JP2015140362A - Polycarbonate resin composition and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a polycarbonate resin composition having no problem of reduction of various physical properties by hydrolysis of a resin caused by moisture in a polyester resin, and having excellent mechanical property, thermostability and appearance, by using the polyester resin having moisture content of 1,000 ppm or more without conducting preliminary drying of the polyester resin.SOLUTION: In manufacturing a polycarbonate resin composition containing total 100 pts.mass of a polycarbonate resin (A) of 50 pts.mass or more and a polyester resin (B) having moisture content of 1,000 ppm or more of 50 pts.mass or less as resin components by using an extruder, the extruder having two or more kneading zones and two or more vents in the downstream of the first kneading zone from an upstream side in an extrusion direction, is used.

Description

  The present invention relates to a polycarbonate resin composition in which a polyester resin is compounded with a polycarbonate resin, a method for producing a polycarbonate resin composition for improving the problems of deterioration of various properties caused by moisture contained in the polyester resin, and the polycarbonate resin composition The present invention relates to a polycarbonate resin composition produced by a method for producing a product, and a polycarbonate resin molded product obtained by molding the polycarbonate resin composition.

Polycarbonate resins are excellent in impact resistance, heat distortion resistance, rigidity, dimensional stability, etc., and are therefore used in a wide range of applications such as electrical equipment, communication equipment, precision machinery, and automobile parts.
In addition, as a polycarbonate resin used for these various uses, a composite of polyester resin such as polyethylene terephthalate resin has been proposed to improve chemical resistance (for example, Patent Documents 1 and 2). / Polyester composite resin compositions are currently widely used in interior and exterior parts for vehicles, taking advantage of their excellent chemical resistance and fluidity.

  The polyester resin which is one of the raw materials of the polycarbonate / polyester composite resin composition usually contains water of 1000 ppm or more. For this reason, when manufacturing a polycarbonate / polyester composite resin composition, there existed a problem that mechanical strength, heat resistance, and an external appearance fell because a resin hydrolyzes with the water | moisture content contained in a polyester resin.

Conventionally, the following measures have been taken to solve this problem.
1) Prior to producing the resin composition, the polyester resin is pre-dried at 120 to 150 ° C. for about 4 to 6 hours.
2) Purchase and use a polyester resin that has been dried and packed in an aluminum moisture-proof bag.

  However, in the above 1), since the polyester resin drying process is a separate process from the production of the resin composition, it takes work and time for the process, and energy consumption for drying and a new one accompanying the drying work. There is concern about the risk of serious contamination. In the above 2), since the polyester resin packed in the aluminum moisture-proof bag is expensive, there is a problem in terms of an increase in waste as well as an increase in cost of raw materials.

  A method for improving thermal stability, hue stability, hydrolysis resistance, and corrosion resistance by removing volatile impurities in the polycarbonate resin with a twin screw extruder with a multistage vent has been proposed. (For example, Patent Documents 3 to 5). Further, a method for removing moisture using a twin-screw extruder having a vacuum vent has been proposed in producing polyester sheets and fibers using the collected used polyester resin as a raw material (for example, Patent Documents 6 and 7). ).

  However, conventionally, it has not been proposed to perform melt kneading using an extruder having a plurality of vents and kneading zones for the purpose of improving the physical properties and residence heat stability of the polycarbonate / polyester composite resin composition. Furthermore, at that time, the positional relationship between the kneading zone and the vent is not considered at all.

Japanese Patent Laid-Open No. 2007-23118 JP 2009-1620 A JP 2001-31754 A JP 2002-187193 A International Publication WO00 / 43436 Pamphlet Japanese Patent Laid-Open No. 9-49118 JP 2001-18223 A

  The present invention uses a polyester resin having a water content of 1000 ppm or more without pre-drying the polyester resin, and is free from problems of deterioration in physical properties due to hydrolysis of the resin due to moisture in the polyester resin. It is an object of the present invention to provide a method for producing a polycarbonate resin composition having mechanical properties, thermal stability and appearance.

  As a result of intensive studies to solve the above problems, the present inventors have two or more kneading zones in the production of a polycarbonate / polyester composite resin composition and the first from the upstream side in the extrusion direction. By using an extruder having two or more vents after the kneading zone, the moisture contained in the polyester resin and further the moisture contained in other raw materials are effectively degassed in the melt-kneading process in the extruder. It was found that mechanical properties, residence heat stability, and appearance deterioration due to hydrolysis of the resin can be suppressed.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] Extruded as a resin component is a polycarbonate resin composition containing 100 parts by mass in total of 50 parts by mass or more of polycarbonate resin (A) and 50 parts by mass or less of polyester resin (B) having a water content of 1000 ppm or more. The extruder has two or more kneading zones, and has two or more vents downstream from the first kneading zone from the upstream side in the extrusion direction. A method for producing a polycarbonate resin composition.

[2] The polycarbonate resin composition according to [1], wherein the first vent from the upstream side in the extrusion direction of the extruder is an open vent or a decompression vent, and the second and subsequent vents are decompression vents. Manufacturing method.

[3] In [2], the first vent from the upstream side in the extrusion direction is a decompression vent, and the decompression degree (P1) of the first vent and the decompression degree (P2) of the second and subsequent vents are , P1 ≧ P2 is satisfied, A method for producing a polycarbonate resin composition,

[4] In [2], the first vent from the upstream side in the extrusion direction is a decompression vent, and the decompression degree (P1) of the first vent and the decompression degree (P2) of the second and subsequent vents are , P1 <P2 is satisfied, and P1 is −0.05 MPa or more, A method for producing a polycarbonate resin composition,

[5] In any one of [1] to [4], the extruder has one or more vents downstream from the most downstream kneading zone in the extrusion direction. Method.

[6] In any one of [1] to [5], the polycarbonate resin composition further comprises a thermoplastic elastomer (C) with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the polyester resin (B). ) Is contained in an amount of 0.5 to 30 parts by mass.

[7] In any one of [1] to [6], the polycarbonate resin composition may further include the following general formula (1) with respect to 100 parts by mass in total of the polycarbonate resin (A) and the polyester resin (B). 0.02-3 mass parts of organophosphate ester compounds (D) represented by this are contained, The manufacturing method of the polycarbonate resin composition characterized by the above-mentioned.
(RO) _n P (O) (OH) _3-n (1)
(In the formula, R represents an alkyl group having 2 to 25 carbon atoms which may have a substituent, and n represents 1 or 2. However, when n is 2, two Rs are the same. May be different or different from each other.)

[8] A polycarbonate resin composition produced by the method for producing a polycarbonate resin composition according to any one of [1] to [7].

[9] A polycarbonate resin molded product obtained by molding a polycarbonate resin composition produced by the method for producing a polycarbonate resin composition according to any one of [1] to [7].

According to the present invention, in the production of the polycarbonate / polyester composite resin composition, it has two or more kneading zones and two or more vents downstream from the first kneading zone from the upstream side in the extrusion direction. By using an extruder, in the melt-kneading process in the extruder, the moisture contained in the polyester resin and further the moisture contained in other raw materials are effectively degassed and removed, and the mechanical properties due to the hydrolysis of the resin In addition, it is possible to suppress the retention heat stability and the appearance deterioration.
For this reason, there is no need to pre-dry the polyester resin, and there is no need to use a polyester resin packed in an aluminum moisture-proof bag, and a polycarbonate resin composition having good mechanical properties, thermal stability and appearance can be efficiently used. Can be manufactured automatically.

  The polycarbonate resin composition produced by the present invention has excellent physical properties such as impact resistance and heat distortion resistance inherent to the polycarbonate resin, and also has excellent chemical resistance because it contains a polyester resin.

