5 to 30 rubber polymer with respect to 100 parts by mass of the total amount of the aromatic polycarbonate resin (A1) and the thermoplastic resin (A2) other than (A1). 1 to 25 parts by mass of a rubbery polymer with respect to 100 parts by mass of the thermoplastic resin, preferably 100 parts by mass. When the blending amount of the rubber polymer is less than 0.5 parts by mass, the effect of improving the impact resistance is small, and when it exceeds 30 parts by mass, the heat resistance and rigidity may be lowered. The compounding amount of the rubber polymer is most preferably 2 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

[6. Other components of thermoplastic resin composition 2: inorganic filler]
Moreover, it is preferable that the thermoplastic composition used for this invention contains an inorganic filler in order to improve intensity | strength and rigidity.
The shape of the inorganic filler is arbitrary such as a needle shape, a plate shape, a granular shape or an amorphous shape. Specific examples of inorganic fillers include glass fillers such as glass fibers (chopped strands), short glass fibers (milled fibers), glass flakes, and glass beads; carbon fillers such as carbon fibers, carbon short fibers, carbon nanotubes, and graphite. ; Whiskers such as potassium titanate and aluminum borate; silicate compounds such as talc, mica, wollastonite, kaolinite, zonotolite, sepiolite, attabargite, montmorillonite, bentonite, smectite; silica, alumina, calcium carbonate, etc. . Among these, talc, mica, wollastonite, and kaolinite are preferable for the purpose of obtaining good surface design properties, and talc and wollastonite are particularly preferable.
Two or more inorganic fillers may be used in combination.

  The preferable content of the inorganic filler is 1 to 60 parts by mass with respect to 100 parts by mass of the total amount of other thermoplastic resins (A2) such as the polycarbonate resin (A1) and the polyester resin. In order to develop the effect of the inorganic filler, at least 1 part by mass should be contained. When the content of the inorganic filler is less than 1 part by mass, the reinforcing effect may not be sufficient. Moreover, when it exceeds 60 mass parts, an external appearance and impact resistance may be inferior, and fluidity | liquidity may not be enough. The more preferable content of the inorganic filler is 3 to 50 parts by mass, particularly 5 to 30 parts by mass.

  From the viewpoint of thermal stability when the inorganic filler is contained in the resin composition, a granular material having an average particle diameter of 0.01 to 100 μm granulated with a binder is preferable. The average particle diameter is more preferably 0.05 to 50 μm, and further preferably 0.1 to 25 μm. If the average particle size is too small, the reinforcing effect tends to be insufficient. Conversely, if the average particle size is too large, the product appearance tends to be adversely affected, and the impact resistance may be insufficient. The most preferable average particle diameter of the inorganic filler is 0.2 to 15 μm, particularly 0.3 to 10 μm.

[6-2. Talc or Wollastonite]
The thermoplastic resin composition (C) used in the present invention has an average particle size of 0.5 to 5.0 μm as measured with a laser diffraction particle size distribution analyzer for the purpose of improving strength and rigidity, and It is preferable to contain talc or wollastonite (D) substantially free of particles having a particle size of 15 μm or more.
When the average particle diameter of talc or wollastonite (D) is less than 0.5 μm, the thermal stability of the thermoplastic resin composition (C) tends to be insufficient, and when it exceeds 5.0 μm, the thermoplastic resin composition μm ( The appearance and rigidity of the molded product of C) are deteriorated. A particularly preferable average particle diameter is 0.5-4.

Furthermore, it is preferable that talc or wollastonite (D) contains substantially no particles having a particle diameter of 15 μm or more.
Since talc or wollastonite (D) does not substantially contain particles having a particle diameter of 15 μm or more, talc or wollastonite (D) can be present in the island portion of the aromatic polyester resin (A2). As a result, since the stress concentration point when stress is applied to the thermoplastic resin composition (C) is reduced, the impact resistance is remarkably increased, and the thermoplastic resin composition (C) is molded from the thermoplastic resin composition (C). The surface property of the molded product is also very excellent.

