JP6314600B2 - Aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition, and more particularly to an aromatic polycarbonate resin composition excellent in mechanical strength and heat-and-moisture resistance and a molded product thereof.

  Aromatic polycarbonate resin is excellent in heat resistance, impact resistance, transparency, dimensional stability, etc., so it can be used in a wide range of applications such as automobiles, OA equipment / electrical / electronic parts, machine parts, vehicle / aircraft parts, and building components. Widely used industrially in the field. Furthermore, a polymer alloy composed of a polycarbonate resin and a polyester resin is a material in which the above-mentioned excellent characteristics of the polycarbonate resin are utilized, and chemical resistance and moldability (fluidity), which are the disadvantages of the polycarbonate resin, are improved. It is used in vehicle interior / exterior parts, various housing members and other wide fields. In recent years, a higher level of appearance quality (such as gloss), chemical resistance, impact resistance, and moist heat resistance have been demanded, and materials with excellent balance in physical properties are required. In particular, impact resistance and heat-and-moisture resistance are very important performances when considering practical aspects.

  About the resin composition (polymer alloy) composed of an aromatic polycarbonate resin and a polyester resin, it contains a specific amount of germanium compound for the purpose of improving fluidity, impact resistance, chemical resistance, moist heat resistance, and recycling characteristics. In addition, it has been reported that a polyethylene terephthalate resin having a specific intrinsic viscosity is used (see, for example, Patent Document 1). In addition, by adding a special phosphate ester compound to a resin composition comprising an aromatic polycarbonate resin and a polyethylene terephthalate resin, fluidity, heat resistance, impact resistance, residence heat stability, chemical resistance, and heat and humidity resistance Has been reported to improve (see, for example, Patent Document 2).

  On the other hand, many studies have been made on a method for producing a polycarbonate resin. Among them, an aromatic polycarbonate resin derived from an aromatic dihydroxy compound such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol A”) is used in both the interfacial polymerization method and the melt polymerization method. It is industrialized by the manufacturing method.

  According to this interfacial polymerization method, the aromatic polycarbonate resin is produced from bisphenol A and phosgene, but toxic phosgene must be used. In addition, there is a risk that the apparatus may be corroded by by-produced hydrogen chloride or sodium chloride and chlorine-containing compounds such as methylene chloride used in large quantities as a solvent. Furthermore, it is difficult to remove impurities such as sodium chloride and residual methylene chloride which affect polymer physical properties, waste water treatment, and the like. As described above, the conventional interfacial polymerization method has many environmental problems.

  As a method for producing an aromatic polycarbonate resin from an aromatic dihydroxy compound and diaryl carbonate, for example, bisphenol A and diphenyl carbonate are polymerized while removing a by-product aromatic monohydroxy compound by a transesterification reaction in a molten state. The melt polymerization method has been known for a long time. Unlike the interfacial polymerization method, the melt polymerization method has many advantages in terms of environment, such as not using a solvent, but the resin obtained by heat retention for a long time contains a heterogeneous structure that is by-produced. In addition, the terminal hydroxyl group concentration (terminal OH concentration) is relatively high. For this reason, even when a polymer alloy with a polyethylene terephthalate resin was produced, satisfactory mechanical strength such as impact resistance and heat-and-moisture resistance could not be achieved.

  As a melt polymerization method for achieving a high polymerization rate and obtaining an aromatic polycarbonate resin of good quality, the present inventors previously connected the end of the aromatic polycarbonate prepolymer with a diol compound to extend the chain. A new method was found (for example, see Patent Document 3). According to these methods, a high molecular weight aromatic polycarbonate resin having an Mw of about 30,000 to 100,000 can be obtained in a short time by linking the chain end of the aromatic polycarbonate prepolymer with a diol compound and extending the chain. Can be manufactured. Furthermore, since the aromatic polycarbonate resin is produced by a high-speed polymerization reaction, branching / crosslinking reaction due to long-time heat retention or the like can be suppressed, and the amount of different structures can be reduced. Further, the terminal hydroxyl group concentration (terminal OH group concentration) is also reduced.

  There have been no reports on aromatic polycarbonate resins obtained by such a new melt polymerization method and polymer alloys of polyethylene terephthalate resins, particularly on resin compositions having satisfactory mechanical strength properties and high heat and heat resistance. .

JP 2008-231301 A JP 2009-1620 A International Publication No. 2012/157766 Pamphlet

  The problem to be solved by the present invention is to provide a resin composition comprising an aromatic polycarbonate resin and a polyethylene terephthalate resin having improved impact resistance and heat and moisture resistance.

  As a result of intensive studies to solve the above problems, the present inventors have a quality advantage such as a low degree of branching and a small number of heterogeneous structures while being manufactured by a melt polymerization method. It is found that when an aromatic polycarbonate resin having a cyclic carbonate of a certain amount or less is mixed with a polyethylene terephthalate resin, a resin composition having practically sufficient impact resistance and moist heat resistance and a molded product thereof can be obtained. The present invention has been reached.

  That is, this invention provides the resin composition shown below and its molded article.

1) An aromatic polycarbonate resin having a structural unit represented by the following general formula (I), a polyethylene terephthalate resin, and a cyclic carbonate represented by the following general formula (II):
The aromatic polycarbonate resin in which the ratio (mass ratio) of the aromatic polycarbonate resin and the polyethylene terephthalate resin is 99: 1 to 40:60, and the cyclic carbonate is present at 3000 ppm or less with respect to the aromatic polycarbonate resin. Composition:
Formula (I):

Wherein R ₁ and R ₂ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryl group of -20, a cycloalkoxy group of 6-20 carbon atoms, or an aryloxy group of 6-20 carbon atoms, p and q represent an integer of 0-4, and X represents a single bond or the following ( Represents a group selected from the group of Ia)

(Here, R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₃ and R ₄ are To form an aliphatic ring)
General formula (II):

(In the formula, Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom which may contain a linear or branched alkyl group having 1 to 30 carbon atoms, an oxygen atom or a halogen atom. A cycloalkyl group having 3 to 30 carbon atoms which may contain, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or a carbon number which may contain an oxygen atom or a halogen atom 1 to 15 represents an alkoxy group, or Ra and Rb may be bonded to each other to form a ring, and R _{5 to} R ₈ each independently represents a hydrogen atom, a halogen atom or a carbon number. 1 to 5 linear or branched alkyl groups, and n represents an integer of 0 to 30).

2) The aromatic polycarbonate resin composition according to 1), further including 0.5 to 40 parts by mass of a rubbery polymer with respect to 100 parts by mass in total of the aromatic polycarbonate resin and the polyethylene terephthalate resin.

3) The aromatic polycarbonate resin composition according to 2), wherein the rubbery polymer is a core / shell type graft copolymer.

4) The aromatic polycarbonate resin composition according to any one of 1) to 3), wherein the cyclic carbonate is a compound represented by the following general formula (IIa):
General formula (IIa):

(In the formula, Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom which may contain a linear or branched alkyl group having 1 to 30 carbon atoms, an oxygen atom or a halogen atom. A cycloalkyl group having 3 to 30 carbon atoms which may contain, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or a carbon number which may contain an oxygen atom or a halogen atom 1 to 15 alkoxy groups are represented, or Ra and Rb may be bonded to each other to form a ring).

5) Any one of 1) to 4), wherein the aromatic polycarbonate resin includes a structural unit represented by the following general formula (III), and the content thereof is less than 2000 ppm in the aromatic polycarbonate resin. The aromatic polycarbonate resin composition according to item:
General formula (III):

(Wherein X has the same meaning as in 1) above).

6) The aromatic according to any one of 1) to 5), wherein the N value (structural viscosity index) of the aromatic polycarbonate resin is 1.25 or less when expressed by the following mathematical formula (1). Polycarbonate resin composition.
N value = (log (Q160 value) -log (Q10 value)) / (log160−log10) (1)

7) The aromatic polycarbonate resin composition according to any one of 1) to 6) above, wherein the terminal hydroxyl group content of the aromatic polycarbonate resin is 1000 ppm or less.

8) High molecular weight in which the aromatic polycarbonate resin and the cyclic carbonate are reacted with an aromatic polycarbonate prepolymer and a diol compound represented by the following general formula (IV) in the presence of a transesterification catalyst to increase the molecular weight. The method according to any one of 1) to 7), which is obtained by a method comprising a step and a cyclic carbonate removing step of removing at least a part of the cyclic carbonate by-produced in the high molecular weight step from the reaction system. Aromatic polycarbonate resin composition:
Formula (IV):

(In the formula, Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom which may contain a linear or branched alkyl group having 1 to 30 carbon atoms, an oxygen atom or a halogen atom. A cycloalkyl group having 3 to 30 carbon atoms which may contain, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or a carbon number which may contain an oxygen atom or a halogen atom 1 to 15 represents an alkoxy group, or Ra and Rb may be bonded to each other to form a ring, and R _{5 to} R ₈ each independently represents a hydrogen atom, a halogen atom or a carbon number. 1 to 5 linear or branched alkyl groups, and n represents an integer of 0 to 30).

9) The aromatic polycarbonate resin composition according to 8), wherein the diol compound is a compound represented by the following general formula (IVa):
Formula (IVa):

(In the formula, Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom which may contain a linear or branched alkyl group having 1 to 30 carbon atoms, an oxygen atom or a halogen atom. A cycloalkyl group having 3 to 30 carbon atoms which may contain, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or a carbon number which may contain an oxygen atom or a halogen atom 1 to 15 alkoxy groups are represented, or Ra and Rb may be bonded to each other to form a ring).

10) The diol compound is 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol, The aromatic polycarbonate resin composition according to 8) or 9) selected from the group consisting of 2,2-diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol. object.

11) A molded article obtained by molding the aromatic polycarbonate resin composition according to any one of 1) to 10).