  Such a polycarbonate resin composition of the present invention is useful for various uses such as electric / electronic equipment parts, OA equipment, machine parts, vehicle parts, building members, various containers, leisure goods and miscellaneous goods, and particularly vehicle exteriors. -Expected to be applied to outer panel parts and vehicle interior parts.

  Examples of vehicle exterior / skin parts to which the polycarbonate resin composition of the present invention is applied include outer door handles, bumpers, fenders, door panels, trunk lids, front panels, rear panels, roof panels, bonnets, pillars, side moldings, garnishes, Wheel caps, hood bulges, fuel lids, various spoilers, motorbike cowls, etc.

  In addition, examples of vehicle interior parts include inner door handles, center panels, instrument panels, console boxes, luggage floor boards, display housings for car navigation, and the like. What is the application field of the polycarbonate resin composition of the present invention? It is not limited to these.

  In particular, the polycarbonate resin composition of the present invention is effective for molding a hollow injection molded product such as gas assist or a large molded product having a hot runner due to its excellent thermal stability.

It is a schematic diagram which shows the structure of the extruder used in the Example.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

  The production method of the polycarbonate resin composition of the present invention comprises, as a resin component, 100 parts by mass in total of 50 parts by mass or more of the polycarbonate resin (A) and 50 parts by mass or less of the polyester resin (B) having a water content of 1000 ppm or more. In producing the contained polycarbonate resin composition using an extruder, the extruder has two or more kneading zones, and 2 downstream from the first kneading zone from the upstream side in the extrusion direction. What has the above vent is used, The polycarbonate resin composition of this invention is manufactured by the manufacturing method of such a polycarbonate resin composition of this invention. The polycarbonate resin molded article of the present invention is formed by molding a polycarbonate resin composition produced by such a method for producing a polycarbonate resin composition of the present invention.

  In the following, extrusion having two or more kneading zones used for producing the polycarbonate resin composition in the present invention and having two or more vents downstream from the first kneading zone from the upstream side in the extrusion direction. The machine is referred to as “the extruder of the present invention”. Further, the upstream side in the extrusion direction of the extruder is simply referred to as “upstream”, and the downstream side is simply referred to as “downstream”. The first kneading zone and the second kneading zone from the upstream side of the extruder are referred to as “first kneading zone” and “second kneading zone”, respectively, and the most downstream kneading zone is designated as “last kneading zone”. This is referred to as a “stage kneading zone”. Similarly, for the vent, the first vent and the second vent from the upstream side in the extrusion direction are referred to as “first vent” and “second vent”, respectively, and the most downstream vent is referred to as “last vent”. .

  First, the extruder (extruder of the present invention) used in the present invention will be described, and then each component included in the method for manufacturing the polycarbonate resin composition of the present invention, its blending composition, manufacturing method, and molding method will be described.

[Extruder of the present invention]
The extruder of the present invention has two or more kneading zones and has two or more vents downstream from the first kneading zone. Usually, the kneading zone and the vent have such a configuration. A twin-screw extruder having is used.

  The kneading zone is a melt-kneading zone configured by arranging a plurality of plate-like kneading disks, each having a substantially elliptical cross section perpendicular to the axial direction of the kneading screw, in the axial direction of the screw. In the kneading zone, the kneading disk rotates as the kneading screw rotates, and the raw material is guided between the kneading disk and the inner wall of the barrel to effectively melt and knead the raw material.

  Since the extruder of the present invention has two or more such kneading zones and two or more vents downstream from the first kneading zone, the raw material passes through the plurality of kneading zones. The polycarbonate resin (A), the polyester resin (B), and other components are sufficiently melted and kneaded, and the kneaded product having reduced viscosity is heated and melted in the first kneading zone. While passing through the vent, the moisture contained in the polyester resin (B) and the moisture contained in other raw materials are effectively removed. As a result, mechanical properties and residence heat stability due to hydrolysis of the resin, A polycarbonate resin composition in which the decrease is suppressed can be produced.

The extruder of the present invention only needs to have two or more kneading zones and two or more vents downstream of the first kneading zone, and the number of kneading zones may be three or more. Good. Further, the number of vents may be three or more, and the vent may also be provided upstream of the first kneading zone.
However, if the kneading zone and the vent are excessively large, the configuration of the extruder becomes complicated. Therefore, it is preferable that the kneading zone is 2 to 8 and the vent is 2 to 5.

Of the plurality of vents of the extruder of the present invention, the first vent may be an open vent or a vacuum vent. Here, the open vent is simply a vent opening, and the degree of decompression is zero (atmospheric pressure). The decompression vent is also called a “evacuation vent” and is a closed vent and is configured to be decompressed in the barrel by being connected to decompression means such as a vacuum pump.
That is, in the present invention, even when two or more vents are provided downstream from the first kneading zone and the first vent is simply opened, the mechanical effect is sufficient with a sufficient water removal effect compared to an extruder provided with one vent. It is possible to improve physical properties, stagnant heat stability, and appearance.
In this case, the second vent and the subsequent vents are preferably decompression vents, and the degree of decompression of the second vent and the subsequent vents is −0.050 MPa or more, for example, −0.053 to −0.100 MPa. It is preferable.

  Here, the degree of decompression of the vent is a gauge pressure that represents the degree of decompression of the decompression vent (degree of vacuum). It is a thing. Therefore, “the degree of decompression is large” means that the absolute value of the negative numerical value is large.

It is preferable that both the first vent and the second and subsequent vents are decompression vents. In this way, all vents are decompression vents, so that the first vent is an open vent compared to the present. In the extruder of the invention, a better moisture removal effect can be obtained, and mechanical properties, residence heat stability and appearance can be further improved. In that case, it is preferable that the degree of decompression of each vent satisfies the following condition (1) or (2), particularly the following condition (1).
(1) The pressure reduction degree (P1) of the first vent and the pressure reduction degree (P2) of the vents after the second vent satisfy the relationship of P1 ≧ P2 (condition (1)).
(2) The pressure reduction degree (P1) of the first vent and the pressure reduction degree (P2) of the vents after the second vent satisfy the relationship of P1 <P2, and P1 ≧ −0.05 MPa (condition (2)).

  As described above, P1 ≧ P2 means that the absolute value of P1 is equal to or larger than the absolute value of P2 in P1 and P2, both of which are negative values, and P1 <P2 is contrary to P1 It means that the absolute value is smaller than the absolute value of P2. Further, P1 ≧ −0.05 MPa means that the absolute value of P1, which is a negative numerical value, is 0.05 or more.

  In the case of the above condition (1), since most of the water can be effectively removed by the first vent with a large degree of vacuum, hydrolysis during the melt-kneading of the resin downstream of the first vent is effectively suppressed. can do. In this case, the decompression degree of the first vent is -0.070 to -0.100 MPa, the decompression degree after the second vent is -0.050 to -0.093 MPa, and the difference between the two is 0.007 to 0.050 MPa. It is preferable to obtain a good water removal effect while suppressing volatilization of low-melting-point substances such as heat stabilizers and mold release agents in the raw material.

On the other hand, in the case of the condition (2), after suppressing the volatilization of the low melting point substance such as the heat stabilizer and the release agent in the raw material in the first vent, the water is removed and the second vent and the subsequent effective. Moisture can be removed. In this case, the decompression degree of the first vent is -0.050 to -0.070 MPa, the decompression degree after the second vent is -0.060 to -0.010 MPa, and the difference between the two is 0.010 to 0.050 MPa. In order to obtain a good moisture removal effect, it is preferable to set the degree to about a level while suppressing volatilization of low-melting-point substances such as a heat stabilizer and a release agent in the raw material.
Even if P1 <P2 and P1 <−0.05 MPa, the water removal effect according to the present invention can be obtained. However, since there is a large amount of water remaining in the polyester resin and other raw materials, As shown in Examples 7 and 13, the moisture removal effect is inferior to the case where the first vent is an open vent (that is, P1 = 0 MPa).