The average particle diameter in the present invention refers to D ₅₀ measured by a laser diffraction type particle size distribution measuring apparatus, the measurement was carried out using a Shimadzu "laser diffraction particle size distribution measuring apparatus SALD-2100".
In addition, the term “substantially does not contain” when the particle diameter does not substantially contain particles having a particle diameter of 15 μm or more includes the case where particles having the prescribed particle diameter are not completely contained, as a matter of course. It means that it is not detected by the measuring device.

The average particle diameter of talc or wollastonite (BD) is preferably 0.5 to 8 μm, more preferably 1 to 5 μm. Further, the particle diameter of the particles not substantially contained is preferably 13 μm or more, more preferably 10 μm or more, and particularly 8 μm or more.
A preferable production of talc or wollastonite (D) substantially free of particles having a particle size of 15 μm or more is obtained by, for example, grinding talc or wollastonite with a jet mill and then passing it through a screen and a screen of a classifier. It can be obtained by a method such as increasing the time required.

Talc is a hydrous magnesium silicate having a layered structure, the chemical formula is represented by _{4SiO 2 · 3MgO · H 2 O} , the normal SiO ₂ 58 to 66 wt%, the MgO 28 to 35 wt%, of _{H 2} O About 5% by mass is contained. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by mass, Al ₂ O ₃ is 0.05 to 1.5% by mass, CaO is 0.05 to 1.2% by mass, and K ₂ O is 0.2 wt% or less, Na ₂ O are contained below 0.2 wt%, a specific gravity of about 2.7.
Wollastonite is a white mineral having needle-like crystals, and its chemical formula is represented by CaO.SiO ₂ . Usually, SiO ₂ contains about 50% by mass, CaO contains about 46% by mass, Fe ₂ O ₃ , Al ₂ O _{3 and the} like, and the specific gravity is 2.9.

  The content of talc or wollastonite (D) is preferably 1 to 60 parts by mass with respect to 100 parts by mass of the total amount of the aromatic polycarbonate resin (A1) and the aromatic polyester resin (A2). In order to express the effect of component (D), at least 1 part by mass should be contained, and if it is less than 1 part by mass, the reinforcing effect is not sufficient. Moreover, when it exceeds 60 mass parts, an external appearance and impact resistance are inferior, and fluidity | liquidity is not enough. (D) The preferable content of a component is 3-50 mass parts, especially 5-30 mass parts.

  Talc or wollastonite (D) is a granulated product obtained by granulating an average particle size of 0.5 to 8 μm using a binder from the viewpoint of surface appearance and thermal stability when contained in a resin composition. Are preferred. The average particle diameter is more preferably 0.5 to 8 μm, and further preferably 1 to 5 μm. If the average particle size is too small, the reinforcing effect tends to be insufficient. Conversely, if the average particle size is too large, the product appearance tends to be adversely affected, and the impact resistance may be insufficient. The most preferred average particle diameter of the granular filler is 1 to 4 μm, particularly 2 to 4 μm.

  The granular talc is preferably subjected to a surface treatment in order to increase the affinity between the aromatic polycarbonate resin (A1) and the aromatic polyester resin (A2). Specific examples of the surface treatment agent include alcohols such as trimethylolethane, trimethylolpropane, and pentaerythritol, alkanolamines such as triethylamine, organosilicone compounds such as organopolysiloxane, higher fatty acids such as stearic acid, Fatty acid metal salts such as calcium stearate and magnesium stearate, polyethylene wax, hydrocarbon lubricants such as liquid paraffin, basic amino acids such as lysine and arginine, polyglycerol and their derivatives, silane coupling agents, titanate couplings And at least one selected from coupling agents such as an agent and an aluminum-based coupling agent.