  The resin composition containing the aromatic polycarbonate resin and the polyethylene terephthalate resin of the present invention has greatly improved impact resistance and moist heat resistance. The aromatic polycarbonate resin in such a resin composition can be obtained by a method of increasing the molecular weight of the aromatic polycarbonate by reacting the aromatic polycarbonate (prepolymer) with a diol compound (linking agent) having a specific structure. . The high molecular weight aromatic polycarbonate resin in the resin composition of the present invention obtained by such a method may contain a very small amount of a cyclic carbonate component derived from a linking agent.

  Accordingly, the aromatic polycarbonate resin has the same physical properties as those of the conventional aromatic polycarbonate resin by the interfacial polymerization method, and has a thermal stability (heat resistance) because the cyclic carbonate component derived from the diol compound (linking agent) is in a very small amount. Is excellent. Furthermore, since the diol compound is made into a high molecular weight at a high speed by using as a linking agent, the polycarbonate has original quality advantages such as a high molecular weight, a low degree of branching, and few heterogeneous structures. When the content of the specific cyclic carbonate is not more than a predetermined value, the impact resistance and moist heat resistance of the composition containing the polycarbonate resin and the polyethylene terephthalate resin are greatly improved.

1. Aromatic polycarbonate resin composition (1) Aromatic polycarbonate resin The aromatic polycarbonate resin composition of the present invention includes an aromatic polycarbonate resin having a structural unit represented by the following general formula (I) as a main structural unit. Here, “main” means that the content of the structural unit represented by the general formula (I) in all structural units in the aromatic polycarbonate resin is 60 mol% or more, and 80 mol% or more. It is preferable that it is 90 mol% or more.
Formula (I):

In general formula (I), R ₁ and R ₂ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms is represented. p and q represent the integer of 0-4. X represents a single bond or a group selected from the following group (Ia).

In (Ia), R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₃ and R ₄ are They may be bonded to each other to form an aliphatic ring.

  Examples of the aromatic dihydroxy compound for deriving the structural unit represented by the general formula (I) include compounds represented by the following general formula (V).

Formula (V):

In the general formula (V), R _{1 to} R ₂ , p, q, and X are the same as those in the general formula (I).

  Specific examples of such aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenyl Ethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2 -Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-phenyl) Enyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (3,5-dibromo- 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methoxyphenyl) propane 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4, , 4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy- , 3'-dimethyl diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone and the like.

  Among these, 2,2-bis (4-hydroxyphenyl) propane is preferable because of its stability as an aromatic dihydroxy compound and the ease of obtaining a product containing a small amount of impurities.

  In the present invention, for the purpose of controlling the glass transition temperature, improving fluidity, and the like, a plurality of kinds of the aromatic dihydroxy compounds may be used in combination as necessary.

  The structural unit constituting the aromatic polycarbonate resin in the thermoplastic resin composition of the present invention may contain a structural unit represented by the following general formula (III) as a heterogeneous structure. In the following general formula (III), X is the same as that in the general formula (I).

General formula (III):

  In the aromatic polycarbonate resin having the structural unit represented by the general formula (I), the content of the structural unit represented by the general formula (III) is less than 2000 ppm, preferably 1500 ppm or less. More preferably, it is 1000 ppm or less, More preferably, it is 800 ppm or less, Especially preferably, it is 700 ppm or less, Most preferably, it is 600 ppm or less. When the content of the structural unit represented by the general formula (III) is less than 2000 ppm, the degree of branching tends to decrease and the thermal stability tends to be improved. On the other hand, when the content of the structural unit is 2000 ppm or more, the mixing / dispersibility with the polyethylene terephthalate resin is deteriorated, the fluidity of the resulting resin composition is lowered, and the moldability and mechanical strength are deteriorated. The demerit may occur.

  The structural unit represented by the general formula (III) is a kind of heterogeneous structure that is easily produced as a by-product during the production of the aromatic polycarbonate resin. The aromatic polycarbonate resin used in the present invention preferably has a small proportion of such different structures. An aromatic polycarbonate resin having a small proportion of different structures can be produced, for example, by a method including a step of increasing the molecular weight of an aromatic polycarbonate prepolymer using a linking compound comprising a diol compound having a specific structure described later.

  In addition, the lower limit of the content of the structural unit represented by the general formula (III) in the aromatic polycarbonate resin is not particularly limited, and may be a detection lower limit (usually about 1 ppm), but generally the general formula (III) The structural unit represented by is permitted to be contained in an amount of 1 ppm or more (lower detection limit), and in some cases 5 ppm or more, or 10 ppm or more.

The content of the structural unit represented by the general formula (III) in the present invention is a mass-based value obtained from the ¹ H-NMR analysis result.

When the aromatic polycarbonate resin used in the present invention is produced by increasing the molecular weight using a specific diol compound described below as a linking agent, the aromatic polycarbonate resin has a structure derived from a diol compound. Units may be included. In that case, the content rate of the structural unit derived from the diol compound with respect to the total structural unit amount of the aromatic polycarbonate resin is, for example, 1 mol% or less, and preferably 0.1 mol% or less. Thus, since the structural unit derived from the diol compound is not contained in the skeleton or is contained in a very small amount, the aromatic polycarbonate resin has the same skeleton as that of the conventional homopolycarbonate resin. It is advantageous in that it has excellent quality such as a low value and a small proportion of units having different structures.
In addition, the content rate of the structural unit derived from the diol compound in this invention can be calculated | required from a < ¹ > H-NMR analysis result.

Furthermore, the aromatic polycarbonate resin preferably has a terminal hydroxyl group concentration of 1000 ppm or less, more preferably 800 ppm or less, still more preferably 600 ppm or less, and particularly preferably 500 ppm or less. When the terminal hydroxyl group concentration is 1000 ppm or less, hydrolysis resistance tends to be further improved.
Generally, the terminal portion of the aromatic polycarbonate resin has a structure sealed with an aromatic monohydroxy compound such as phenol, but a part thereof may be a hydroxyl group. Therefore, the terminal hydroxyl group concentration of the aromatic polycarbonate resin is the content ratio of the hydroxyl group in the aromatic polycarbonate resin. The terminal hydroxyl group concentration can be measured, for example, by ¹ H-NMR analysis.

  The weight average molecular weight (Mw) of the aromatic polycarbonate resin used in the present invention is preferably 35,000 to 100,000, more preferably 35,000 to 80,000, particularly preferably 35,000 to 75,000. 000, most preferably 40,000 to 65,000, and also has high fluidity while having a high molecular weight. When the weight average molecular weight is within this range, the formability and productivity when used for applications such as extrusion molding and injection molding are good by blending with polyethylene terephthalate resin. Further, the obtained molded article has good physical properties such as mechanical properties, heat resistance, and organic solvent resistance.

The molecular weight distribution (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in the aromatic polycarbonate resin used in the present invention is, for example, 1.9 to 2.5, 2 It is preferable that it is 0.0-2.4.
In addition, a number average molecular weight (Mn) and a weight average molecular weight (Mw) are measured as a polystyrene conversion value using GPC.

In the aromatic polycarbonate resin used in the present invention, the N value (structural viscosity index) represented by the following mathematical formula (1) is preferably 1.3 or less, more preferably 1.28 or less, particularly preferably. 1.25 or less, most preferably 1.23 or less.
N value = (log (Q160 value) -log (Q10 value)) / (log160−log10) (1)

  In the above formula (1), the Q160 value represents the melt flow volume per unit time (ml / sec) measured at 280 ° C. and a load of 160 kg, and the Q10 value is the melt flow per unit time measured at 280 ° C. and a load of 10 kg. Represents volume (ml / sec).

  The structural viscosity index “N value” is an index of the degree of branching of the polycarbonate resin. In the aromatic polycarbonate resin used in the present invention, it is preferable that the N value is low, the content ratio of the branched structure is small, and the ratio of the linear structure is high. In general, the polycarbonate resin tends to have higher fluidity (Q value becomes higher) when the proportion of the branched structure is increased in the same Mw. The aromatic polycarbonate resin produced by using a specific diol compound described below as a linking agent and having a high molecular weight achieves high fluidity (high Q value) while keeping the N value low. Preferred for use in the present invention.

(2) Polyethylene terephthalate resin The aromatic polycarbonate resin composition of the present invention contains a polyethylene terephthalate resin. The polyethylene terephthalate resin used in the present invention is a polyester having a structure in which a terephthalic acid unit and an ethylene glycol unit are ester-bonded, 50 mol% or more of dicarboxylic acid units are composed of terephthalic acid units, and 50 mol% or more of diol units. Is a polymer composed of ethylene glycol units. And it is preferable that an ethylene terephthalate unit occupies 80 mol% or more of a structural repeating unit, and it is further more preferable to occupy 90 mol% or more. A polyethylene terephthalate resin having an ethylene terephthalate unit of 80 mol% or more is excellent in mechanical properties and heat resistance.

  The method for producing the polyethylene terephthalate resin of the present invention is any conventionally known production method. For example, in the presence of a polymerization catalyst for an antimony compound, the dicarboxylic acid component and the diol component are reacted while heating. The by-product water or lower alcohol is discharged out of the system. Here, this condensation reaction may be carried out by either a batch or continuous polymerization method, and the degree of polymerization may be increased by solid phase polymerization.

  In the polyethylene terephthalate resin used in the present invention, the dicarboxylic acid component other than terephthalic acid that can be copolymerized is not particularly limited, and any conventionally known dicarboxylic acid component can be used, and the content thereof is the dicarboxylic acid component. As a ratio in it, it is 20 mol% or less normally, Preferably it is 15 mol% or less, More preferably, it is 10 mol% or less.