  Further, the extruder of the present invention has one or more vents downstream from the last stage kneading zone, and highly moisture and volatile impurities are obtained from the resin composition completely melt-kneaded in the last stage kneading zone. It is preferable in removing.

  The extruder of the present invention is not limited as long as it has two or more kneading zones, and the length and position of the kneading zone are not particularly limited, but the length of one kneading zone is the barrel length of the extruder. The total length of the two or more kneading zones is preferably about 1/12 to 1/3 of the barrel length L.

  The first kneading zone is preferably provided at a position about 1/4 to 1/2 of the barrel length L from the most upstream raw material supply section (hopper) of the barrel of the extruder. The interval between the bonding zones is about 1/12 to 1/2 of the barrel length L, and the interval between the last kneading zone and the most downstream resin composition extrusion portion of the barrel of the extruder is the barrel length L. It is preferable that it is 1/6 to 1/3.

  The distance between the first kneading zone and the first vent is preferably about 1/12 to 1/2 of the barrel length L, and the distance between the vents is 1/6 to 1 of the barrel length L. The distance between the last kneading zone and the downstream vent is preferably about 1/12 to 1/4 of the barrel length L. Moreover, it is preferable that the space | interval of the last stage vent and the resin composition extrusion part of the most downstream of the barrel of an extruder is about 1/12-1/4 of the barrel length L. FIG.

  There is no restriction | limiting in particular about L / D (barrel length / screw diameter) of the extruder of this invention, and it is about 25-50 normally. Moreover, it is preferable to set screw rotation speed to 150-600 rpm and cylinder temperature to about 250-290 degreeC.

[Polycarbonate resin (A)]
As the polycarbonate resin (A) used for the polycarbonate resin of the present invention, any conventionally known polycarbonate resin can be used. Examples of the polycarbonate resin (A) include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins, and aromatic polycarbonate resins are preferable.

  The aromatic polycarbonate resin is an optionally branched aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with a phosgene or carbonic acid diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and may be a conventional method such as a phosgene method (interfacial polymerization method) or a melting method (transesterification method). Further, it may be a polycarbonate resin produced by a melting method and produced by adjusting the amount of OH groups of terminal groups.

Typical examples of the aromatic dihydroxy compound that is one of the raw materials of the aromatic polycarbonate resin used in the present invention include, for example, bis (4-hydroxyphenyl) methane and 2,2-bis (4-hydroxyphenyl). Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like.
Further, polyhydric phenols having 3 or more hydroxy groups in the molecule such as 1,1,1-tris (4-hydroxylphenyl) ethane, 1,3,5-tris (4-hydroxyphenyl) benzene, etc. are branched. A small amount can be used in combination as an agent.
Among these aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable. These aromatic dihydroxy compounds can be used alone or in admixture of two or more.

  In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1 -Polyhydroxy compounds such as tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. May be used as a part of the aromatic dihydroxy compound, and the amount used thereof may be And from 0.01 to 10 mol% against, and preferably 0.1 to 2 mol%.

  In the polymerization by the transesterification method, carbonic acid diester is used as a monomer instead of phosgene. Representative examples of the carbonic acid diester include substituted diaryl carbonates typified by diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates typified by dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable.

  Moreover, said carbonic acid diester may substitute the quantity of the 50 mol% or less preferably 30 mol% or less with the dicarboxylic acid or dicarboxylic acid ester preferably. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

  When an aromatic polycarbonate resin is produced by a transesterification method, a catalyst is usually used. Although there is no limitation on the catalyst species, generally basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds are used. Of these, alkali metal compounds and / or alkaline earth metal compounds are particularly preferred. These may be used alone or in combination of two or more. In the transesterification method, the polymerization catalyst is generally deactivated with p-toluenesulfonic acid ester or the like.

  Preferred as the polycarbonate resin (A) is an aromatic polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds. And aromatic polycarbonate copolymers derived from the above. Further, for the purpose of imparting flame retardancy and the like, a polymer or oligomer having a siloxane structure can be copolymerized. The polycarbonate resin (A) may be a mixture of two or more polymers and / or copolymers of different raw materials, and may have a branched structure up to 0.5 mol%.

  The terminal hydroxyl group content of the polycarbonate resin (A) such as an aromatic polycarbonate resin has a great influence on the thermal stability, hydrolysis stability, color tone and the like. In order to give practical physical properties, the terminal hydroxyl group content of the polycarbonate resin (A) is usually 30 to 2000 ppm, preferably 100 to 1500 ppm, more preferably 200 to 1000 ppm. As the end-capping agent to be adjusted, p-tert-butylphenol, phenol, cumylphenol, p-long chain alkyl-substituted phenol or the like can be used.

  As a residual monomer amount in the polycarbonate resin (A) such as an aromatic polycarbonate resin, the aromatic dihydroxy compound is 150 ppm or less, preferably 100 ppm or less, and more preferably 50 ppm or less. When synthesized by the transesterification method, the residual amount of carbonic acid diester is 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less.

  The molecular weight of the polycarbonate resin (A) such as aromatic polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent, and preferably in the range of 10,000 to 50,000. More preferably, it is a thing of 10,000-40,000, Especially preferably, it is a thing of the range of 12,000-30,000. By setting the viscosity average molecular weight to 10,000 or more, the mechanical properties are more effectively exhibited, and by setting the viscosity average molecular weight to 50,000 or less, the molding process becomes easier. Further, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed, or a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed to be within the above molecular weight range.

[Polyester resin (B)]
The polyester resin (B) used in the present invention contains water at 1000 ppm or more. That is, in the present invention, by using the above-described extruder of the present invention, even such a polyester resin (B) having a relatively high water content, the polycarbonate resin by the extruder can be used without prior drying. During the melt-kneading with (A), it is possible to effectively remove moisture and produce a high-quality polycarbonate resin composition.

  Usually, the water content of the polyester resin (B) produced industrially is about 2000 to 4000 ppm. In the present invention, the polyester resin (B) having such a water content is not dried in advance. It can be used as it is for the production of a polycarbonate resin composition.

  In the present invention, the moisture content of the polyester resin (B) is measured by the method described in the Examples section below. In the present invention, the moisture content of the polyester resin (B) is The value measured immediately before feeding into the extruder.

  As the polyester resin (B), any conventionally known polyester resin can be used, and among them, aromatic polyester resins are preferable. Here, the aromatic polyester resin refers to a polyester resin having an aromatic ring in a polymer chain unit, and includes, for example, an aromatic dicarboxylic acid component and a diol (and / or its ester or halide) component as main components. These are polymers or copolymers obtained by polycondensation of these.

  Examples of the aromatic dicarboxylic acid component include phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2, 2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4 , 4′-dicarboxylic acid, diphenylisopropylidene-4,4′-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p-terphenylene-4,4′-dicarboxylic acid, Pyridine-2,5-dicarboxylic acid, succinic acid, adipic acid, sebacic acid, suberic acid, Line acid, and dimer acid.

  Only 1 type may be used for these aromatic dicarboxylic acid components, and 2 or more types may be used together in arbitrary ratios. Of these aromatic dicarboxylic acids, terephthalic acid is preferred. As long as the effects of the present invention are not impaired, an alicyclic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, sebacic acid, dimer acid or the like is used in combination with these aromatic dicarboxylic acids. May be.

  Examples of the diol component include aliphatic glycols, polyoxyalkylene glycols, alicyclic diols, and aromatic diols. Examples of the aliphatic glycols include ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, decanediol and the like having 2 to 2 carbon atoms. Among these, aliphatic glycols having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms are preferable.