  The bulk density of granular talc or wollastonite is 0.4 to 1.5 g / ml, more preferably 0.5 to 1.3 g / ml, particularly preferably 0.6 to 1.1 g / ml. is there. When the bulk density is 0.4 g / ml or more, the thermal stability and impact resistance of the resin composition tend to be further improved. On the other hand, when the bulk density is less than 1.5 g / ml, the thermoplastic resin The appearance and impact resistance of the molded product of the composition (C) tend to be further improved.

Here, the bulk density is a value obtained by the following method.
(1) A sample of granular talc or wollastonite is placed on a sieve having an opening of 1.4 mm and passed through the sieve while being evenly lightly swabbed with a brush.
(2) The sample passed through the sieve is put into a receiver attached to the bulk density measuring device specified in JIS K5101 until it reaches a heap.
(3) The sample piled up at the top from the inlet of the receiver is scraped off with a spatula, the mass of the sample in the receiver is measured, and the bulk density is calculated by the following equation.
Bulk density (g / ml) = mass of sample in receiver (g) / capacity of receiver (ml)

  As the granular talc or wollastonite, those having a mesh ratio of 55% by mass or more are usually used because the thermal stability of the resin composition tends to be further improved. It is preferable to use a sieve having a ratio of 60% by mass or more, more preferably 70% by mass or more. Most preferably, the sieve is 90% by mass or more.

Here, the particle size of granular talc or wollastonite is a value determined by the following method in accordance with JIS Z8801.
(1) Place the sample on a sieve having an opening of 2 mm, and pass through the sieve while sweeping lightly with a brush.
(2) Put the above sample passed through a sieve into a 200 ml beaker and use a sample reducer (for example, sample reducer “13056 6” (groove width 6 mm) manufactured by Yoshida Seisakusho) until it reaches about 30 ml. Perform reduction.
(3) Using a sieve having an opening of 500 μm, the above-mentioned reduced sample is sieved, the mass that does not pass through the 500 μm sieve is determined, and the ratio from the total amount is determined. In addition, sieving is performed for 10 minutes at a vibration frequency of 120 times / second using a vibration sieve (for example, “Electromagnetic Vibrating Sieve M-100 Model” manufactured by Tsutsui Chemical Co., Ltd.).

  As a binder used when producing granular talc or wollastonite, it has a high granulation property with raw material talc or wollastonite, is almost colorless or white, and is an inert and stable substance. Any material that does not decrease the physical properties of the molded article to be produced, such as clay minerals, colloidal silica, gypsum, water-soluble polymers, waxes, higher fatty acids, resin powders and the like that exhibit high caking properties under wet conditions such as bentonite, etc. Is mentioned. Of these, clay minerals and water-soluble polymers are preferable, and water-soluble polymers are more preferable from the viewpoint of thermal stability, impact resistance, and rigidity of the resin composition.

Examples of the water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, sodium polyacrylate, sodium alginate, agar, and polysaccharides (cellulose cellulose such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose sodium). Derivatives, starch, etc.), proteins (gelatin, glue, etc.), dicarboxylic acid components composed of dicarboxylic acids or reactive derivatives thereof, diol components composed of diols or ester derivatives thereof, and water-solubilizing components. Examples thereof include water-soluble polyester copolymers obtained by using a raw material as a main component and subjecting them to a condensation reaction.
Among these, a water-soluble polyester having a high affinity for the resin and a high adsorptivity to talc or wollastonite is more preferable, and specific examples thereof include terephthalic acid, ethylene glycol, and 5-sodium sulfoisophthalic acid. And “Plus Coat Z-221”, “Plus Coat Z-561”, “Plus Coat Z-446”, etc. manufactured by Kyoyo Chemical Industry Co., Ltd., and the like.