  Examples of the dicarboxylic acid component other than terephthalic acid include aromatic dicarboxylic acids other than terephthalic acid, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and ester-forming derivatives thereof. Specifically, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4 , 4'-diphenylsulfone dicarboxylic acid, aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid; alicyclic ring such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid And dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. These dicarboxylic acid components can be introduced into the polymer skeleton as dicarboxylic acids or as dicarboxylic acid derivatives such as dicarboxylic acid esters and dicarboxylic acid halides.

  In the polyethylene terephthalate resin used in the present invention, the diol component other than ethylene glycol that can be copolymerized is not particularly limited, and any conventionally known diol component can be used, and the content thereof is a ratio in the diol component, Usually, it is 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less.

  Examples of diol components other than ethylene glycol include diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neo Aliphatic diols such as pentyl glycol, 1,6-hexanediol, 1,8-octanediol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedi Alicyclic diols such as methylol; aromatic diols such as xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, etc. And the like.

  In the polyethylene terephthalate resin used in the present invention, lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid, etc. Hydroxycarboxylic acid; monofunctional component such as alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid, tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, Trifunctional or higher polyfunctional components such as gallic acid, trimethylolethane, trimethylolpropane, glycerol and pentaerythritol can be used as the copolymerization component. Furthermore, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polyethylene oxide-added bisphenol A, polypropylene oxide-added bisphenol A, polytetrahydrofuran-added bisphenol A, polytetramethylene glycol, etc. It is also possible to partially copolymerize polyalkylene glycol units derived from the polymer chain.

  Specific examples of the antimony compound include antimony trioxide, antimony acetate, methoxyantimony, sodium antimonate, and the like, and antimony trioxide is preferred from the viewpoint of residence heat stability of the resin composition. The content of the antimony compound used as the polymerization catalyst is preferably 50 to 500 ppm, more preferably 100 to 400 ppm as antimony atoms in the polyethylene terephthalate resin, from the viewpoint of residence heat stability of the resin composition and polymerization rate. It is. The content of the antimony atom can be measured by a method such as atomic emission, atomic absorption, or inductively coupled plasma (ICP) by recovering the metal in the polymer by a method such as wet ashing.

  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 0.7 to 1.5 dL / g, particularly 0.95 to 1. It is preferably 3 dL / g. By setting the intrinsic viscosity to 0.5 dL / g or more, particularly 0.95 dL / g or more, mechanical properties, residence heat stability, chemical resistance, and heat-and-moisture resistance tend to be improved in the resin composition of the present invention. And preferred. Conversely, it is preferable that the intrinsic viscosity is less than 2 dL / g, particularly less than 1.3 dL / g, because the fluidity of the resin composition tends to be improved.

  The intrinsic viscosity 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 setting the terminal carboxyl group to 60 μeq / g or less, the mechanical properties of the resin composition tend to be improved. Conversely, by setting the terminal carboxyl group concentration to 1 μeq / g or more, the heat resistance of the resin composition, It is preferable because the residence heat stability and hue tend to be improved.

  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.

  Furthermore, the polyethylene terephthalate resin used in the present invention may be one that can be obtained from a reagent supplier, and is not only a virgin raw material but also a polyethylene terephthalate resin recycled from a used product, so-called material recycled polyethylene. A terephthalate resin may be used. Used products include containers, films, sheets, fibers, non-conforming products of products, sprues, runners, etc., and pulverized products obtained from these or pellets obtained by melting them can also be used. .

  In the aromatic polycarbonate resin composition of the present invention, the blending ratio (mass ratio) of the aromatic polycarbonate resin and the polyethylene terephthalate resin is 99: 1 to 40:60, preferably 95: 5 to 51:49. More preferably, it is 90: 10-55: 45. When the aromatic polycarbonate resin is 40% by mass or more, impact resistance tends to be improved, and when it is less than 99% by mass, fluidity and chemical resistance tend to be improved.

(3) Cyclic carbonate The aromatic polycarbonate resin composition of the present invention includes a cyclic carbonate represented by the following general formula (II) with respect to the aromatic polycarbonate resin having the structural unit represented by the general formula (I). Is present at 3000 ppm or less. The cyclic carbonate represented by the following general formula (II) is a conventionally known compound, which can be obtained from a reagent supplier or the like, or can be easily synthesized by any conventionally known method. May be added to the aromatic polycarbonate resin composition of the present invention. Alternatively, the cyclic carbonate represented by the following general formula (II) may be a by-product produced in the production process of the aromatic polycarbonate resin. For example, in aromatic polycarbonate resins, cyclic carbonates corresponding to diol compounds used as linking agents in the production process may be by-produced, but even after removal from the reaction system, a small amount of cyclic polycarbonate remains. The cyclic polycarbonate is contained in the aromatic polycarbonate resin finally obtained. When the cyclic carbonate is present at 3000 ppm or less, the fluidity of the aromatic polycarbonate resin composition may be improved. Moreover, each component which comprises an aromatic polycarbonate resin composition is mixed more uniformly, and there exists a tendency for a moldability and mechanical strength to improve. In addition, when cyclic carbonate exceeds 3000 ppm, there may be demerits, such as a fall of the mechanical strength of a resin composition.

General formula (II):

In general formula (II), Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a linear or branched alkyl group having 1 to 30 carbon atoms which may contain a halogen atom, an oxygen atom Alternatively, a cycloalkyl group having 3 to 30 carbon atoms which may contain a halogen atom, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or an oxygen atom or halogen atom may be contained. It represents a good alkoxy group having 1 to 15 carbon atoms, or Ra and Rb may be bonded to each other to form a ring. As the halogen atom, a fluorine atom is preferable.
R _{5 to} R ₈ each independently represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. As the halogen atom, a fluorine atom is preferable.
n represents an integer of 0 to 30, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and particularly preferably 1.

In general formula (II), Ra and Rb are preferably each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, It represents an aryl group having 6 to 10 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, or Ra and Rb may be bonded to each other to form an alicyclic ring having 3 to 8 carbon atoms. . As the halogen atom, a fluorine atom is preferable.
R _{5 to} R ₈ preferably each independently represent a hydrogen atom, a fluorine atom or a methyl group. n preferably represents an integer of 1 to 6.

In general formula (II), Ra and Rb are more preferably each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a straight chain having 1 to 4 carbon atoms. A chain or branched alkyl group. Particularly preferred specific examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, and an i-butyl group. R _{5 to} R ₈ are more preferably each a hydrogen atom. n preferably represents an integer of 1 to 3.

The cyclic carbonate represented by the general formula (II) is more preferably a compound represented by the following general formula (IIa). In general formula (IIa), n, Ra and Rb are the same as those in general formula (II) described above.
General formula (IIa):

Specific examples of the cyclic carbonate include compounds having the following structures.

  In the aromatic polycarbonate resin composition of the present invention, the cyclic carbonate represented by the general formula (II) is on a mass basis with respect to the aromatic polycarbonate resin having the structural unit represented by the general formula (I). It is 3000 ppm or less, preferably 1000 ppm or less, more preferably 500 ppm or less, particularly preferably 300 ppm or less, and still more preferably 100 ppm or less. The lower limit value of the cyclic polycarbonate is usually the detection lower limit value, but is preferably 0.0005 ppm, more preferably 0.005 ppm, still more preferably 0.05 ppm, and particularly preferably 0.1 ppm. The presence of such a cyclic carbonate may improve the fluidity of the polycarbonate resin composition. If the cyclic carbonate exceeds 3000 ppm, there may be disadvantages such as a decrease in resin strength. If the cyclic carbonate is too low, the fluidity may be deteriorated, or it may have sufficient impact resistance and moist heat resistance. It can be difficult.

(4) Rubber polymer In the aromatic polycarbonate resin composition of the present invention, in addition to the essential components, a rubber polymer can be blended for the purpose of improving impact resistance. The rubbery polymer indicates a glass transition temperature of 0 ° C. or lower, particularly −20 ° C. or lower, and includes a polymer obtained by copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. . As the rubbery polymer used in the present invention, any conventionally known polymer which is generally blended with an aromatic polycarbonate resin and can improve its impact resistance can be used.

  Specific examples of the rubbery polymer include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer; polyorganosiloxane rubber In addition to silicone rubber such as butadiene-acrylic composite rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α-olefin rubber (ethylene-propylene rubber, ethylene -Butene rubber, ethylene-octene rubber, etc.), ethylene-acrylic rubber, fluororubber and the like. Two or more of these may be used in combination. Among these, in terms of impact resistance, any one selected from the group of polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber. Species are preferred.

  Specific examples of monomer components copolymerizable with the rubber polymer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, etc. 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 An anhydride (for example, maleic anhydride etc.) etc. are mentioned. Two or more of these monomer components may be used in combination. Among these, from the viewpoint of impact resistance, it is preferably any one selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds. Yes, and more preferably a (meth) acrylic acid ester 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. It is done.

  The rubbery polymer used in the present invention is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance. In this case, the core layer is at least one rubber component selected from the group of polybutadiene-containing rubber, polybutylacrylate-containing rubber, IPN (Interpenetrating polymer network) type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber. The shell layer is preferably formed of (meth) acrylic acid ester and acrylonitrile-styrene copolymer.

  Preferable specific examples of the core / shell type graft copolymer include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer. Polymer (MABS), methyl methacrylate-acrylic rubber copolymer (MA), acrylonitrile-styrene-acrylic rubber copolymer (ASA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic Examples thereof include a butadiene rubber copolymer, a methyl methacrylate-acrylic / butadiene rubber-styrene copolymer, and a methyl methacrylate- (acrylic / silicone IPN rubber) copolymer. Two or more of these may be used in combination.

  In addition, examples of the core / shell type graft copolymer include “STAPHYLOID MG1011” manufactured by GANTZ Kasei Co., Ltd., “PARALLOID EXL2315”, “EXL2602” manufactured by Rohm and Haas Japan, Ltd., “ Examples include the EXL series such as EXL2603, the KM series such as “KM330” and “KM336P”, the KCZ series such as “KCZ201”, “Metablene S-2001” and “SRK-200” manufactured by Mitsubishi Rayon Co., Ltd.