  Examples of the polyoxyalkylene glycols include glycols having 2 to 4 carbon atoms in the alkylene group and having a plurality of oxyalkylene units, such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, Examples include tritetramethylene glycol.

  Examples of alicyclic diols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethylol, hydrogenated bisphenol A, and the like. Examples of aromatic diols include 2,2-bis- (4- (2-hydroxyethoxy) phenyl) propane and xylylene glycol.

  Examples of other diol components include esters of the diols described above, and halogenated diols such as halides such as adducts of tetrabromobisphenol A and alkylene oxide (such as ethylene oxide and propylene oxide) of tetrabromobisphenol A. These diol components may use only 1 type and may use 2 or more types together in arbitrary ratios. If the amount is small, long chain diols having a molecular weight of 400 to 6000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol may be used.

  The aromatic polyester resin used in the present invention is preferably a polyalkylene terephthalate resin. Here, the polyalkylene terephthalate resin refers to a resin containing an alkylene terephthalate structural unit, and may be a copolymer of an alkylene terephthalate structural unit and another structural unit.

  Examples of the polyalkylene terephthalate resin used in the present invention include polyethylene terephthalate (PET) resin, polypropylene terephthalate resin, polybutylene terephthalate (PBT) resin, polyethylene naphthalate (PEN) resin, polybutylene naphthalate (PBN) resin, poly (Cyclohexane-1,4-dimethylene-terephthalate) resin, polytrimethylene terephthalate resin, and the like.

  In addition to the above, the polyalkylene terephthalate resin used in the present invention includes an alkylene terephthalate copolymer having an alkylene terephthalate structural unit as a main structural unit, and a polyalkylene terephthalate mixture having a polyalkylene terephthalate resin as a main component. Furthermore, what contains or copolymerized elastomer components, such as polyoxytetramethylene glycol (PTMG), can also be used.

  Examples of the alkylene terephthalate copolyester include a copolyester composed of two or more diol components and terephthalic acid, and a copolyester composed of a diol component, terephthalic acid, and a dicarboxylic acid other than terephthalic acid. When two or more kinds of diol components are used, they may be appropriately selected and determined from the above-mentioned diol components. However, the monomer unit copolymerized with the alkylene terephthalate resin, which is the main structural unit, should be 25% by mass or less. Therefore, it is preferable because heat resistance is improved.

  For example, ethylene glycol / isophthalic acid / terephthalic acid copolymer (isophthalic acid copolymerized polyethylene terephthalate resin), 1,4-butanediol / isophthalic acid / terephthalic acid copolymer (isophthalic acid copolymerized polybutylene terephthalate resin), etc. In addition to the alkylene terephthalate copolyester having an alkylene terephthalate structural unit as a main structural unit, 1,4-butanediol / isophthalic acid / decanedicarboxylic acid copolymer and the like can be mentioned. Of these, an alkylene terephthalate copolyester is preferred.

  As the polyester resin (B) used in the present invention, when an alkylene terephthalate copolyester is used, the above-mentioned isophthalic acid copolymerized polybutylene terephthalate resin, isophthalic acid copolymerized polyethylene terephthalate resin, and the like are preferable. From the viewpoint of heat resistance, those having an isophthalic acid component of 25% by mass or less are preferable.

<Polyethylene terephthalate resin>
As the polyester resin (B), it is particularly preferable to use a polyethylene terephthalate resin. Here, the polyethylene terephthalate resin is a ratio of an oxyethyleneoxyterephthaloyl unit (hereinafter sometimes referred to as “ET unit”) composed of terephthalic acid and ethylene glycol with respect to all repeating units (hereinafter referred to as “ET ratio”) The polyethylene terephthalate resin is preferably 90 equivalent% or more, and the polyethylene terephthalate resin in the present invention may contain constituent repeating units other than ET units in a range of less than 10 equivalent%. The polyethylene terephthalate resin in the present invention is produced using terephthalic acid or a lower alkyl ester thereof and ethylene glycol as main raw materials, but other acid components and / or other glycol components may be used together as raw materials.

  Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples thereof include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid or derivatives thereof.

  Examples of diol components other than ethylene glycol include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, aliphatic glycols such as pentamethylene glycol, hexamethylene glycol, and neopentyl glycol, cyclohexane Examples include alicyclic glycols such as dimethanol, and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S.

  The intrinsic viscosity of the polyethylene terephthalate resin used in the present invention may be appropriately selected and determined, but is usually 0.5 to 2 dl / g, particularly 0.6 to 1.5 dl / g, particularly 0.7 to 1. It is preferably 0 dl / g. By setting the intrinsic viscosity to 0.5 dl / g or more, particularly 0.7 dl / g or more, the mechanical properties, residence heat stability, chemical resistance, and heat and humidity resistance in the polycarbonate resin composition of the present invention are improved. It tends to be preferable. On the other hand, the intrinsic viscosity is preferably 2 dl / g or less, particularly 1.0 dl / g or less, because the processability of the resin during the production of the polycarbonate resin composition tends to be improved.

  In the present invention, the intrinsic viscosity of the polyethylene terephthalate resin is a value measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1).

  The density | concentration of the terminal carboxyl group of the polyethylene terephthalate resin used for this invention is 1-60microeq / g normally, and it is preferable that it is 3-50microeq / g especially 5-40microeq / g. By making the terminal carboxyl group concentration 60 μeq / g or less, the heat resistance, residence heat stability and hue of the polycarbonate resin composition tend to be improved. Conversely, by making the terminal carboxyl group concentration 1 μeq / g or more. The processability during the production of the polycarbonate resin composition tends to be improved, which is preferable.

  The terminal carboxyl group concentration of the polyethylene terephthalate resin can be determined by dissolving 0.5 g of polyethylene terephthalate resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide. it can.

<Polybutylene terephthalate resin>
A polybutylene terephthalate resin may be used as the polyester resin (B). Here, the polybutylene terephthalate resin refers to a resin having a structure in which a terephthalic acid unit and a 1,4-butanediol unit are ester-bonded. In the present invention, it is preferable to use a polybutylene terephthalate resin in which 50 mol% or more of dicarboxylic acid units are terephthalic acid units and 50 mol% or more of diol components are 1,4-butanediol units. The proportion of terephthalic acid units in all dicarboxylic acid units is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more, and optimally 98 mol% or more. The proportion of 1,4-butanediol units in all diol units is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more, and optimally 98 mol% or more. If the terephthalic acid unit or the 1,4-butanediol unit is in the above range, the crystallization speed is in an appropriate range, and thus the moldability is good.

  As described above, the polybutylene terephthalate resin may contain dicarboxylic acid units other than terephthalic acid. The dicarboxylic acid other than terephthalic acid is not particularly limited, and examples thereof include phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4, Aromatic dicarboxylic acids such as 4′-diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; . These dicarboxylic acid units can be introduced into the polymer skeleton by using a dicarboxylic acid or a dicarboxylic acid derivative such as a dicarboxylic acid ester or a dicarboxylic acid halide as a raw material.

  As described above, the polybutylene terephthalate resin may contain a diol unit other than 1,4-butanediol. Diols other than 1,4-butanediol are not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, and dibutylene. Aliphatic diols such as glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1- Cycloaliphatic diols such as cyclohexane dimethylol and 1,4-cyclohexane dimethylol; xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) Nyl) sulfone and other aromatic diols;

  The polybutylene terephthalate resin further includes hydroxycarboxylic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid; alkoxy Monofunctional compounds such as carboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid; tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylol A unit derived from a trifunctional or more polyfunctional compound such as ethane, trimethylolpropane, glycerol, pentaerythritol and the like may be contained.

