JP2015189905A - aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition which contains additives, such as a stabilizer, an ultraviolet absorber and a mold release agent, and is improved in flowability, color tone and mechanical strength.SOLUTION: An aromatic polycarbonate resin composition comprises: an aromatic polycarbonate resin having a structural unit represented by general formula (I); at least one additive selected from the group consisting of stabilizers, ultraviolet absorbers and mold release agents; and a cyclic carbonate represented by general formula (II) whose content is 3000 ppm or less based on the aromatic polycarbonate resin.

Description

  The present invention relates to an aromatic polycarbonate resin composition.

  Polycarbonate is excellent in heat resistance, impact resistance, transparency and so on. For example, it is widely used in many fields as raw materials for automobiles, OA equipment, electrical / electronics, household goods, building materials, etc. Are also widely used industrially. In this way, while the applications are expanding, it is required to respond to various demands such as improvement of moldability (improving fluidity), further improvement of hue, and enhancement of mechanical strength.

  For example, Japanese Patent Application Laid-Open No. 2002-308975 discloses a polycarbonate resin composition excellent in combustion resistance and hydrolysis resistance, in which a stabilizer, an ultraviolet absorber, a release agent, a colorant and the like are blended with a polycarbonate resin. doing. Japanese Patent Application Laid-Open No. 2012-207173 discloses a polycarbonate resin composition excellent in hue and weather resistance, in which a benzotriazole compound is added to a polycarbonate resin. Japanese Patent No. 4401608 discloses a polycarbonate resin composition excellent in hue, melting characteristics, heat resistance, and weather resistance by adding a heat stabilizer or an ultraviolet absorber to a polycarbonate resin containing a large amount of a different structure skeleton. Is disclosed.

On the other hand, many studies have been made on the production method of polycarbonate resin. Among them, an aromatic polycarbonate resin derived from an aromatic dihydroxy compound such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter also referred to as “bisphenol A” or “BPA”) is obtained by an interfacial polymerization method or It is industrialized by both production methods of the melt polymerization method.
Of these, the interfacial polymerization method has many environmental problems.

  In addition, as a melt polymerization method, a method for producing a polycarbonate from an aromatic dihydroxy compound and diaryl carbonate, for example, by removing a by-product aromatic monohydroxy compound by transesterification in a molten state of bisphenol A and diphenyl carbonate. The method of polymerizing has been known for a long time. Unlike the interfacial polymerization method, the melt polymerization method has many environmental advantages, such as not using a solvent. However, the resin obtained as exemplified in the aforementioned Japanese Patent Application Laid-Open No. 2003-119369 contains a large amount of a skeleton having a heterogeneous structure that occurs naturally and has a relatively high terminal hydroxyl group concentration (terminal OH concentration). Therefore, even if various conventional additives are blended, satisfactory moldability (fluidity), hue, mechanical strength, etc. have not been achieved yet.

  As a method for achieving a high polymerization rate and obtaining an aromatic polycarbonate resin of good quality, the present inventors have previously proposed a new method in which the end of the aromatic polycarbonate prepolymer is connected by a diol compound to extend the chain. (See, for example, International Publication No. 2012/157766). According to these methods, the aromatic polycarbonate prepolymer having a high degree of polymerization having a Mw of about 30,000 to 100,000 is shortened by connecting the end of the aromatic polycarbonate prepolymer with a diol compound to extend the chain. Can be manufactured in time. Furthermore, since the aromatic polycarbonate resin is produced by a high-speed polymerization reaction, the branching / crosslinking reaction due to long-time heat retention or the like is suppressed, and the amount of different structures can be reduced. Further, the terminal hydroxyl group concentration (terminal OH group concentration) is also reduced.

JP 2002-308975 A JP 2012-207173 A JP 2003-119369 A International Publication No. 2012/157766

  However, additives such as stabilizers, UV absorbers and mold release agents are blended into the aromatic polycarbonate resin obtained using the melt polymerization method in consideration of the environment, resulting in high fluidity, high mechanical strength characteristics and good An aromatic polycarbonate resin composition that has a good hue has not yet been proposed at a satisfactory level. Therefore, the problem to be solved by the present invention is to provide an aromatic polycarbonate resin composition containing additives such as a stabilizer, an ultraviolet absorber and a release agent, which have improved fluidity, hue and mechanical strength. That is.

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 different structures in spite of the melting method. The present inventors have found that a polycarbonate resin composition having excellent fluidity, hue and mechanical strength can be constituted by blending a polycarbonate resin contained below a predetermined amount and various additives, and reached the present invention.
That is, this invention provides the aromatic polycarbonate resin composition shown below.