  Specific examples of other rubbery polymers include styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), Examples thereof include styrene-ethylene / propylene-styrene block copolymer (SEPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), and acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES).

  The content of the rubber polymer is, for example, 0.5 to 40 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 25 parts by mass with respect to 100 parts by mass in total of the aromatic polycarbonate resin and the polyethylene terephthalate resin. Part. When the content of the rubber polymer is 1 part by mass or more, impact resistance tends to be improved, and when it is less than 40 parts by mass, rigidity, heat resistance, and moist heat resistance tend to be improved.

(5) Other components The aromatic polycarbonate resin composition of the present invention may further contain other components as long as the effects of the present invention such as improvement in impact resistance and moist heat resistance are not impaired. Other components include, for example, heat stabilizers, hydrolysis stabilizers, antioxidants, pigments, dyes, reinforcing agents and fillers, UV absorbers, lubricants, mold release agents, crystal nucleating agents, plasticizers, flow Examples include property improvers, antistatic agents, and antibacterial agents.

As the heat stabilizer, a known one such as triphenylphosphine (P-Ph ₃ ) can be used.
As the mold release agent, known ones such as fatty acid esters, polyolefin waxes, fluoro oils, paraffin waxes, and the like can be used. In particular, pentaerythritol fatty acid esters such as pentaerythritol tetrastearate can be used.

  Antioxidants include tris- (2,4-di-t-butylphenyl) phosphite, octadecyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate, pentaerythrityl-tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Triethylene glycol-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenylpropionate), 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triphenylphospho Phyto, trisnonylphenyl phosphite, tris- (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphonite, Tricresyl phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, and the like can be used. Of these, tris- (2,4-di-t-butylphenyl) phosphite and octadecyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate are preferred.

(6) Manufacturing method of aromatic polycarbonate resin composition As a manufacturing method of the aromatic polycarbonate resin composition of this invention, the manufacturing method of a conventionally well-known resin composition is employable. For example, the essential components and optional components may be dispersed and mixed with a high speed mixer represented by a turnbull mixer, a Henschel mixer, a ribbon blender, a super mixer, etc., and then melt kneaded with an extruder, a Banbury mixer, a roll, or the like. . In addition, you may add an additive to each essential component before dispersion | distribution mixing.

2. Molded products Aromatic polycarbonate resin compositions comprising the polycarbonate resin, polyethylene terephthalate resin and cyclic carbonate of the present invention are various molded products and various members obtained by injection molding, blow molding, extrusion molding, rotational molding, compression molding, etc. It can be preferably used for the following purposes. When used in these applications, the aromatic polycarbonate resin composition of the present invention alone or a blend with another polymer may be used. Depending on the application, processing such as hard coating can be preferably used.

  Particularly preferably, the aromatic polycarbonate resin composition of the present invention is used for extrusion molding, injection molding and the like. Due to its excellent mechanical properties, the obtained molded products include extrusion molded products, precision parts and injection molded products, raw materials in the automotive field, OA equipment field, electronic / electric field, etc., and raw materials in the general industrial field. However, it is not limited to these.

  Specific examples of molded products include various raw materials in the electrical and electronic fields, various raw materials in the automobile and aircraft industries, other optical equipment parts, in-vehicle supplies such as trains and automobiles, various building materials, copiers, facsimiles, personal computers, and other OA. Various parts charges for equipment, various parts materials for home appliances such as TVs and microwave ovens, electronic parts applications such as connectors and IC trays, protective equipment such as helmets, protectors, protective surfaces, members for different medical devices, etc. It can mention, but it is not limited to these. As described above, the use of the aromatic polycarbonate resin composition of the present invention that is particularly preferable includes a molded product that particularly requires high strength (high Charpy strength) and precision moldability.

3. Production method of aromatic polycarbonate resin The production method of the aromatic polycarbonate resin used in the present invention is not particularly limited, and those obtained by any known production method can be used, but those obtained by the production methods shown below can be used. Is preferably used. By adopting such a production method, it is possible to efficiently produce an aromatic polycarbonate resin having a low degree of branching, a low content of different structures, a low concentration of terminal hydroxyl groups, and a cyclic carbonate having a specific structure at a desired content. Can be manufactured.

  A preferred production method is to increase the molecular weight of an aromatic polycarbonate resin obtained by reacting an aromatic polycarbonate prepolymer with a diol compound represented by the following general formula (IV) in the presence of a transesterification catalyst. And a cyclic carbonate removing step of removing at least a part of the cyclic carbonate by-produced in the high molecular weight step from the reaction system.

(1) Diol compound The diol compound used by a preferable manufacturing method is represented by the following general formula (IV).

Formula (IV):

In general formula (IV), Ra and Rb each independently represent a hydrogen atom, a halogen atom, an oxygen atom or a linear or branched alkyl group having 1 to 30 carbon atoms which may contain a halogen atom, an oxygen atom or A cycloalkyl group having 3 to 30 carbon atoms which may contain a halogen atom, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or an oxygen atom or a halogen atom may be contained. It represents an alkoxy group having 1 to 15 carbon atoms, or Ra and Rb may be bonded to each other to form a ring. As the halogen atom, a fluorine atom is preferable.
R _{5 to} R ₈ each independently represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. As the halogen atom, a fluorine atom is preferable.
n represents an integer of 0 to 30, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and particularly preferably 1.

In the general formula (IV), Ra and Rb are preferably each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, It represents an aryl group having 6 to 10 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, or Ra and Rb may be bonded to each other to form an alicyclic ring having 3 to 8 carbon atoms. . As the halogen atom, a fluorine atom is preferable.
R _{5 to} R ₈ preferably each independently represent a hydrogen atom, a fluorine atom or a methyl group. n preferably represents an integer of 1 to 6.

In general formula (IV), Ra and Rb are more preferably each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a straight chain having 1 to 4 carbon atoms. A chain or branched alkyl group. Particularly preferred specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. R _{5 to} R ₈ are more preferably each a hydrogen atom. n preferably represents an integer of 1 to 3.

  More preferred as the diol compound represented by the general formula (IV) is a compound represented by the following general formula (IVa). In the formula, Ra and Rb are the same as those in formula (IV).

Formula (IVa):

  In general formula (IVa), Ra and Rb are more preferably each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear chain having 1 to 4 carbon atoms. Or it is a branched alkyl group, More preferably, it is a C2-C4 linear or branched alkyl group. Particularly preferred specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and preferably an ethyl group, a propyl group, a butyl group, and an isobutyl group.

  Examples of the diol compound include 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol, 2, 2-diethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, propane-1,2-diol, propane-1,3-diol, ethane-1,2-diol ( 1,2-ethylene glycol), 2,2-diisoamylpropane-1,3-diol, and 2-methylpropane-1,3-diol.

Other examples of the diol compound include compounds having the following structural formula.

  Of these, particularly preferred are 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol. It is a compound selected from the group consisting of diol, 2,2-diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol.

(2) Aromatic polycarbonate prepolymer The aromatic polycarbonate prepolymer used in the preferred production method is a polycondensation having the main structural unit represented by the general formula (I) constituting the aromatic polycarbonate resin of the present invention. It is a polymer.

  The production method of the present invention includes a step of linking the aromatic polycarbonate prepolymer with the diol compound represented by the general formula (IV) by transesterification under reduced pressure. As a result, while maintaining the original properties of polycarbonate resin such as impact resistance, it provides high fluidity while being high in molecular weight, and also has a low proportion of different structural units represented by the above general formula (III) and heat resistance. A significantly improved aromatic polycarbonate resin is obtained.

  Such an aromatic polycarbonate prepolymer is a known transesterification method in which an aromatic dihydroxy compound that induces a structural unit represented by the general formula (I) is reacted with a carbonic acid diester in the presence of a transesterification catalyst such as a basic compound, Alternatively, it can be easily obtained by any known interfacial polycondensation method in which the aromatic dihydroxy compound is reacted with phosgene or the like in the presence of an acid binder.

  Examples of the aromatic dihydroxy compound for deriving the structural unit represented by the general formula (I) include a compound represented by the general formula (V).

  The aromatic polycarbonate prepolymer used in the present invention may be synthesized by an interfacial polymerization method or may be synthesized by a melt polymerization method, and may be a solid phase polymerization method or a thin film polymerization method. It may be synthesized. Further, it is also possible to use polycarbonate recovered from used products such as used disk molded products. These polycarbonates can be mixed and used as a polymer before reaction. For example, a polycarbonate polymerized by an interfacial polymerization method and a polycarbonate polymerized by a melt polymerization method may be mixed, and a polycarbonate polymerized by a melt polymerization method or an interfacial polymerization method and a polycarbonate recovered from a used disk molded product, etc. May be used in combination.

The aromatic polycarbonate prepolymer used in the present invention is preferably an end-capped aromatic polycarbonate prepolymer satisfying specific conditions.
That is, at least a part of the aromatic polycarbonate prepolymer is sealed with an aromatic monohydroxy compound-derived terminal group or terminal phenyl group (hereinafter also referred to as “sealing terminal group”). preferable.

The ratio of the sealed end groups is preferably 60 mol% or more with respect to the total terminal amount. Further, the terminal phenyl group concentration (ratio of blocked end groups to all structural units) is 2 mol% or more, preferably 2 to 20 mol%, particularly preferably 2 to 12 mol%. When the terminal phenyl group concentration is 2 mol% or more, the reaction with the diol compound proceeds rapidly, and the above-mentioned specific effect is particularly remarkable. The ratio of the amount of capped ends to the total amount of ends of the aromatic polycarbonate prepolymer can be analyzed by ¹ H-NMR analysis of the aromatic polycarbonate prepolymer.