  The binder content in the granular talc or wollastonite is preferably 0.01 to 5% by mass, more preferably 0.05 to 3.5% by mass, in 100% by mass of the granular talc or wollastonite, Most preferably, it is 0.1-2 mass%. When the binder content is 0.01% by mass or more, granular talc or wollastonite is difficult to collapse during handling, and when the binder content is less than 5% by mass, disintegration and dispersion in the resin composition Tends to be more favorable, and the appearance and impact resistance of the molded product of the resin composition tend to be further improved.

In the production of granular talc or wollastonite, the kneadability between talc or wollastonite and a binder is enhanced, and the kneaded product is made plastic during granule production, facilitating production, and wear of the granulator. It is preferable to add a wetting agent in order to reduce the viscosity and to further adjust the hardness of the granular material. Usually, a lubricant is added to talc or wollastonite and a binder, and if necessary, a dispersant and other additives are added, and the mixture is stirred with a mixer such as a Henschel mixer or a super mixer.
This mixture is kneaded with a screw type extruder such as a single screw or a twin screw, then extruded into a strand, cut and granulated, and dried by using a fluid dryer, a band heater or the like to produce.

  The shape of granular talc or wollastonite is not particularly limited, such as rod-shaped, cylindrical, needle-shaped, spherical, granular, flake-shaped, and amorphous, and various types can be produced depending on the molding conditions and sizing conditions. it can. For example, when producing rod-shaped or cylindrical particles, the shaft diameter can be appropriately set by changing the size of the screen opening of the screen-type extruder, and after shaping, the particles can be sized and cut to the desired shaft length. it can. If it is in the range of said bulk density and a particle size, there will be no restriction | limiting in particular also in the magnitude | size.

  Examples of the lubricant include water and organic solvents, but water is preferable from the viewpoint of cost and workability, and alcohols may be mixed with water. It is possible to dissolve or suspend the binder in water, which is a wetting agent. Additives required for granules, such as dispersants, surfactants, and various synthetic resin additives The uniformity can be further improved by dissolving or suspending the dye or pigment. Further, when water is used as the lubricant, it is preferable to dry the moisture contained using a fluid dryer or the like so that the moisture content is 1% or less, and more preferably 0.3% or less. 80-150 degreeC is suitable for drying temperature, Preferably it is 80-110 degreeC.

  In the present invention, a granular talc or wollastonite resin is obtained by adding 0.05 to 2.0% by mass, preferably 0.1 to 0.5% by mass of a dispersant in granular talc or wollastonite. Since disintegration and dispersibility in the molded product of the composition are improved, it may be preferable. Dispersants to be used may be those generally known. For example, alcohols, alkanolamines, organic silicone compounds, higher fatty acids, fatty acid metal salts, hydrocarbon lubricants, basic amino acids, polyglycerols and derivatives thereof as described above may be used. Can be mentioned.

  Furthermore, the granular talc / wollastonite may contain various additives in addition to the dispersant as long as the characteristics of the present invention are not impaired. Such additives include various antioxidants such as hindered phenols, various heat stabilizers such as phosphites, various ultraviolet absorbers such as benzotriazoles, benzophenones, and triazines, silicones, and metal salts. Various flame retardants such as olefins, various release agents such as olefin waxes and fatty acid esters, antibacterial and antifungal agents such as phenols, anionic, cationic and nonionic antistatic agents, colorants, talc / Fillers other than wollastonite, light stabilizers, plasticizers, foaming agents, anti-dripping agents, and the like. Further, the organophosphate compound (C) can be contained in granular talc and contained in the resin composition. In addition, these various additives are contained in the granular talc / wollastonite, the thermoplastic resin (A), the rubber polymer (B), the organic phosphate compound (C), the inorganic filler ( When producing pellets by melt-kneading D) or the like, they may be blended alone.

[7. Other component 3 of thermoplastic resin composition: organophosphate compound]
Moreover, it is preferable that the thermoplastic resin composition used in the present invention contains an organic phosphate compound.
The organic phosphate ester compound has a partial structure in which 1 to 3 alkoxy groups or aryloxy groups are bonded to a phosphorus atom. In addition, a substituent may further be bonded to these alkoxy groups and aryloxy groups.