The intrinsic viscosity of the polybutylene terephthalate resin used in the present invention is not particularly limited, but the lower limit may be determined from the viewpoint of mechanical properties, and the upper limit may be determined from the viewpoint of molding processability. The intrinsic viscosity of the polybutylene terephthalate resin is preferably 0.70 to 3.0 dl / g, more preferably 0.80 to 1.5 dl / g, and particularly preferably 0.80 to 1.2 dl / g. is there. When the intrinsic viscosity is within the above range, good mechanical properties can be exhibited and good moldability can be obtained. The value of the intrinsic viscosity is a value measured at a temperature of 30 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (mass ratio).
In the present invention, two or more polybutylene terephthalate resins having different intrinsic viscosities may be used in combination.

  The terminal carboxyl group concentration of the polybutylene terephthalate resin used in the present invention is preferably 120 μeq / g or less, more preferably 2 to 80 μeq / g, and particularly preferably 5 to 60 μeq / g. When the terminal carboxyl group concentration is 120 μeq / g or less, hydrolysis resistance and fluidity are improved, and it is preferably 2 μeq / g or more from the viewpoint of productivity. The terminal carboxyl group concentration can be determined by dissolving polybutylene terephthalate resin in benzyl alcohol and titrating with an aqueous solution of 0.1N (mol / L) sodium hydroxide. The above value is the carboxyl group per gram. Is equivalent.

  A polyester resin (B) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

[Blend ratio of resin component]
The polycarbonate resin composition of the present invention has a polycarbonate resin (A) of 50 parts by mass or more (ie, 50 parts by mass or more and less than 100 parts by mass) and a polyester resin (B) of 50 parts by mass or less (ie, more than 0 parts by mass and more than 50 parts by mass). In a total of 100 parts by mass).
The content ratio of the polycarbonate resin (A) and the polyester resin (B) is preferably 55 to 95 parts by mass of the polycarbonate resin (A) and 5 to 45 parts by mass of the polyester resin (B), more preferably 60 of the polycarbonate resin (A). -90 mass parts, polyester resin (B) 10-40 mass parts (however, the total of polycarbonate resin (A) and polyester resin (B) is 100 mass parts).

  If the content ratio of the polycarbonate resin (A) is less than the above lower limit, the polycarbonate resin (A) inherent properties such as impact resistance, heat resistance and dimensional stability cannot be sufficiently obtained, and the above upper limit is satisfied. When it exceeds, the content rate of a polyester resin (B) will decrease relatively and the effect by mix | blending a polyester resin (B) cannot fully be acquired.

  Moreover, when the content ratio of the polyester resin (B) is not less than the above lower limit value, the chemical resistance improvement effect by blending the polyester resin (B) can be sufficiently obtained and is not more than the above upper limit value. Thus, physical properties such as good impact resistance and thermal stability can be obtained without impairing the original properties of the polycarbonate resin (A).

[Thermoplastic elastomer (C)]
The polycarbonate resin composition of the present invention may further contain a thermoplastic elastomer (C) as an impact resistance improver for the molded product, if necessary, and by blending the thermoplastic elastomer (C), It is possible to impart impact resistance, and it is possible to prevent cracking and damage of the molded product due to unexpected external stress.

  As the thermoplastic elastomer (C), a copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith is preferable. Such a graft copolymer may be produced by any production method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the copolymerization method may be a single-stage graft or a multi-stage graft. Also good.

  The rubber component generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Ethylene-α olefins such as silicone rubber, butadiene-acrylic composite rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber And rubbers such as ethylene-acrylic rubber and fluororubber. These may be used alone or in admixture of two or more. Among these, in view of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable.

  Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The thermoplastic elastomer (C) used in the present invention is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. In particular, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and (meth) acrylic acid ester around it. Particularly preferred is a core / shell type graft copolymer comprising a shell layer formed by copolymerizing. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid components is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such commercially available core / shell type graft copolymers include the EXL series such as Paraloid EXL2315, EXL2602, and EXL2603 manufactured by Rohm and Haas Japan, the KM series such as KM330 and KM336P, and the KCZ201. The KCZ series, Metablene S-2001, SRK-200 manufactured by Mitsubishi Rayon Co., Ltd., Staphyloid MG-1011 manufactured by Takeda Pharmaceutical Co., Ltd., Kaneace M721 manufactured by Kaneka Corporation, and the like.

  When the polycarbonate resin composition of the present invention contains the above-described thermoplastic elastomer (C), the thermoplastic elastomer (C) is added to 100 parts by mass in total of the polycarbonate resin (A) and the polyester resin (B). It is preferable to contain 0.5-30 mass parts, especially 2-25 mass parts, especially 5-20 mass parts. If the content of the thermoplastic elastomer (C) in the polycarbonate resin composition is too small, the impact resistance improving effect due to the blending of the thermoplastic elastomer (C) cannot be sufficiently obtained, and if it is too much, the surface Hardness, heat resistance and rigidity tend to decrease.

[Organic Phosphate Ester Compound (D)]
The polycarbonate resin composition of the present invention may contain an organic phosphate compound represented by the following general formula (1) for improving thermal stability.
(RO) _n P (O) (OH) _3-n (1)
(In the formula, R represents an alkyl group having 2 to 25 carbon atoms which may have a substituent, and n represents 1 or 2. However, when n is 2, two Rs are the same. May be different or different from each other.)

  Examples of the unsubstituted alkyl group represented by R include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, hexadecyl group, octadecyl group Groups and stearyl groups. Examples of the alkyl group having a substituent include those in which a chain hydrocarbon group such as a butyl group, an allyl group, or a methallyl group is bonded to the alkyl group by an ether bond or an ester bond. R is preferably an alkyl group having these substituents. Moreover, it is preferable that the total carbon number in R including the carbon of a substituent is 5 or more.

  The organic phosphate compound (D) may be a mixture of compounds having different R and n in the general formula (1).

  When the polycarbonate resin composition of the present invention contains an organophosphate compound (D), the content is usually 0.02 with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the polyester resin (B). It is preferable that it is -3 mass parts, especially 0.03-1 mass parts, especially 0.04-0.5 mass parts. When the compounding amount of the organic phosphate compound (D) is equal to or more than the above lower limit, the effect of improving the thermal stability due to the compounding of the organic phosphate compound (D) can be sufficiently obtained. However, even if the amount of the organophosphate compound (D) is too large, the effect reaches a peak and is not economical, so the upper limit is not exceeded.

[Other resin components]
The polycarbonate resin composition of the present invention may contain other resin components and rubber components other than the polycarbonate resin (A), the polyester resin (B), and the thermoplastic elastomer (C). In this case, as other resin or rubber component, for example, polyolefin resin such as styrene resin, polyethylene resin or polypropylene resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, Polysulfone resin, polymethacrylate resin, phenol resin, epoxy resin, etc. are mentioned, but the content of these other resins or rubber components is the original characteristics of polycarbonate resin (A), and also polyester resin (B) is used in combination In order to sufficiently secure the effect of the operation, it is preferable that the amount is 20 parts by mass or less with respect to 100 parts by mass in total of the polycarbonate resin (A) and the polyester resin (B).

[Other additives]
In the polycarbonate resin composition of the present invention, the polycarbonate resin (A), the polyester resin (B), the thermoplastic elastomer (C), and the organic phosphate compound (D) described above are within a range not impairing the effects of the present invention. In addition, you may contain the other various additive contained in a normal polycarbonate resin composition.