Further, the terminal hydroxyl group concentration can be measured by spectroscopic measurement using a Ti complex. Furthermore, the terminal hydroxyl group concentration can also be measured by ¹ H-NMR analysis. The terminal hydroxyl group concentration by the same evaluation is preferably 1,500 ppm or less, more preferably 1,000 ppm or less. If the amount of hydroxyl groups is within this range or the amount of blocked ends is within this range, a sufficient high molecular weight effect tends to be obtained by transesterification with the diol compound.

  As used herein, “total amount of terminal groups of aromatic polycarbonate” or “total amount of terminal groups of aromatic polycarbonate prepolymer” refers to, for example, 0.5 mol of unbranched polycarbonate (that is, chain polymer) The base weight is calculated as 1 mole.

  Specific examples of the sealing end group include phenyl end group, cresyl end group, o-tolyl end group, p-tolyl end group, pt-butylphenyl end group, biphenyl end group, o-methoxycarbonylphenyl end group. , And p-cumylphenyl end groups.

  In these, the terminal group comprised with the low boiling point aromatic monohydroxy compound which is easy to remove from a reaction system by transesterification with a diol compound is preferable, and a phenyl terminal group, pt-butylphenyl terminal group, etc. Particularly preferred.

  Such a sealed end group can be introduced by using an end-stopper during the production of the aromatic polycarbonate prepolymer in the interfacial method. Specific examples of the terminal terminator include pt-butylphenol, phenol, p-cumylphenol, and long-chain alkyl-substituted phenol. The amount of the terminal stopper used can be appropriately determined according to the desired terminal amount of the aromatic polycarbonate prepolymer (that is, the molecular weight of the desired aromatic polycarbonate prepolymer), the reaction apparatus, the reaction conditions, and the like.

  In the melting method, a capped end group can be introduced by using an excess of a carbonic acid diester such as diphenyl carbonate with respect to the aromatic dihydroxy compound during the production of the aromatic polycarbonate prepolymer. Although it depends on the apparatus and reaction conditions used for the reaction, specifically, 1.00 to 1.30 mol, more preferably 1.02 to 1.20 mol of carbonic acid diester is used per 1 mol of the aromatic dihydroxy compound. . Thereby, an aromatic polycarbonate prepolymer satisfying the end capping amount is obtained.

  Preferably, an end-capped polycondensation polymer obtained by reacting an aromatic dihydroxy compound and a carbonic acid diester (ester exchange reaction) is used as the aromatic polycarbonate prepolymer.

  When producing an aromatic polycarbonate prepolymer, a polyfunctional compound having three or more functional groups in one molecule can be used in combination with the aromatic dihydroxy compound. As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferably used.

  Further, when an aromatic polycarbonate prepolymer is produced, a dicarboxylic acid compound may be used in combination with the aromatic dihydroxy compound to form a polyester carbonate. As the dicarboxylic acid compound, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like are preferable, and these dicarboxylic acids are preferably reacted as an acid chloride or an ester compound. Moreover, when manufacturing polyester carbonate resin, it is preferable to use dicarboxylic acid in 0.5-45 mol% when the sum total of the said dihydroxy component and dicarboxylic acid component is 100 mol%. It is more preferable to use in the range of ˜40 mol%.

  The molecular weight of the aromatic polycarbonate prepolymer is preferably Mw of 5,000 to 35,000. More preferably, Mw is in the range of 15,000 to 35,000, more preferably 20,000 to 35,000, and particularly preferably 20,000 to 33,000.

  When an aromatic polycarbonate prepolymer having a molecular weight within this range is used, the viscosity of the aromatic polycarbonate prepolymer itself is low, so that it is not necessary to produce the prepolymer at high temperature, high shear, and long time, and / or Or, it tends to be unnecessary to carry out the reaction with the diol compound at a high temperature, high shear, and a long time.

(3) Cyclic carbonate In a preferred production method, the aromatic polycarbonate prepolymer is made to have a high molecular weight by allowing the end-capped aromatic polycarbonate prepolymer to act under reduced pressure conditions in the presence of a transesterification catalyst. Aromatic polycarbonate resin is obtained. This reaction proceeds at a high speed under mild conditions, and a high-quality aromatic polycarbonate resin having a high molecular weight is obtained.

  In the method of reacting the diol compound having the specific structure, the reaction between the aromatic polycarbonate prepolymer and the diol compound proceeds, and a cyclic carbonate which is a cyclic body having a structure corresponding to the structure of the diol compound is by-produced. By removing the cyclic carbonate produced as a by-product from the reaction system, the molecular weight of the aromatic polycarbonate prepolymer is increased, and finally the structure is almost the same as a conventional homopolycarbonate (for example, a homopolycarbonate resin derived from bisphenol A). An aromatic polycarbonate resin having

  The high molecular weight process and the cyclic carbonate removing process are not necessarily physically and temporally separate processes, and are actually performed simultaneously. In a preferred production method of the present invention, an aromatic polycarbonate resin is reacted with an diol compound in the presence of a transesterification catalyst to obtain a high molecular weight aromatic polycarbonate resin, and a cyclic product by-produced in the high molecular weight reaction. It includes a step of removing at least a part of the carbonate out of the reaction system.

  The cyclic carbonate produced as a by-product has a structure corresponding to the diol compound used, and is specifically a compound represented by the general formula (II). Specific embodiments thereof are also as described above. In addition, the reaction mechanism by which cyclic carbonate is by-produced with such high molecular weight is not necessarily clear.

  For example, the mechanism shown in the following scheme (1) or (2) can be considered, but it is not always clear. In the production method using the diol compound having the structure represented by the general formulas (IV) to (IVa) of the present invention, the aromatic polycarbonate prepolymer is reacted with a diol compound as a linking agent. Are linked together to increase the molecular weight, and the cyclic carbonate having a structure corresponding to the structure of the diol compound by-produced therein is removed, and the reaction mechanism is not limited to a specific reaction mechanism.

Scheme (1):

Scheme (2):

  The aromatic polycarbonate resin having a high molecular weight obtained by the production method using the diol compound having the structure represented by the general formula (IV) of the present invention contains almost no structural unit derived from the diol compound. The skeleton is almost the same as homopolycarbonate resin.

  That is, since the structural unit derived from the diol compound as the linking agent is not contained in the skeleton or is contained in a very small amount, the thermal stability is extremely high and the heat resistance is excellent. On the other hand, while having the same skeleton as a conventional homopolycarbonate resin, it can be provided with excellent quality such as a low N value, a small proportion of different structural units, and excellent color tone.

  Here, the heterogeneous structural unit refers to a structural unit that may cause an undesirable effect, and examples thereof include branch point units contained in a large amount in a polycarbonate obtained by a conventional melt polymerization method. According to a preferred production method, the content of the structural unit represented by the general formula (III) can be reduced. More specifically, reducing the content of the structural unit represented by the general formula (III) to 2000 ppm or less with respect to the aromatic polycarbonate resin having the structural unit represented by the general formula (I). Can do.

  In addition, the structural unit derived from a diol compound may be contained in the frame | skeleton of the aromatic polycarbonate resin composition obtained by the manufacturing method of this invention. In that case, the content of the structural unit derived from the diol compound with respect to the total structural unit amount of the high molecular weight aromatic polycarbonate resin is, for example, 1 mol% or less, preferably 0.1 mol% or less.

(4) Manufacturing method The detailed conditions of the preferable manufacturing method of the aromatic polycarbonate resin used by this invention are demonstrated below.
(I) Addition of diol compound In a preferred production method, a diol compound represented by the general formula (IV) is added to and mixed with an aromatic polycarbonate prepolymer, and a high molecular weight reaction (transesterification) is carried out in a high molecular weight reactor. Reaction).

  The amount of the diol compound used is preferably 0.01 to 1.0 mol, more preferably 0.1 to 1.0 mol, based on 1 mol of all terminal groups of the aromatic polycarbonate prepolymer. More preferably, it is 0.2-0.7 mol. However, when a product having a relatively low boiling point is used, an excessive amount may be added in advance in consideration of the possibility that a part of the reaction may go out of the system without being involved in the reaction due to volatilization or the like depending on the reaction conditions. For example, a maximum of 50 moles, preferably 10 moles, more preferably 5 moles can be added to 1 mole of all terminal groups of the aromatic polycarbonate prepolymer.

  The method for adding and mixing the diol compound is not particularly limited, but when a diol compound having a relatively high boiling point (boiling point of about 350 ° C. or higher) is used, the diol compound has a degree of vacuum of 10 torr (1333 Pa or lower). It is preferable to supply directly to a high molecular weight reactor under high vacuum. More preferably, the degree of vacuum is 2.0 torr or less (267 Pa or less), more preferably 0.01 to 1 torr (1.3 to 133 Pa or less). If the degree of pressure reduction when supplying the diol compound to the high molecular weight reactor is insufficient, the cleavage reaction of the prepolymer main chain by the by-product (phenol) proceeds, and in order to increase the molecular weight, the reaction mixture It may be necessary to lengthen the reaction time.

  On the other hand, when a diol compound having a relatively low boiling point (boiling point less than about 350 ° C.) is used, the aromatic polycarbonate prepolymer and the diol compound can be mixed at a relatively moderate pressure. For example, an aromatic polycarbonate prepolymer and a diol compound are mixed at a pressure close to normal pressure to obtain a prepolymer mixture, and then the prepolymer mixture is subjected to a high molecular weight reaction under reduced pressure conditions, thereby having a relatively low boiling point. Volatilization is minimized even with diol compounds, eliminating the need for excessive use.

(Ii) Transesterification reaction (high molecular weight reaction)
The temperature used in the transesterification reaction (polymerization reaction) between the aromatic polycarbonate prepolymer and the diol compound is preferably in the range of 240 ° C to 320 ° C, more preferably 260 ° C to 310 ° C, and even more preferably 280 ° C. ~ 310 ° C.