<1> An aromatic polycarbonate resin having a structural unit represented by the following general formula (I), at least one additive selected from the group consisting of a stabilizer, an ultraviolet absorber and a release agent, and the following general formula The cyclic carbonate content represented by the following general formula (II) including the cyclic carbonate represented by (II) with respect to the aromatic polycarbonate resin having the structural unit represented by the following general formula (I) It is an aromatic polycarbonate resin composition which is 3000 ppm or less.

In the formula, 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 to 6 carbon atoms. 20 represents an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, p and q represent an integer of 0 to 4, and X represents a single bond or the following (Ia ) Represents a group selected from the group of

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 mutually It may combine to form an aliphatic ring.

In the formula, each of Ra and Rb independently represents 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 halogen atom. An optionally substituted cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms that may contain an oxygen atom or a halogen atom, or 1 carbon atom that may contain an oxygen atom or a halogen atom R _{15 to} R ₈ 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 of 1 to 15 Represents a linear or branched alkyl group of -5, and n represents an integer of 0-30.

<2> The aromatic polycarbonate resin composition according to <1>, wherein the terminal hydroxyl group concentration of the aromatic polycarbonate resin having the structural unit represented by the general formula (I) is 1000 ppm or less.
<3> The weight average molecular weight of the aromatic polycarbonate resin having the structural unit represented by the general formula (I) is in the range of 35,000 to 100,000, according to <1> or <2>. It is an aromatic polycarbonate resin composition.

<4> The aromatic polycarbonate resin composition according to any one of <1> to <3>, wherein the stabilizer is at least one antioxidant selected from the group consisting of a hindered phenol compound and a phosphorus compound. It is a thing.
<5> The ultraviolet absorber is a benzotriazole compound, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3, Any one of <1> to <4>, which is at least one compound selected from the group consisting of [1-benzoxazin-4-one] and [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester It is an aromatic polycarbonate resin composition as described in one.
<6> The aromatic polycarbonate according to any one of <1> to <5>, wherein the release agent is at least one compound selected from the group consisting of aliphatic carboxylic acids and aliphatic carboxylic acid esters. It is a resin composition.

<7> The catalyst is a catalyst deactivator during or during the polymerization reaction for producing the aromatic polycarbonate resin having the structural unit represented by the general formula (I) or at the end of the polymerization reaction. The aromatic polycarbonate resin composition according to any one of <1> to <6>, which is added at any time after deactivation and before pelletization.
<8> The aromatic polycarbonate resin according to any one of <1> to <7>, wherein the cyclic carbonate represented by the general formula (II) is a compound represented by the following general formula (IIa): It is a composition.

  In formula, Ra and Rb are synonymous with Ra and Rb in general formula (II), respectively.

<9> When the N value (structural viscosity index) of the aromatic polycarbonate resin having the structural unit represented by the general formula (I) is represented by the following mathematical formula (1), it is 1.25 or less. It is an aromatic polycarbonate resin composition as described in any one of 1>-<8>.
N value = (log (Q160 value) −log (Q10 value)) / (log160−log10) (1)

<10> The aromatic polycarbonate resin having the structural unit represented by the general formula (I) includes a structural unit represented by the following general formula (III), and the content thereof is the general formula (I). It is an aromatic polycarbonate resin composition as described in any one of <1>-<9> which is less than 2000 ppm in the aromatic polycarbonate resin which has a structural unit represented.

  In formula, X is synonymous with X in general formula (I).

<11> The aromatic polycarbonate resin having the structural unit represented by the general formula (I) and the cyclic carbonate represented by the general formula (II) are represented by an aromatic polycarbonate prepolymer and the following general formula (IV). The diol compound is reacted in the presence of a transesterification catalyst to obtain a high molecular weight aromatic polycarbonate resin, and at least a part of the cyclic carbonate by-produced in the high molecular weight process. It is an aromatic polycarbonate resin composition as described in any one of <1>-<10> obtained by the method including the cyclic carbonate removal process removed to the outside of a reaction system.

Wherein, Ra, Rb and _R 5 to R ₈ is Ra in formula (II), and Rb and _R 5 to R ₈ respectively the same.

<12> The aromatic polycarbonate resin composition according to <11>, wherein the diol compound represented by the general formula (IV) is a compound represented by the following general formula (IVa).

  In formula, Ra and Rb are synonymous with Ra and Rb in general formula (IV), respectively.