  Specific examples of the organic phosphate ester compound include bis (distearyl acid phosphate) zinc salt, monostearyl acid phosphate zinc salt, tris (distearyl acid phosphate) aluminum salt, one monostearyl acid phosphate and two And salts with monostearyl acid phosphate aluminum, monostearyl acid phosphate, distearyl acid phosphate and the like. These may be used alone or as a mixture. Examples of commercially available products include “LBT-1830” (zinc stearyl acyl phosphate) manufactured by Sakai Chemical Industry Co., Ltd., and “LBT-1813” (phosphate aluminum salt based phosphate), Johoku Chemical Industry Co., Ltd. There are a product name “JP-518Zn” (oleyl acid phosphate type), a product name “Adeka Stab AX-71” (octadecanoxy phosphate type) manufactured by ADEKA, and the like.

  The organophosphate compound is preferably blended in an amount of 0.02 to 1 part by mass with respect to 100 parts by mass of the thermoplastic resin composition (c). If the blending amount is small, it becomes difficult to sufficiently ensure the impact resistance, residence heat stability, and chemical resistance of the resin composition. On the other hand, when the blending amount is too large, mold contamination occurs when the resin composition is extruded, and the impact strength of the molded product tends to decrease. A more preferable blending amount is 0.05 parts by mass or more, particularly 0.1 parts by mass or more, with respect to 100 parts by mass of the thermoplastic resin composition (c). The amount is preferably 3 parts by mass.

[8. Other components of thermoplastic resin composition]
The thermoplastic resin composition (C) in the present invention may contain other components in addition to those described above, as required, as long as the desired physical properties are not significantly impaired. Can be mentioned. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.
-Other additives The thermoplastic resin composition in the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include heat stabilizers, antioxidants, mold release agents, flame retardants, dyes and pigments, fluorescent whitening agents, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, flow Examples include property improvers, plasticizers, dispersants, and antibacterial agents.

[9. Method for producing thermoplastic resin composition (C)]
There is no restriction | limiting in the manufacturing method of a thermoplastic resin composition (C), The manufacturing method of a well-known polycarbonate-type resin composition can be employ | adopted widely.
Specific examples include each component according to the present invention, and other components blended as necessary, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single or twin screw extruder, a kneader. And the like, and the like. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

  When the molten resin is made into pellets, the molten resin is extruded in a strand shape, passed through a discharge die, and usually provided with a cooling water tank. After the cooling treatment, the molten resin is cut by a cutting means such as a pelletizer to obtain an average particle size of 1 The pellet is about ˜5 mm.

[8. Gas injection injection molding]
Such a pellet for molding raw material produced according to the present invention can be formed into a molded product by various molding methods, but a molded product having a hollow portion is manufactured by injection molding, particularly gas injection injection molding. It is suitable for.
In gas injection injection molding, the above-mentioned thermoplastic resin composition (C) pellets are melted in an injection molding machine, and a certain amount is injected into a mold cavity, and a high-pressure inert gas (usually at an appropriate timing) Nitrogen gas) is usually injected from a nozzle or a mold cavity, and shaping is performed by gas. This method is also called gas-assisted injection molding.
The preferred gas holding pressure is 10 to 24 MPa, and the mold surface temperature is preferably in the range of 40 to 100 ° C.

Further, in the present invention, the gas injection injection molding should not be construed as limited to the above, but includes air-assisted injection press molding, PFP (Partial Frame Process), high hollow body molding (H ² M molding), It broadly refers to a molding method in which the injected resin is shaped by gas, such as channel molding (CGM) using an insulating layer and External Gas Injection.