  The degree of reduced pressure is preferably 13 kPaA (100 torr) or less, more preferably 1.3 kPaA (10 torr) or less, more preferably 0.67 to 0.013 kPaA (5 to 0.1 torr).

  Examples of the transesterification catalyst used in the transesterification reaction include basic compounds such as alkali metal compounds and / or alkaline earth metal compounds, nitrogen-containing compounds, and the like.

  Examples of such compounds include organic acid salts such as alkali metal and alkaline earth metal compounds, inorganic salts, oxides, hydroxides, hydrides or alkoxides, quaternary ammonium hydroxides and salts thereof, amines, and the like. These compounds are preferably used, and these compounds can be used alone or in combination.

  Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, acetic acid. Cesium, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium tetraphenylborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, phosphoric acid Disodium hydrogen, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, sodium gluconate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, phenol Sodium salt, potassium salt, cesium salt, lithium salt or the like is used.

  Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate. Strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate, and the like are used.

  Specific examples of nitrogen-containing compounds include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and other alkyl groups and / or aryl groups. Quaternary ammonium hydroxides, tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole Imidazoles such as 2-phenylimidazole and benzimidazole, ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, Rafeniruhou tetrabutyl ammonium, basic or basic salts such as tetraphenyl borate tetraphenyl ammonium or the like is used.

  As the transesterification catalyst, salts of zinc, tin, zirconium and lead are also preferably used, and these can be used alone or in combination.

  Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, and dibutyltin. Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate and the like are used.

These catalysts are used in a ratio of 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁷ to 1 to 1 mol in total of the aromatic dihydroxy compounds constituting the aromatic polycarbonate prepolymer. It is used at a ratio of × 10 ⁻⁵ mol.

(Iii) Cyclic carbonate removal step The aromatic polycarbonate prepolymer is polymerized by the polymerisation reaction to obtain an aromatic polycarbonate resin having a desired molecular weight, and at the same time, at least one of the cyclic carbonates by-produced in the reaction. Part is removed out of the reaction system. By removing at least a part of the cyclic carbonate produced as a by-product from the reaction system, the high molecular weight reaction of the aromatic polycarbonate prepolymer further proceeds.

  Examples of the method for removing the cyclic carbonate include a method of distilling off from the reaction system together with an aromatic monohydroxy compound such as phenol and an unreacted diol compound which are also by-produced. The temperature at the time of distilling from a reaction system is 240-320 degreeC, for example, Preferably it is 260-310 degreeC, More preferably, it is 280-310 degreeC.

The removal of the cyclic carbonate is performed on at least a part of the cyclic carbonate by-produced. The upper limit with preferable residual amount of the cyclic carbonate byproduced is 3000 ppm. That is, in the production method using the diol compound having the structure represented by the general formula (IV) of the present invention, the cyclic carbonate having the structure represented by the general formula (II) is 3000 ppm or less, preferably 1000 ppm or less. More preferably, an aromatic polycarbonate resin composition containing 500 ppm or less, particularly preferably 300 ppm or less is obtained. In that case, the lower limit of the content ratio of the cyclic carbonate having the structure represented by the general formula (II) is usually a detection limit value, and is preferably 0.0005 ppm or more.
In addition, the content rate of cyclic carbonate is the value measured by GC-MS.

  The cyclic carbonate distilled out of the reaction system can then be recovered and reused (recycled) through processes such as hydrolysis and purification. The phenol distilled off together with the cyclic carbonate can also be recovered and supplied to the diphenyl carbonate production process for reuse.

(Iv) Other production conditions In the present invention, the weight average molecular weight (Mw) of the aromatic polycarbonate resin after the reaction is the weight of the aromatic polycarbonate prepolymer by the transesterification reaction between the aromatic polycarbonate prepolymer and the diol compound. It is preferable to increase the molecular weight (Mw) by 5,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more.

Any kind of known apparatus may be used in the transesterification reaction with the diol compound, the material of the kettle, etc., and it may be a continuous type or a batch type. The reaction apparatus used for carrying out the above reaction is equipped with paddle blades, lattice blades, glasses blades, etc., even with vertical types equipped with vertical stirring blades, Max blend stirring blades, helical ribbon stirring blades, etc. It may be a horizontal type or an extruder type equipped with a screw, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer. It is preferable to have a rotary blade with good horizontal agitation efficiency and a unit that can be decompressed.
More preferably, a twin screw extruder or a horizontal reactor having a polymer seal and having a devolatilization structure is suitable.

  The material of the apparatus is preferably stainless steel such as SUS310, SUS316 or SUS304, or a material that does not affect the color tone of the polymer such as nickel or nitrided steel. Further, the inner side of the device (the portion in contact with the polymer) may be subjected to buffing or electropolishing, or may be subjected to metal plating such as chromium.

  A catalyst deactivator may be added to the high molecular weight aromatic polycarbonate resin. In general, the catalyst deactivator includes a known acidic substance, and a method of deactivating the catalyst by the addition thereof is preferably carried out. Specific examples of these substances include aromatic sulfonic acids such as paratoluenesulfonic acid, aromatic sulfonic acid esters such as butyl paratoluenesulfonate, tetrabutylphosphonium salt of dodecylbenzenesulfonic acid, tetratoluenesulfonic acid tetra Aromatic sulfonates such as butylammonium salts, stearic acid chloride, butyric acid chloride, benzoyl chloride, toluene sulfonic acid chloride, organic halides such as benzyl chloride, alkyl sulfates such as dimethyl sulfate, phosphoric acids, phosphorous acids, etc. Can be mentioned.

  The addition amount of the catalyst deactivator is not particularly limited, but is preferably 3 ppm or more, more preferably 5 ppm or more with respect to the aromatic polycarbonate resin. When the content of the catalyst deactivator is 3 ppm or more, an effect of improving thermal stability can be expected. The upper limit of the addition amount of the catalyst deactivator is not particularly limited, but is preferably 30 ppm or less, more preferably 20 ppm or less.

Of these, a catalyst deactivator selected from the group consisting of paratoluenesulfonic acid, paratoluenesulfonic acid butyl, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, and paratoluenesulfonic acid tetrabutylammonium salt is preferably used. .
The addition of the catalyst deactivator can be mixed with the polycarbonate resin by a conventionally known method after the completion of the high molecular weight reaction. For example, a method of appropriately mixing and kneading with an extruder, a Banbury mixer, a roll or the like after being dispersed and mixed with a high speed mixer represented by a turnbull mixer, a Henschel mixer, a ribbon blender, or a super mixer is appropriately selected.

  After catalyst deactivation, a step of devolatilizing and removing low-boiling compounds in the polymer at a pressure of 0.013-0.13 kPaA (0.1-1 torr) and a temperature of 200-350 ° C. may be provided. A horizontal apparatus equipped with a stirring blade having excellent surface renewability, such as a paddle blade, a lattice blade, or a glasses blade, or a thin film evaporator is preferably used. A twin screw extruder or a horizontal reactor having a polymer seal and a vent structure is preferable.

  Examples The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the measured value in an Example is the following method or apparatus for the analysis and physical-property evaluation of the obtained polycarbonate or polycarbonate resin composition (Hereinafter, it may be called "polycarbonate." It measured using.

1) Polystyrene equivalent weight average molecular weight (Mw) and polystyrene equivalent number average molecular weight (Mn):
A calibration curve was prepared using standard polystyrene (manufactured by Tosoh Corporation, “PStQuick MP-M”) having a known molecular weight (molecular weight distribution = 1) using GPC and chloroform as a developing solvent. The elution time and molecular weight value of each peak were plotted from the measured standard polystyrene, and approximated by a cubic equation to obtain a calibration curve. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were obtained from the following calculation formulas.

[a formula]
Mw = Σ (Wi × Mi) ÷ Σ (Wi)
Mn = Σ (Ni × Mi) ÷ Σ (Ni)
Here, i is the i-th dividing point when the molecular weight M is divided, Wi is the i-th weight, Ni is the number of the i-th molecule, and Mi is the i-th molecular weight. The molecular weight M represents a polystyrene molecular weight value at the same elution time of the calibration curve.

2) Molecular weight distribution (Mw / Mn)
It calculated | required from the following formula from the polystyrene conversion weight average molecular weight (Mw) and the polystyrene conversion number average molecular weight (Mn).

[a formula]
Molecular weight distribution = Mw / Mn

[Measurement condition]
Device: HLC-8320GPC, manufactured by Tosoh Corporation
Column; Guard column: TSKguardcolumn SuperMPHZ-M x 1
Analytical column: TSKgel SuperMultiporeHZ-M × 3 solvents; HPLC grade chloroform injection volume: 10 μL
Sample concentration; 0.2 w / v% HPLC grade chloroform solution solvent flow rate; 0.35 ml / min
Measurement temperature: 40 ° C
Detector; RI

3) Terminal hydroxyl group concentration (ppm): Measured by observing the terminal hydroxyl group from the analysis result of ¹ H-NMR.
^The concentration of the terminal hydroxyl group in the prepolymer (PP) by ¹ H-NMR was determined by dissolving 0.05 g of a resin sample in 1 ml of deuterium-substituted chloroform (containing 0.05 w / v% TMS), and ¹ H-NMR at 23 ° C. It was obtained by measuring. Specifically, the terminal hydroxyl group concentration (OH) in PP was determined from the integral ratio of the hydroxyl group peak at 4.7 ppm and the phenyl and phenylene groups (terminal phenyl group and phenylene group derived from the BPA skeleton) in the vicinity of 7.0 to 7.5 ppm. Concentration) was calculated. The terminal hydroxyl group concentration in the aromatic polycarbonate resin can also be measured and calculated in the same manner.