  Various additives that can be included include phosphorus heat stabilizers, phenolic antioxidants, colorants (dyeing pigments), reinforcing agents, flame retardants, impact modifiers, antistatic agents, antifogging agents, lubricants, Antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, inorganic fillers and the like can be mentioned. Two or more of these may be used in combination. Hereinafter, an example of an additive suitable for the polycarbonate resin composition of the present invention will be specifically described.

<Phosphorus heat stabilizer>
The polycarbonate resin composition of the present invention may contain a phosphorus-based heat stabilizer, and the phosphorus-based heat stabilizer generally generally has a residence stability or resin molding at a high temperature when the resin component is melt-kneaded. It is effective for improving the heat resistance stability during product use.

  Examples of the phosphorus-based heat stabilizer used in the present invention include phosphorous acid, phosphoric acid, phosphite ester, and phosphate ester (excluding the above-mentioned organic phosphate ester compound (D)). Phosphites such as phosphites and phosphonites are preferable in that they contain trivalent phosphorus and easily exhibit a discoloration suppressing effect.

  Examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite. Phyto, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, water Bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butyl) Ruphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidene diphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilaurylpentaerythritol diphosphite Phosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

  Examples of phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6- -Tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert) -Butylphenyl) -3,3'-biphenylenediphosphonite and the like.

  Among the phosphites, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferable, and heat resistance is good. Tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred in that it is difficult to hydrolyze.

  A phosphorus heat stabilizer may be used individually by 1 type, and may use 2 or more types together.

  When the polycarbonate resin composition of the present invention contains a phosphorus-based heat stabilizer, the content is usually 0.02 to 3 mass with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the polyester resin (B). Parts, particularly 0.03-1 parts by mass, especially 0.04-0.5 parts by mass. When the blending amount of the phosphorus-based heat stabilizer is equal to or more than the above lower limit, the effect of improving the thermal stability by blending the phosphorus-based heat stabilizer can be sufficiently obtained. However, even if the amount of the phosphorus-based heat stabilizer is too large, the effect reaches a peak and is not economical, so the upper limit is not more than the above.

<Phenolic antioxidant>
The polycarbonate resin composition of the present invention may further contain a phenolic antioxidant, if desired. By containing a phenolic antioxidant, it is possible to suppress deterioration in hue and mechanical properties during heat retention. can do.

  Examples of phenolic antioxidants include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, ''-(Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert- Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5- Di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4 6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Examples of such commercially available phenolic antioxidants include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-60”, “Adekastab AO-50” manufactured by ADEKA, and the like. It is done.

  One of these phenolic antioxidants may be contained, or two or more thereof may be contained in any combination and ratio.

  When the polycarbonate resin composition of the present invention contains a phenolic antioxidant, the content is usually 0.02 to 3 mass with respect to a total of 100 mass parts of the polycarbonate resin (A) and the polyester resin (B). Parts, particularly 0.03-1 parts by mass, especially 0.04-0.5 parts by mass. When the blending amount of the phenolic antioxidant is equal to or more than the above lower limit value, the above-described effect by blending the phenolic antioxidant can be effectively obtained. However, even if the amount of the phenolic antioxidant is too large, the effect reaches its peak and is not economical.

  In addition, when the polycarbonate resin composition of the present invention contains both a phosphorus-based heat stabilizer and a phenol-based antioxidant, the phosphorus-based heat stabilizer and the phenol-based antioxidant are combined with a phosphorus-based heat stabilizer: phenol. System antioxidant: It is a mass ratio of 1: 0.2-3, and it contains 0.04-2 mass parts with respect to the total 100 mass parts of polycarbonate resin (A) and polyester resin (B) as a total amount. It is preferable.

<Release agent>
The release agent includes at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oil. Can be mentioned.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Is mentioned.

  In addition, said ester compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.

  When using a mold release agent, the content in the polycarbonate resin composition of the present invention is usually 0.05 to 2 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the polyester resin (B). Preferably it is 0.1-1 mass part. If the content of the release agent is not less than the above lower limit value, the effect of improving the releasability can be sufficiently obtained, and if it is not more than the above upper limit value, degradation of hydrolysis resistance due to excessive mixing of the release agent, injection Problems such as mold contamination during molding can be prevented.

<Ultraviolet absorber>
Specific examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. Of these, organic ultraviolet absorbers are preferred. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- ON], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol condensate. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], [methyl-3- [3-tert-butyl-5- (2H -Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate and the like. Two or more of these may be used in combination.

  Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl)- 6- (2N-benzotriazol-2-yl) phenol].

  When using an ultraviolet absorber, the content in the polycarbonate resin composition of the present invention is usually 0.05 to 2 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the polyester resin (B). Preferably it is 0.1-1 mass part. When the content of the ultraviolet absorber is not less than the above lower limit value, the effect of improving weather resistance can be sufficiently obtained, and by being not more than the above upper limit value, problems such as mold deposit can be reliably prevented. it can.

<Colorant (dyeing pigment)>
Examples of the colorant (dye pigment) include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, titanium oxide, iron black, titanium yellow, and zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments. Organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, and isoindolinone. And condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like. Two or more of these may be used in combination. Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

  When the polycarbonate resin composition of the present invention contains a colorant (dye pigment), the content of the colorant (dye pigment) in the polycarbonate resin composition is the sum of the polycarbonate resin (A) and the polyester resin (B). The amount is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 2 parts by mass or less with respect to 100 parts by mass. When the content of the colorant (dye pigment) exceeds 5 parts by mass, the impact resistance may not be sufficient.

<Flame Retardant>
Examples of the flame retardant include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, diphenylsulfone-3,3 ′. -Organic metal salt flame retardants such as dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate, potassium perfluorobutanesulfonate, and polyorganosiloxane flame retardants are preferable, but phosphate ester flame retardants are particularly preferable. .

  Specific examples of the phosphate ester flame retardant include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′-biphenol bis (dixylenyl phosphate), bisphenol A Examples thereof include bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4′-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Two or more of these may be used in combination. In these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.

  When using a flame retardant, the content in the polycarbonate resin composition of the present invention is usually 0.05 to 30 parts by mass, preferably 100 parts by mass in total of the polycarbonate resin (A) and the polyester resin (B). Is 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass. Sufficient flame retardancy can be obtained when the content of the flame retardant is equal to or higher than the above lower limit value, and reliably lowering of heat resistance due to excessive blending of the flame retardant can be prevented by being equal to or lower than the upper limit value. Can do.

<Anti-dripping agent>
Examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene having fibril forming ability is particularly preferable. This shows the tendency to disperse | distribute easily in a polymer and to couple | bond together polymers and to make a fibrous material. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Polytetrafluoroethylene can be used in solid form or in the form of an aqueous dispersion. Examples of polytetrafluoroethylene having fibril-forming ability include “Teflon (registered trademark) 6J” or “Teflon (registered trademark) 30J” from Mitsui DuPont Fluorochemical Co., Ltd. and “Polyflon (trade name) from Daikin Industries, Ltd. Is commercially available.

  When using a dripping inhibitor, the content in the polycarbonate resin composition of the present invention is usually 0.1 to 2 parts by mass with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the polyester resin (B). Preferably it is 0.2-1 mass part. When there are too many compounding quantities of a dripping prevention agent, the fall of a molded article appearance may arise.

<Inorganic filler>
Examples of the inorganic filler include glass fiber, carbon fiber, metal fiber, ceramic fiber, milled fiber thereof, slag fiber, rock wool, wollastonite, zonotlite, potassium titanate whisker, aluminum borate whisker, and boron whisker. , Fibrous inorganic fillers such as basic magnesium sulfate whiskers, glass flakes, glass beads, graphite, talc, mica, kaolinite, sepiolite, attabargite, montmorillonite, bentonite, smectite and other silicate compounds, silica, alumina, carbonic acid Examples thereof include inorganic fillers such as calcium, and among these, glass fiber, talc, and wollastonite are preferable because they have a particularly excellent balance between reinforcing effect, physical properties, and appearance. These inorganic fillers may have a surface coated with a different material such as metal-coated glass fiber or metal-coated carbon fiber. These inorganic fillers may be used alone or in combination of two or more.