The hollow molded product obtained by gas injection injection molding has excellent mechanical strength such as thermoplastic resin composition (C), low temperature impact resistance, tensile strength, bending strength, heat resistance, chemical resistance, surface design, Since it has excellent cycle stability during molding, the sea-island structure of the molded product becomes even more pronounced, it can achieve exceptionally excellent impact resistance, and the molded product has excellent surface properties with no occurrence of pinholes etc. Become.
Such molded products have excellent impact resistance, chemical resistance, and dimensional stability, so interior parts, exterior parts, electrical / electronic / OA equipment parts, mobile phones, machines, etc. Suitable for a wide range of applications such as parts, building materials, recreational goods and miscellaneous goods.

  Specifically, for example, there are outer handles, door mirror sticks, fenders, garnishes, bumpers, roof rails, wiper arms, etc. as automotive exterior parts, and inner handles, center console, instrument panel, assist grip, seats as automotive interior parts. Examples include belt stoppers.

Rail vehicle parts include table arms, suspension hands, and assist grips. Electric parts include shaver frames, dryers, refrigerator handles and pullers, microwave oven doors, portable MD system handles, and headphone arms. And a housing for an electric screwdriver. Examples of building material parts include door handles, crescents, and French droppings.
In particular, because of its excellent appearance, productivity, etc., it is preferably used particularly for outer / inner handle applications for vehicles and aircraft.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The raw materials used in the examples and comparative examples are as follows.

Polycarbonate resin Aromatic polycarbonate resin Bisphenol A-type aromatic polycarbonate produced by the interfacial polymerization method Iupilon E-2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 28,000

Polyester resin Polybutylene terephthalate resin (PBT (1)):
NOVADURAN 5020, intrinsic viscosity 1.20 dl / g, manufactured by Mitsubishi Engineering Plastics
Polybutylene terephthalate resin (PBT (2)):
NOVADURAN 5008, inherent viscosity 0.85 dl / g, manufactured by Mitsubishi Engineering Plastics
Polyethylene terephthalate resin (PET):
Novapex GG500 manufactured by Mitsubishi Chemical Corporation
Germanium atom content 28ppm, intrinsic viscosity 0.76dl / g
The intrinsic viscosity of each polyester resin described above is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solution of phenol and tetrachloroethane.

Rubber polymer:
Core / shell type graft copolymer comprising polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (shell) EXL2603 manufactured by Rohm and Haas Japan, softening point temperature of about 105 ° C.

Organophosphate compounds:
Butoxyethyl acid phosphate Product name JP-506H (C ₄ H ₉ OC ₂ H ₄ O) _n P (O) (OH) _3-n n = 1, 2 manufactured by Johoku Chemical Industry Co., Ltd.
Thermal stabilizer: Tris (2,4-di-tert-butylphenyl) phosphite Product name ADK STAB AS2112 manufactured by Asahi Denka Kogyo Co., Ltd.

Talc: Matsumura Industrial Co., Ltd. granular talc (hereinafter referred to as granular talc A)
Average particle size: 3.7 μm, particle top size: 14 μm
Measured using a laser diffraction particle size distribution analyzer “SALD2100” manufactured by Shimadzu Corporation.
Bulk density 0.72 g / ml
The ratio of the particle size / aperture on the 500 μm sieve is 98% by mass.
Particle shape / cylindrical shape, average shaft diameter 1.2 mm, average shaft length 1.5 mm
Binder type / water-soluble polyester

(Examples 1-6 and Comparative Examples 1-4)
<Preparation of resin composition>
Thermoplastic resin compositions 1 and 2 having the proportions shown in Table 1 as shown in Table 1 were prepared as follows.

  The components shown in composition C1 in Table 1 above were uniformly mixed by a tumbler-mixer at the ratio shown in the same table, then fed to a twin-screw extruder (“TEX30XCT” manufactured by Nippon Steel Works), and supplied to a supply zone (a ) Set temperature (Ta) and melt kneading zone (b) set temperature (Tb) as described below, the melt-kneaded resin composition is rapidly cooled in a water tank, pelletized using a pelletizer, A pellet of the composition was obtained.