The details of the ¹ H-NMR measurement conditions are as follows.
Device: LA-500 (500MHz) manufactured by JEOL Ltd.
Measuring nucleus: 1H
relaxation delay: 1s
x_angle: 45deg
x_90_width: 20μs
x_plus: 10μs
scan: 500times

4) Terminal phenyl group concentration (sealing terminal group concentration, Ph terminal concentration; mol%): From the analysis result of ¹ H-NMR, the following formula was used.

Specifically, 0.05 g of a resin sample was dissolved in 1 ml of deuterium-substituted chloroform (containing 0.05 w / v% TMS), a ¹ H-NMR spectrum was measured at 23 ° C., and a terminal of about 7.4 ppm was obtained. The terminal phenyl group amount and terminal phenyl group concentration of PP were measured from the integration ratio of the phenyl group and the phenylene group in the vicinity of 7.0 to 7.3 ppm (derived from the BPA skeleton). The details of ¹ H-NMR measurement conditions are the same as described above.

  The total terminal group amount of the polymer can be calculated from the terminal hydroxyl group concentration and the terminal phenyl group concentration.

5) Amount of heterogeneous structure A resin sample of 0.05 g was dissolved in 1 ml of deuterium-substituted chloroform (containing 0.05 w / v% TMS), and the molecular weight was increased using a nuclear magnetic resonance analyzer ¹ H-NMR at 23 ° C. The amount of different structures in the polycarbonate (PC) was measured. The amounts of the following heterostructure units were measured by assignment of ¹ H-NMR of Ha and Hb described in P.7659 in the document Polymer 42 (2001) 7653-7661. The details of ¹ H-NMR measurement conditions are the same as described above.

[Calculation]
Signals of Ha (near 8.01 ppm) and Hb (near 8.15 ppm) and phenyl and phenylene groups (terminal phenyl group and phenylene group derived from BPA skeleton) around 7.0 to 7.5 ppm in the heterogeneous structural unit. The amount of heterogeneous structure was calculated from the signal integration ratio.

6) N value Aromatic polycarbonate (sample) dried at 120 ° C for 5 hours using Koka-type flow tester CFT-500D (manufactured by Shimadzu Corporation), die having a hole diameter of 1.0 mmφ and a length of 10 mm The melt flow volume per unit time measured at 280 ° C. and a load of 160 kg is set as Q160 value, and the melt flow volume per unit time measured at 280 ° C. and a load of 10 kg is set as Q10 value. It calculated | required by Formula (1).
N value = (log (Q160 value) -log (Q10 value)) / (log160−log10) (1)

7) Impact resistance (Charpy impact test)
After the pellets of the aromatic polycarbonate resin composition are dried at 120 ° C. for 5 hours, the cylinder temperature is 280 ° C., the mold temperature is 80 ° C., and the molding cycle is performed with an injection molding machine (“SG75Mk-II” manufactured by Sumitomo Heavy Industries, Ltd.). Injection molding was carried out under the condition of 50 seconds to produce an ISO multipurpose test piece (3 mm thickness), and a Charpy impact test (notched, unit: kJ / m ² ) was conducted at 23 ° C. based on the ISO-179 standard. .

8) Wet heat test After pellets of the aromatic polycarbonate resin composition were dried at 120 ° C. for 5 hours, the cylinder temperature was 280 ° C. and the mold temperature was 80 with an injection molding machine (“SG75Mk-II” manufactured by Sumitomo Heavy Industries, Ltd.). Injection molding was carried out under the conditions of C. and a molding cycle of 50 seconds to produce an ISO multipurpose test piece (3 mm thick). Using a steam pressure tester (“HAESTEST PC-SIII type” manufactured by Hirayama Seisakusho Co., Ltd.), it was kept in steam at 100 ° C. for 24 hours (wet heat treatment). Each test piece after the wet heat treatment is subjected to tensile test measurement based on ISO-527 standard under room temperature (23 ° C.) conditions, tensile modulus (unit: MPa), yield stress (unit: MPa), Tensile fracture nominal strain (unit:%) was measured. went.

9) Method for measuring content of cyclic carbonate in resin 10 g of sample resin was dissolved in 100 ml of dichloromethane and dropped into 1000 ml of methanol while stirring. The precipitate was filtered off and the solvent in the filtrate was removed. The obtained solid was analyzed by GC-MS under the following measurement conditions. The detection limit value under this measurement condition is 0.0005 ppm.
[GC-MS measurement conditions]
Measuring device: Agilent HP6890 / 5973MSD
Column: Capillary column DB-5MS, 30m × 0.25mm ID, film thickness 0.5μm
Temperature rise conditions: 50 ℃ (5min hold) -300 ℃ (15min hold), 10 ℃ / min
Inlet temperature: 300 ° C, implantation amount: 1.0 µl (split ratio 25)
Ionization method: EI method Carrier gas: He, 1.0 ml / min
Aux temperature: 300 ° C
Mass scan range: 33-700
Solvent: Chloroform for HPLC Internal standard substance: 2,4,6-trimethylolphenol

In addition, the chemical purity of the diol compound used in the following Examples and Comparative Examples is 98 to 99% in all, the chlorine content is 0.8 ppm or less, alkali metal, alkaline earth metal, titanium and heavy metal (iron, nickel, The content of chromium, zinc, copper, manganese, cobalt, molybdenum, tin) is 1 ppm or less. Chemical purity of aromatic dihydroxy compound and carbonic acid diester is 99% or more, chlorine content is 0.8 ppm or less, alkali metal, alkaline earth metal, titanium and heavy metal (iron, nickel, chromium, zinc, copper, manganese, cobalt, The contents of molybdenum and tin are each 1 ppm or less.
In the following examples, 2,2-bis (4-hydroxyphenyl) propane may be abbreviated as “BPA”, the prepolymer as “PP”, the hydroxyl group as “OH group”, and the phenyl group as “Ph”.

[Aromatic polycarbonate resin production example 1: PC-1]
66.480 kg (291.209 mol) of 2,2-bis (4-hydroxyphenyl) propane, 70.179 kg (327.610 mol) of diphenyl carbonate and 0.17 μmol / mol of cesium carbonate as catalyst (based on BPA) The number of moles) was put into a 300 L reaction equipped with a stirrer and a distillation apparatus, and the inside of the system was replaced with a nitrogen atmosphere. The degree of vacuum was adjusted to 0.046 MPa (345 torr), the raw material was heated and melted at 160 ° C., and stirred for 1 hour.

  Thereafter, the ester exchange reaction was carried out over 9 hours while gradually raising the temperature and reducing the degree of vacuum while agglomerating and removing phenol distilled from the reaction system with a cooling tube. Finally, the inside of the system was 260 ° C., the degree of vacuum was 0.05 kPa (0.38 torr) or less, and was further maintained for 1 hour to obtain an aromatic polycarbonate prepolymer (hereinafter sometimes abbreviated as “PP-E”). It was.

The resulting aromatic polycarbonate prepolymer (PP-E) had a polystyrene equivalent weight average molecular weight (Mw) of 27900, an OH concentration of 280 ppm, and a phenyl terminal concentration (Ph terminal concentration) of 5.8 mol%. The OH concentration is a value calculated from ¹ H-NMR and indicates the OH group concentration contained in the entire polymer. The Ph terminal concentration is a value calculated from ¹ H-NMR, and indicates the terminal concentration of all phenylene groups and phenyl groups in the phenyl terminal (including phenyl groups substituted with hydroxyl groups).

  The resin temperature of the aromatic polycarbonate prepolymer (PP-E) was melted to 280 ° C. by a melter (biaxial extruder) and continuously supplied to a kneader having a rotation speed of 180 rpm heated to 300 ° C. at a speed of 13300 g / hr. .

At the same time, 3000 g of 2-butyl-2-ethylpropane-1,3-diol (BEPG), which is a diol compound, is heated and melted at 75 to 80 ° C. in a coupling agent adjusting tank equipped with an anchor blade, and 0.005 mol / L 82 ml of an aqueous solution of cesium carbonate (Cs ₂ CO ₃ ) was added and stirred, followed by dehydration treatment (water content below the detection limit) at 0.1 torr for 1 hour. BEPG containing the obtained catalyst was continuously fed together with PP-E to the kneader at a rate of 124 g / hr.

BEPG and catalyst cesium carbonate (Cs ₂ CO ₃ ) are 0.33 μmol to 1 mol of BPA at a flow rate of 0.25 mol with respect to 1 mol of the total terminal amount of PP-E (the amount of phenyl group at the capping end). Continuous feed at a rate of / mol.

  Subsequently, the mixture of BEPG to which PP-E and cesium carbonate were added was supplied to the horizontal stirring reactor at a flow rate of 13425 g / hr through a transport pipe kept at 280 ° C. from the kneader outlet to carry out a high molecular weight reaction. It was. The internal pressure of the horizontal stirring reactor at this time was 0.5 torr, and the resin temperature was 300 ° C.

  The liquid level was controlled so that the average residence time of the horizontal stirring reactor was 60 minutes, and phenol and cyclic carbonate (5-butyl-5-ethyl-1,3-dioxane-) produced as a by-product simultaneously with the high molecular weight reaction. 2-one) was distilled off. The stirring blade of the horizontal stirring reactor was stirred at 20 rpm.

Furthermore, 5 ppm of p-toluenesulfonic acid butyl (p-TSB) as a catalyst deactivator and octadecyl 3- (3,3) as an antioxidant were obtained with respect to the polycarbonate resin obtained after conducting a linked high molecular weight reaction in a horizontal stirring reactor. 1000 ppm of 5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by BASF) was kneaded with a biaxial kneader. The obtained polycarbonate resin has a polystyrene-equivalent weight average molecular weight (Mw) of 42300, a molecular weight distribution (Mw / Mn) of 2.4, and the obtained polycarbonate resin has an N value of 1.19 and a terminal hydroxyl group concentration. 400 ppm, the amount of heterogeneous structure (PSA; a structural unit represented by the general formula (III) where X = C (CH ₃ ) ₂ ) is 500 ppm, cyclic carbonate (5-butyl-5-ethyl-1 , 3-dioxan-2-one) was 1 ppm.