When an inorganic filler is used, the content in the polycarbonate resin composition of the present invention is usually 1 to 60 parts by mass, preferably 100 parts by mass, preferably 100 parts by mass of the polycarbonate resin (A) and the polyester resin (B). 5-40 mass parts, More preferably, it is 10-30 mass parts.
When the content ratio of the inorganic filler is not less than the above lower limit value, the effect of improving the dimensional stability and rigidity due to the blending of the inorganic filler can be sufficiently obtained. The problem of a drop in impact strength due to an excessive blending of fillers can be prevented.

  In the present invention, the inorganic filler is effective not only for improving the dimensional stability and rigidity but also for suppressing the thickening of the resin composition during heat retention. In particular, inorganic fillers that have been surface-treated and improved in adhesion to resin components can be used to suppress poor dispersion of inorganic fillers during heat retention and prevent thickening due to aggregation. In addition, the molding stability of the polycarbonate resin composition can be improved, which is preferable.

[Production Method of Polycarbonate Resin Composition]
The polycarbonate resin composition of the present invention comprises a polycarbonate resin (A) and a polyester resin (B), a thermoplastic elastomer (C) used as necessary, an organic phosphate ester compound (D), a phosphorus heat stabilizer, Other additives and other resin components are preliminarily mixed using various mixers such as a tumbler and a Henschel mixer and then melt-kneaded using the above-described extruder of the present invention. In addition, it can also manufacture, without mixing each component previously or by mixing only one part component previously and supplying to the extruder of this invention using a feeder and melt-kneading.

[Polycarbonate resin molded product]
The method for producing the polycarbonate resin molded product of the present invention by molding the polycarbonate resin composition of the present invention is not particularly limited, and a molding method generally adopted for thermoplastic resins, that is, general injection molding. Method, ultra high speed injection molding method, injection compression molding method, multicolor injection molding method, gas assist injection molding method, molding method using heat insulation mold, molding method using rapid heating / cooling mold, foam molding (supercritical Including fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, and the like. Also, in various injection molding methods, a molding method using a hot runner method can be selected.

  Further, the polycarbonate resin composition of the present invention can be subjected to multicolor composite molding with other thermoplastic resin compositions to form composite molded products.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the summary is exceeded.

[Materials used]
The raw material components used in the following examples and comparative examples are as follows.

In addition, the moisture content of the polyester resin (B) shown below is a value measured in advance according to the following moisture content measurement method in the production of the resin composition.
<Method for measuring water content>
Using a moisture vaporizer (VA-100 model manufactured by Mitsubishi Chemical Corporation), 0.5 g of the polyester resin was heated and melted at 200 ° C. to vaporize water in the polyester resin, and then the total amount of vaporized water was traced. The moisture content (mass ppm) in the polyester resin was determined by quantification by a coulometric titration method based on the principle of Karl Fischer reaction using a moisture measuring device (CA-100 model manufactured by Mitsubishi Chemical Corporation).

<Polycarbonate resin (A)>
Polycarbonate resin-A: “Iupilon (registered trademark) E-2000” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (bisphenol A type aromatic polycarbonate resin produced by interfacial polymerization method, viscosity average molecular weight: 28,000)
Polycarbonate resin-B: “Iupilon (registered trademark) S-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (bisphenol A type aromatic polycarbonate resin produced by an interfacial polymerization method, viscosity average molecular weight: 22,000)

<Polyester resin (B)>
PET resin: THAI SHINKING INDUSTY COLOR LTD LTD. “5511HF” manufactured by using an antimony catalyst as a polycondensation catalyst, intrinsic viscosity: 0.81 dl / g, terminal carboxyl group concentration: 27 μeq / g, melting point: 252 ° C., water content: 3200 ppm
PBT resin: “Novaduran (registered trademark) 5020” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (intrinsic viscosity: 1.20 dl / g, terminal carboxyl group concentration: 22 μeq / g, water content: 2000 ppm)

<Thermoplastic elastomer (C)>
Thermoplastic Elastomer 1: “Paraloid KCZ201” manufactured by Rohm and Haas (core / shell type graft copolymer comprising polybutadiene-polystyrene (core) / alkyl acrylate-alkyl methacrylate copolymer (shell))
Thermoplastic Elastomer 2: “Paraloid EXL2603” manufactured by Rohm and Haas (core / shell type graft copolymer comprising polybutadiene (core) / alkyl acrylate-alkyl methacrylate copolymer (shell))

<Organic phosphate compound (D)>
Organophosphate compound: “Adekastab AX-71” (mono, distearyl acid phosphate: chemical formula (C ₁₈ H ₃₇ O) _n P (O) (OH) _3-n (n = 1 and Asahi Denka Kogyo Co., Ltd.) Mixture of 2))

<Other additives>
Phosphorus heat stabilizer: “Adeka Stub AS2112” (Tris (2,4-di-tert-butylphenyl) phosphite) manufactured by Asahi Denka Kogyo Co., Ltd.
Carbon black: “# 1000” (oil furnace carbon black) manufactured by Mitsubishi Chemical Corporation

[Examples 1-13, Comparative Examples 1-2]
After each component shown in Table 1 is uniformly mixed with a tumbler-mixer at the ratio shown in the same table, a twin-screw extruder having a barrel, vent and screw configuration shown in FIG. 1 ("TEM-37BS" manufactured by Toshiba Machine) , L / D = 42), and melt kneading at a cylinder temperature of 270 ° C. and a screw rotation speed of 250 rpm, thereby producing a polycarbonate / polyethylene terephthalate resin composition (PC / PET resin composition) or a polycarbonate / polybutylene terephthalate resin. A pellet of the composition (PC / PBT resin composition) was obtained.
At that time, the first vent and the second vent of the extruder were opened or closed as shown in Tables 2 and 3, and the degree of vacuum P1 and P2 were set to the conditions shown in Tables 2 and 3.
A closed vent with a reduced pressure of 0 corresponds to a closed vent not provided with a vent. A closed vent whose degree of vacuum is greater than 0 corresponds to a vacuum vent.

As shown in FIG. 1, the barrel 1 of the used extruder is composed of 12 blocks (elements) C1 to C12, a hopper 2 for raw material charging is provided in C1, and a first vent V1 is provided in C7. A second vent V2 is provided at C11. Further, the screw has a first kneading zone N1 in the C5 to C6 region and a second kneading zone N2 in the C10 region.
The first kneading zone N1 is provided in the range of about 4.5 / 12 to 5.5 / 12 of the barrel length L from the most upstream side of the barrel and about 1/12 of the barrel length L. The second kneading zone N2 is provided in the range of about 9/12 to 10/12 of the barrel length L from the most upstream of the barrel, and about 1/12 of the barrel length L, The distance between the first kneading zone N1 and the second kneading zone N2 is about 3.5 / 12 of the barrel length L.
In addition, the first vent V1 exists in the portion of about 6.5 / 12 of the barrel length L from the most upstream of the barrel, and the second vent V2 exists in the portion of about 10.5 / 12 of the barrel length L.

[Evaluation of characteristics]
The polycarbonate resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Tables 2 and 3.