  This twin screw extruder has L / D = 42, the number of barrels is 12, the screw diameter is 30 mm, the screw configuration is 1250 mm in the total length of the supply zone, the melt-kneading zone, and the melt zone, and the supply zone (a) Corresponding barrel is 4 barrels (C1 to C4), groove depth is 6mm, barrel corresponding to melt kneading zone (b) is 2 barrels (C5 to C6), groove depth is 6mm, corresponding to melting zone (c) The barrel to be performed is 6 barrels (C6 to C12), and the groove depth is 6 mm.

  While setting the cylinder set temperatures Ta, Tb, Tc of the supply zone (a), the melt-kneading zone (b) and the melt zone (c) to the temperatures described in Table 2, while maintaining the temperature of each zone at the set temperature, It carried out on the conditions of screw rotation speed 250rpm.

(Examples 7 to 10 and Comparative Examples 5 to 6)
<Preparation of resin composition>
The components shown in composition C1 in Table 1 above were uniformly mixed with a tumbler-mixer at the ratio shown in the table, and then fed to a twin-screw extruder (“OTE-57” manufactured by Osaka Seiki Co., Ltd.) The set temperature (Ta) of (a) and the set temperature (Tb) of the melt-kneading zone (b) are controlled as described below, and the melt-kneaded resin composition is rapidly cooled in a water tank and pelletized using a pelletizer. A pellet of the resin composition was obtained.

  This twin-screw extruder has L / D = 31.6, the number of barrels is 10, the screw diameter is 57 mm, the screw configuration is 1800 mm in total length of the supply zone, the melt-kneading zone, and the melt zone. ) Corresponds to 4 barrels (C1 to C6), the groove depth is 10 mm, the barrel corresponding to the melt kneading zone (b) is 1 barrel (C7), the groove depth is 10 mm, and corresponds to the melting zone (c). The barrel is 7 barrels (C8 to C10) and the groove depth is 10 mm.

  The cylinder set temperatures Ta, Tb, and Tc of the supply zone (a), the melt kneading zone (b), and the melt zone (c) are set to the temperatures shown in Table 3 below, while maintaining the temperatures of the zones at the set temperatures. The screw rotation was performed at 200 rpm.

(Examples 11 to 16 and Comparative Examples 7 to 10)
<Preparation of resin composition>
The components shown in the composition C2 in Table 1 described above were uniformly mixed at a ratio shown in the same table using a tumbler mixer, and then fed to a twin-screw extruder (“TEX30XCT” manufactured by Nippon Steel Works) to supply a zone ( The set temperature (Ta) of a) and the set temperature (Tb) of the melt-kneading zone (b) are controlled as described later, the melt-kneaded resin composition is rapidly cooled in a water tank, pelletized using a pelletizer, A pellet of the resin composition was obtained.

  This twin screw extruder has L / D = 42, the number of barrels is 12, the screw diameter is 30 mm, the screw configuration is 1250 mm in the total length of the supply zone, the melt-kneading zone, and the melt zone, and the supply zone (a) Corresponding barrel is 4 barrels (C1 to C4), groove depth is 6mm, barrel corresponding to melt kneading zone (b) is 2 barrels (C5 to C6), groove depth is 6mm, corresponding to melting zone (c) The barrel is 7 barrels (C7 to C12), and the groove depth is 6 m.

  The cylinder set temperatures Ta, Tb, and Tc of the supply zone (a), the melt kneading zone (b), and the melt zone (c) are set to the temperatures shown in Table 4 below, while maintaining the temperature of each zone at the set temperature. The screw rotation was performed under the condition of 250 rpm.