[Aromatic polycarbonate resin production example 2: PC-2]
64,662 kg (283.245 mol) of 2,2-bis (4-hydroxyphenyl) propane, 63.710 kg (297.41 mol) of diphenyl carbonate and 1.0 μmol / mol of cesium carbonate as catalyst (based on BPA) The number of moles) was put into a 300 L reaction equipped with a stirrer and a distillation apparatus, and the inside of the system was replaced with a nitrogen atmosphere. The degree of vacuum was adjusted to 0.046 MPa (345 torr), the raw material was heated and melted at 160 ° C., and stirred for 1 hour.

  Thereafter, the ester exchange reaction was carried out over 10 hours while gradually raising the temperature and reducing the degree of vacuum while agglomerating and removing the phenol distilled from the reaction system with a cooling tube. Finally, the inside of the system was 260 ° C., the degree of vacuum was 0.05 kPa (0.38 torr) or less, and was further maintained for 1 hour to obtain an aromatic polycarbonate prepolymer (hereinafter sometimes abbreviated as “PP-F”). It was.

  The obtained aromatic polycarbonate prepolymer (PP-F) had a polystyrene-reduced weight average molecular weight (Mw) of 30000, an OH concentration of 1200 ppm, and a phenyl terminal concentration (Ph terminal concentration) of 2.0 mol%. The OH concentration is a value calculated from NMR, and indicates the OH group concentration contained in the entire polymer. The Ph terminal concentration is a value calculated from NMR, and represents the terminal concentration of all phenylene groups and phenyl groups (including phenyl groups substituted by hydroxyl groups) in the phenyl terminals.

  The resin temperature of the aromatic polycarbonate prepolymer (PP-F) was melted to 280 ° C. by a melter (biaxial extruder) and continuously supplied to a kneader having a rotation speed of 140 rpm heated to 300 ° C. at a speed of 13300 g / hr. .

  Subsequently, an aromatic polycarbonate prepolymer (PP-F) was supplied to the horizontal stirring reactor at a flow rate of 13300 g / hr through a transport pipe kept at 280 ° C. from the kneader outlet to carry out a high molecular weight reaction. The internal pressure of the horizontal stirring reactor at this time was 0.5 torr, and the resin temperature was 300 ° C.

  The liquid level was controlled so that the average residence time in the horizontal stirring reactor was 120 minutes, and phenol produced as a by-product was distilled off simultaneously with the high molecular weight reaction. The stirring blade of the horizontal stirring reactor was stirred at 20 rpm.

  Furthermore, 5 ppm of p-toluenesulfonic acid butyl (p-TSB) as a catalyst deactivator and octadecyl 3- (3,3) as an antioxidant were obtained with respect to the polycarbonate resin obtained after conducting a linked high molecular weight reaction in a horizontal stirring reactor. 1000 ppm of 5-di-t-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured by BASF) was kneaded with a biaxial kneader. The polystyrene equivalent weight average molecular weight (Mw) of the obtained polycarbonate resin was 44700, the molecular weight distribution (Mw / Mn) was 2.6, the N value of the obtained polycarbonate resin was 1.29, the terminal hydroxyl group concentration was 1100 ppm, The amount of heterogeneous structure (PSA) was 2000 ppm. Cyclic carbonate was not detected.

[Example 1, Comparative Example 1]
PC-1 and PC-2 prepared according to the above production examples and various additives were blended at a mass ratio shown in Table 1, mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works (TEX30HSST) equipped with 1 vent. , Kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 280 ° C., the molten resin extruded into a strand is rapidly cooled in a water tank, pelletized using a pelletizer, and aromatic polycarbonate A pellet of the resin composition was obtained.

[Example 2, Comparative Example 2]
PC-1 and PC-2 prepared according to the above production examples and various additives were blended at a mass ratio shown in Table 1, mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works (TEX30HSST) equipped with 1 vent. , Kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 280 ° C., the molten resin extruded into a strand is rapidly cooled in a water tank, pelletized using a pelletizer, and aromatic polycarbonate A pellet of the resin composition was obtained.

PET: Polyethylene terephthalate resin (GG900DN, Mitsubishi Chemical Corporation)
Elastomer: Polybutadiene core / polymethylmethacrylate shell copolymer (Paraloid EXL2633, manufactured by Kureha Chemical Industry Co., Ltd.)
CB: Polystyrene masterbatch of carbon black. 40% carbon black, RB904G manufactured by Koshigaya Kasei Co., Ltd.
PTS: Pentaerythritol tetrastearate (Roxyol VPG861, manufactured by Cognis Japan Co., Ltd.) / Releasing agent ADK2112: Tris (2,4-di-t-butylphenyl) phosphite (Adeka Stub 2112, manufactured by Asahi Denka Co., Ltd.) /Antioxidant

Claims (11)

An aromatic polycarbonate resin having a structural unit represented by the following general formula (I), a polyethylene terephthalate resin, and a cyclic carbonate represented by the following general formula (II),
The aromatic polycarbonate resin in which the ratio (mass ratio) of the aromatic polycarbonate resin and the polyethylene terephthalate resin is 99: 1 to 40:60, and the cyclic carbonate is present at 3000 ppm or less with respect to the aromatic polycarbonate resin. Composition:
Formula (I):

Wherein R ₁ and R ₂ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or 6 carbon atoms. Represents an aryl group of -20, a cycloalkoxy group of 6-20 carbon atoms, or an aryloxy group of 6-20 carbon atoms, p and q represent an integer of 0-4, and X represents a single bond or the following ( Represents a group selected from the group of Ia)

(Here, R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₃ and R ₄ are To form an aliphatic ring)
General formula (II):

(In the formula, Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom which may contain a linear or branched alkyl group having 1 to 30 carbon atoms, an oxygen atom or a halogen atom. A cycloalkyl group having 3 to 30 carbon atoms which may contain, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or a carbon number which may contain an oxygen atom or a halogen atom 1 to 15 represents an alkoxy group, or Ra and Rb may be bonded to each other to form a ring, and R _{5 to} R ₈ each independently represents a hydrogen atom, a halogen atom or a carbon number. 1 to 5 linear or branched alkyl groups, and n represents an integer of 0 to 30).   Furthermore, the aromatic polycarbonate resin composition of Claim 1 containing 0.5-40 mass parts of rubbery polymers with respect to a total of 100 mass parts of the said aromatic polycarbonate resin and the said polyethylene terephthalate resin.   The aromatic polycarbonate resin composition according to claim 2, wherein the rubbery polymer is a core / shell type graft copolymer. The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the cyclic carbonate is a compound represented by the following general formula (IIa):
General formula (IIa):

(In the formula, Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom which may contain a linear or branched alkyl group having 1 to 30 carbon atoms, an oxygen atom or a halogen atom. A cycloalkyl group having 3 to 30 carbon atoms which may contain, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or a carbon number which may contain an oxygen atom or a halogen atom 1 to 15 alkoxy groups are represented, or Ra and Rb may be bonded to each other to form a ring). The said aromatic polycarbonate resin contains the structural unit represented by the following general formula (III), The content is less than 2000 ppm in the said aromatic polycarbonate resin, It is any one of Claims 1-4. Aromatic polycarbonate resin composition:
General formula (III):

(Wherein X is as defined in claim 1). The aromatic polycarbonate resin composition according to any one of claims 1 to 5, wherein an N value (structural viscosity index) of the aromatic polycarbonate resin is 1.25 or less when expressed by the following mathematical formula (1). object.
N value = (log (Q160 value) -log (Q10 value)) / (log160−log10) (1)   The aromatic polycarbonate resin composition according to any one of claims 1 to 6, wherein a terminal hydroxyl group content of the aromatic polycarbonate resin is 1000 ppm or less. A high molecular weight process in which the aromatic polycarbonate resin and the cyclic carbonate are polymerized by reacting an aromatic polycarbonate prepolymer and a diol compound represented by the following general formula (IV) in the presence of a transesterification catalyst; The aromatic of any one of Claims 1-7 obtained by the method including the cyclic carbonate removal process of removing at least one part of the cyclic carbonate byproduced in the said high molecular weight formation process out of a reaction system. Polycarbonate resin composition:
Formula (IV):

(In the formula, Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom which may contain a linear or branched alkyl group having 1 to 30 carbon atoms, an oxygen atom or a halogen atom. A cycloalkyl group having 3 to 30 carbon atoms which may contain, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or a carbon number which may contain an oxygen atom or a halogen atom 1 to 15 represents an alkoxy group, or Ra and Rb may be bonded to each other to form a ring, and R _{5 to} R ₈ each independently represents a hydrogen atom, a halogen atom or a carbon number. 1 to 5 linear or branched alkyl groups, and n represents an integer of 0 to 30). The aromatic polycarbonate resin composition according to claim 8, wherein the diol compound is a compound represented by the following general formula (IVa):
Formula (IVa):

(In the formula, Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a halogen atom which may contain a linear or branched alkyl group having 1 to 30 carbon atoms, an oxygen atom or a halogen atom. A cycloalkyl group having 3 to 30 carbon atoms which may contain, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or a carbon number which may contain an oxygen atom or a halogen atom 1 to 15 alkoxy groups are represented, or Ra and Rb may be bonded to each other to form a ring).   The diol compound is 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol, 2, The aromatic polycarbonate resin composition according to claim 8 or 9, which is selected from the group consisting of 2-diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol.   The molded article formed by shape | molding the aromatic polycarbonate resin composition as described in any one of Claims 1-10.