<Flow value and flow value after retention molding>
The polycarbonate resin composition pellets were dried at 120 ° C. for 5 hours or more. Thereafter, the polycarbonate resin composition pellets are molded normally using an injection molding machine (FANUC “ROBOSHOT α2000i-150T type”) under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 55 seconds. A strip-shaped test piece (normally molded product) having a thickness of 2 mm was produced.
Separately, a strip-shaped test piece after residence molding was performed in the same manner as the molding method of the above-mentioned normal molded product, except that the polycarbonate resin composition pellet was dried and held in the cylinder of the injection molding machine for 40 minutes before injection molding. (Molded product after residence) was produced.
For each of the obtained normal molded article and molded article after residence, the flow value was measured under the conditions of 280 ° C. and 160 kgf / cm ² using an orifice having an inner diameter of 1 mm and a length of 10 mm in accordance with JIS K7120. Went.
The smaller the degree of decrease in the flow value of the molded product after retention relative to the flow value of the normal molded product, the less hydrolysis of the resin during melt-kneading and the better the thermal stability of residence.

<Load deflection temperature and load deflection temperature after retention molding>
The polycarbonate resin composition pellets were dried at 120 ° C. for 5 hours or more. Thereafter, the polycarbonate resin composition pellets are molded normally using an injection molding machine (FANUC “ROBOSHOT α2000i-150T type”) under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 55 seconds. A bending test piece (normally molded product) having a thickness of 6.4 mm was produced.
Separately, after the polycarbonate resin composition pellets were dried and held in the cylinder of the injection molding machine for 20 minutes before injection molding, the bending test piece after retention molding ( A molded product after residence) was produced.
With respect to each of the obtained normal molded product and post-residual molded product, the deflection temperature under load was measured under the condition of a load of 18.6 kgf / cm ² according to ASTM D648.
The lower the degree of decrease in the deflection temperature under load of the molded product after residence relative to the deflection temperature under load of the normal molded product, the less hydrolysis of the resin during melt-kneading, indicating better residence heat stability and mechanical properties.

<Izod impact strength and Izod impact strength after retention molding>
The polycarbonate resin composition pellets were dried at 120 ° C. for 5 hours or more. Thereafter, the polycarbonate resin composition pellets are molded normally using an injection molding machine (FANUC “ROBOSHOT α2000i-150T type”) under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 55 seconds. Then, an ASTM notched Izod test piece (normally molded product) having a thickness of 3.2 mm was produced.
Separately, the ASTM notched Izod after residence molding was performed in the same manner as the above-mentioned normal molding method except that the polycarbonate resin composition pellets were dried and held in the cylinder of the injection molding machine for 40 minutes before injection molding. A test piece (molded product after residence) was prepared.
The obtained Izod impact strength (unit: J / m) was measured at 23 ° C. in accordance with ASTM D256 for each of the obtained normal molded product and molded product after residence.
The smaller the degree of decrease in the Izod impact strength of the molded product after residence relative to the Izod impact strength of the molded product, the less the hydrolysis of the resin during melt kneading and the better the thermal stability and mechanical properties.

<Appearance after retention molding>
The pellets of the polycarbonate resin composition were dried at 120 ° C. for 5 hours or more. Thereafter, the polycarbonate resin composition pellets are held in the cylinder of the injection molding machine for 40 minutes using an injection molding machine (FANUC “ROBOSHOT α2000i-150T type”), cylinder temperature 280 ° C., mold temperature 80 ° C. Residual molding was performed under the condition of a molding cycle of 55 seconds to form a three-stage plate (molded product after residence) having a size of 90 × 50 mm and a thickness of 3/2/1 mm.
The appearance of the obtained molded product after staying was visually observed and evaluated based on the following criteria.
◎: No silver streak on the surface ○: Slight silver streak on the surface △: Silver streak on the surface ×: Silver streak on the surface is remarkable The appearance of the molded product after retention is good because of the resin during melt-kneading It shows little hydrolysis and excellent residence heat stability.

The following can be understood from the above results.
The extruders used in Comparative Examples 1 and 2 correspond to those in which the first vent is a closed vent and only the second vent is a decompression vent, that is, an extruder having only one vent, Since the removal is not sufficient, the flow value after residence molding, the deflection temperature under load and the Izod impact strength are greatly reduced, and the appearance after residence molding is also poor.

  In Examples 7 and 13, the first vent and the second vent are reduced pressure vents, and P1 <P2. However, the pressure reduction degree P1 of the first vent is less than −0.05 MPa, and the above-described condition (1) And condition (2) are not satisfied. However, since there are two vents downstream from the first kneading zone, the flow values after stay forming, the deflection temperature under load, and the degree of decrease in Izod impact strength are kept small compared to Comparative Examples 1 and 2, respectively. In particular, in Example 7, the appearance after retention molding was also improved, and the effect of removing moisture by an extruder was obtained.

  In Examples 1 and 8, the first vent is an open vent and the second vent is a decompression vent. Thus, even if two vents are provided downstream from the first kneading zone and the first vent is an open vent, the effect of removing moisture can be obtained, and results better than those of Examples 7 and 13, respectively. can get.

  Examples 2 to 4, 9 to 11 satisfy the condition (1), and Examples 5, 6, and 12 satisfy the condition (2). Thus, the conditions (1) and (2), particularly the conditions It can be seen that satisfying (1) provides particularly good results.

1 Barrel 2 Hopper V1 1st vent V2 2nd vent N1 1st kneading zone N2 2nd kneading zone

Claims (9)

  As the resin component, a polycarbonate resin composition containing 100 parts by mass in total of 50 parts by mass or more of the polycarbonate resin (A) and 50 parts by mass or less of the polyester resin (B) having a water content of 1000 ppm or more is used using an extruder. A polycarbonate characterized in that the extruder has two or more kneading zones and has two or more vents downstream from the first kneading zone from the upstream side in the extrusion direction. A method for producing a resin composition.   The method for producing a polycarbonate resin composition according to claim 1, wherein the first vent from the upstream side in the extrusion direction of the extruder is an open vent or a reduced pressure vent, and the second and subsequent vents are reduced pressure vents. .   In Claim 2, the first vent from the upstream side in the extrusion direction is a decompression vent, and the decompression degree (P1) of the first vent and the decompression degree (P2) of the second and subsequent vents are P1 ≧ A method for producing a polycarbonate resin composition, which satisfies the relationship of P2.   In Claim 2, the first vent from the upstream side in the extrusion direction is a decompression vent, and the decompression degree (P1) of the first vent and the decompression degree (P2) of the second and subsequent vents are P1 < A method for producing a polycarbonate resin composition, wherein the relationship of P2 is satisfied and P1 is -0.05 MPa or more.   5. The method for producing a polycarbonate resin composition according to claim 1, wherein the extruder has one or more vents downstream from the most downstream kneading zone in the extrusion direction.   In any 1 item | term of the Claims 1 thru | or 5, this polycarbonate resin composition is further 0 thermoplastic elastomer (C) with respect to a total of 100 mass parts of this polycarbonate resin (A) and this polyester resin (B). The manufacturing method of the polycarbonate resin composition characterized by containing 5-30 mass parts. The polycarbonate resin composition according to any one of claims 1 to 6, further represented by the following general formula (1) with respect to a total of 100 parts by mass of the polycarbonate resin (A) and the polyester resin (B). The manufacturing method of the polycarbonate resin composition characterized by containing 0.02-3 mass parts of organophosphate ester compounds (D).
(RO) _n P (O) (OH) _3-n (1)
(In the formula, R represents an alkyl group having 2 to 25 carbon atoms which may have a substituent, and n represents 1 or 2. However, when n is 2, two Rs are the same. May be different or different from each other.)   The polycarbonate resin composition manufactured by the manufacturing method of the polycarbonate resin composition of any one of Claims 1 thru | or 7.   A polycarbonate resin molded article obtained by molding the polycarbonate resin composition produced by the method for producing a polycarbonate resin composition according to any one of claims 1 to 7.

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