<13> 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 according to <11> or <12>, selected from the group consisting of 2,2-diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol It is a composition.

  According to the present invention, it is possible to provide an aromatic polycarbonate resin composition containing additives such as a stabilizer, an ultraviolet absorber and a release agent, which have improved fluidity, hue and mechanical strength.

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Further, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

Aromatic polycarbonate resin composition The aromatic polycarbonate resin composition of the present invention (hereinafter also simply referred to as “resin composition”) is an aromatic polycarbonate resin having a structural unit represented by the following general formula (I) (hereinafter, referred to as “resin composition”). Simply referred to as “aromatic polycarbonate resin”), at least one additive selected from the group consisting of a stabilizer, an ultraviolet absorber and a release agent, and a cyclic carbonate represented by the following general formula (II): In addition, the cyclic carbonate content represented by the following general formula (II) is 3000 ppm or less with respect to the aromatic polycarbonate resin having the structural unit represented by the following general formula (I).

In the formula, each of R ₁ and R ₂ independently represents 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, or a cyclohexane having 6 to 20 carbon atoms. An alkoxy group or an aryloxy group having 6 to 20 carbon atoms is represented, p and q represent an integer of 0 to 4, and X represents a single bond or a group selected from the following group (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 mutually It may combine to form an aliphatic ring.

In the formula, each of Ra and Rb independently represents 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 halogen atom. An optionally substituted cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms that may contain an oxygen atom or a halogen atom, or 1 carbon atom that may contain an oxygen atom or a halogen atom R _{15 to} R ₈ 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 of 1 to 15 Represents a linear or branched alkyl group of -5, and n represents an integer of 0-30.

  The aromatic polycarbonate resin composition of the present invention is an aromatic polycarbonate resin composition containing various additives such as a stabilizer, an ultraviolet absorber, and a release agent, and has fluidity, hue (YI value) and resistance. The impact is greatly improved. An aromatic polycarbonate resin that can constitute such a resin composition is obtained by, for example, a method of increasing the molecular weight of an aromatic polycarbonate prepolymer by a reaction between an aromatic polycarbonate prepolymer and a linking compound containing a diol compound having a specific structure. Can be obtained. The aromatic polycarbonate resin obtained by such a method has a structure substantially equivalent to that of the polycarbonate obtained by the conventional interface method, or a structure containing a partial structure derived from a very small amount of a connecting agent in some cases.

  Therefore, such an aromatic polycarbonate resin has the same physical properties as an aromatic polycarbonate resin produced by a conventional interface method, and does not contain or contain a partial structure derived from a linking agent containing a diol compound having a specific structure. Is excellent in thermal stability (heat resistance) due to its small amount. Furthermore, because it is a high molecular weight polymerized at high speed using a diol compound as a linking agent, the original quality advantages of the aromatic polycarbonate resin such as high molecular weight, low degree of branching, and few heterogeneous structures. Have. In addition, when the resin composition is composed of various additives such as stabilizers, ultraviolet absorbers, mold release agents, etc., by including cyclic carbonates of a specific structure and the content thereof being below a predetermined value. However, it is possible to obtain an aromatic polycarbonate resin composition having improved fluidity, hue, and mechanical strength at each stage as compared with the case of using a polycarbonate resin obtained by a conventional melting method. As a result, the aromatic polycarbonate resin composition can be obtained by using an aromatic polycarbonate resin having high heat resistance, high impact resistance, high transparency, etc. even if an aromatic polycarbonate resin using a melt polymerization method considering the environment is used. The effects of various additives can be sufficiently exhibited while maintaining the advantages.

(1) Aromatic polycarbonate resin The aromatic polycarbonate resin composition of this invention contains the aromatic polycarbonate resin which has 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.

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 derived from the structural unit represented by the general formula (I) include compounds represented by the following general formula (V).

In the general formula _{(V), R 1, R} 2, p, q and X have the same meanings as _{R 1, R 2, p,} q and X in each 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) Nylphenyl) 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'-dihydro Shi-3,3'-dimethyl diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone and the like.

  Among them, 2,2-bis (4-hydroxyphenyl) propane is preferable because of its stability as an aromatic dihydroxy compound, and the fact that it can be easily obtained with a small amount of impurities contained therein.

  In the present invention, one kind of aromatic dihydroxy compound may be used alone. For the purpose of controlling the glass transition temperature, improving the fluidity, etc., a plurality of kinds of the various aromatic dihydroxy compounds may be combined as necessary. May be used.