<Measurement of impact resistance (Izod impact strength with notch)>
After drying the resin composition obtained above at 120 ° C. for 5 hours or more, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, cylinder temperature 280 ° C., mold temperature 80 ° C., molding cycle An ASTM test piece (a 3.2 mm thick notched test piece) was injection molded under the condition of 55 seconds. In accordance with ASTM D256, the ASTM test piece prepared above (a test piece with a notch of 3.2 mm thickness) was used, and the Izod impact strength (unit: J / m) was measured in a 23 ° C. environment. The results are shown in Table 1.
The results are shown in Tables 2-4.

<Evaluation of pinhole resistance by gas injection injection molding>
After drying the resin composition pellets obtained above at 120 ° C. for 5 hours or more, attach it to the J-220EV-P type injection molding machine manufactured by Nippon Steel, with the handshake part at the center and the vehicle body at both ends. A mold for molding an outer handle for an automobile having a part (having a nozzle for gas injection) is attached, cylinder temperature is 280 ° C., mold temperature is 70 ° C., filling time is 7 seconds, gas injection delay is 8 seconds, gas pressure is 10 MPa, gas holding 30 shots were continuously molded under the conditions of a pressure time of 35 seconds and a molding cycle of 80 seconds. The number of pinholes generated during 30 shots was counted.
The results are shown in Tables 2-4.

  As can be seen from the results of Examples and Comparative Examples, when the pellets obtained by the production method of the present invention are used as raw materials and gas injection injection molding is performed, the impact resistance is excellent, and at the same time, there are few pinholes. It can be seen that a hollow molded article having a surface appearance can be obtained.

  According to the method for producing a molded article of the present invention, it is possible to provide a raw material pellet for gas injection injection molding capable of giving a molded article having sufficient mechanical strength and good surface appearance by gas injection injection molding. Therefore, it can be applied to a wide range of fields such as automobile interior / exterior parts field, electric / electronic parts field, etc., and industrial applicability is very high.

Claims (10)

The aromatic polycarbonate resin (A1) and the other thermoplastic resin (A2) other than (A1) are contained in a mass ratio of (A1) / (A2) at a ratio of 50 to 99/50 to 1, and The thermoplastic resin composition (C) containing 0.5 to 30 parts by mass of the rubbery polymer (B) is melt kneaded in an extruder with respect to 100 parts by mass of the total amount of the components (A1) and (A2). To produce pellets,
In the heating barrel of the extruder having at least one melt kneading zone, the set temperature (Ta) of the supply zone (a) for feeding the resin composition forward is set to the first melting for melt kneading the resin composition. A method for producing a raw material pellet for molding, characterized in that the temperature is controlled to be lower by 10 ° C. or more than the set temperature (Tb) of the kneading zone (b). The set temperature (Ta) of the supply zone zone (a) is relative to the softening point Tm of the rubber polymer (C).
Formula: Tm-100 <Ta <Tm + 150 ° C.
The manufacturing method according to claim 1, wherein:   The method according to claim 1 or 2, wherein the temperature of the first melt-kneading zone (b) is 300 ° C or lower.   The other thermoplastic resin (A2) is polybutylene terephthalate or polyethylene terephthalate, The production method according to any one of claims 1 to 3.   The thermoplastic resin composition (C) has a mean particle diameter of 0.5 to 5.0 μm measured by a laser diffraction particle size distribution analyzer and substantially free of particles having a particle diameter of 15 μm or more. Or 1 to 60 mass parts is contained for wollastonite (D) with respect to 100 mass parts of total amounts of said (A1) and (A2). The production method according to item.   6. The component (D) is granular talc having a bulk density of 0.4 to 1.5 g / ml granulated using talc and a binder. The manufacturing method as described in.   The production method according to claim 1, wherein at least one of the component (A1) or the component (A2) has a pellet shape.   The rubbery polymer (B) is supplied as a resin composition that has been previously masterbatched by the component (A1) or the component (A2). The manufacturing method as described in.   A method for producing a molded product comprising producing a molded product having a hollow portion by a gas injection injection molding method using the raw material pellets produced by the production method according to any one of claims 1 to 8. .   A molded product produced by the production method according to claim 9.

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