  The aromatic polycarbonate resin may further contain other structural units other than the structural unit represented by the general formula (I). Examples of the other structural unit include a heterogeneous structural unit having a branch represented by the structural unit represented by the following general formula (III), a structural unit derived from a linking agent described later, and the like.

X in the general formula (III) has the same meaning as X in the general formula (I).
When the aromatic polycarbonate resin contains a structural unit represented by the general formula (III), the content thereof is, for example, less than 2000 ppm, preferably 1500 ppm or less, more preferably, in the aromatic polycarbonate resin, based on mass. 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 further improved. These heterogeneous structural units are naturally occurring branched structures. Therefore, if the content of these different structural units is a predetermined amount or more, it becomes difficult to easily control the degree of branching depending on the amount of branching agent added, and the blending / dispersibility with various additives deteriorates. In some cases, there are disadvantages such as a decrease in fluidity of the resulting resin composition and deterioration of moldability.

  The structural unit represented by the general formula (III) is a kind of heterogeneous structure that is easily generated during the production of the aromatic polycarbonate resin, and the aromatic polycarbonate resin constituting the resin composition has a small proportion of the heterogeneous structure. It is preferable. 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 agent containing a diol compound having a specific structure described later.

  The lower limit of the content of the structural unit represented by the general formula (III) is not particularly limited, and can be, for example, a detection lower limit (usually about 1 ppm). The lower limit of the content rate of the structural unit represented by the general formula (III) in the aromatic polycarbonate resin is, for example, 1 ppm or more (detection lower limit value), and in some cases, 5 ppm or more, and further 10 ppm or more is allowed. .

In addition, the content rate of the structural unit represented by the said general formula (III) is the value of the mass reference | standard measured by < ¹ > H-NMR analysis.

When the aromatic polycarbonate resin is produced by a method using a linking agent containing a diol compound having a specific structure described later, it may contain a structural unit derived from the diol compound used in the high molecular weight process. When the aromatic polycarbonate resin includes a structural unit derived from a diol compound, the content of the structural unit derived from the diol compound with respect to the total amount of the structural unit of the aromatic polycarbonate resin is, for example, 1 mol% or less, preferably 0.8. 1 mol% or less.
The content rate of the structural unit derived from a diol compound is the value calculated | required by measuring by < ¹ > H-NMR analysis.

Furthermore, the aromatic polycarbonate resin preferably has a terminal hydroxyl group concentration of 1000 ppm or less on a mass basis, 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 is preferably 35,000 to 100,000, more preferably 35,000 to 80,000, particularly preferably 35,000 to 75,000, most preferably 40,000. It is 000-65,000, and also has high fluidity while having a high molecular weight. When the weight average molecular weight is within this range, the moldability and productivity when blended with various additives and used for applications such as extrusion molding and injection molding are better. Furthermore, the physical properties such as mechanical properties, heat resistance, and organic solvent resistance of the obtained molded product are better.

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 is, for example, 1.9 to 2.5, and is 2.0 to 2.4. Preferably there is.
In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are measured as a polystyrene conversion value using GPC.

In the aromatic polycarbonate resin, the N value (structural viscosity index) represented by the following formula (1) is preferably 1.30 or less, more preferably 1.28 or less, particularly preferably 1.25 or less, and most preferably. Is 1.23 or less.
N value = (log (Q160 value) −log (Q10 value)) / (log160−log10) (1)

  In the 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 aromatic polycarbonate resin. In the aromatic polycarbonate resin, 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 aromatic polycarbonate resin tends to have higher fluidity (Q value becomes higher) when the proportion of the branched structure increases in the same Mw. However, the aromatic polycarbonate resin obtained by the production method described later has an N value. High fluidity (high Q value) can be achieved while keeping the temperature low.

(2) Cyclic carbonate In the aromatic polycarbonate resin composition, the cyclic carbonate represented by the following general formula (II) is present at 3000 ppm or less with respect to the aromatic polycarbonate resin. The cyclic carbonate represented by the following general formula (II) is a known compound and can be obtained from a reagent supplier or can be easily synthesized by a known method. It may be added to the group polycarbonate resin composition. 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, the aromatic polycarbonate resin obtained by the production method described later may be a by-product of cyclic carbonate corresponding to the diol compound used as a linking agent in the production process, but even after removing this from the reaction system, A small amount of cyclic polycarbonate remains, and 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 tends to 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 content of cyclic carbonate exceeds 3000 ppm, there may be demerits, such as a fall of the mechanical strength of a resin composition.

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 the 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 isobutyl 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), Ra and Rb are respectively synonymous with Ra and Rb in general formula (II) mentioned above.

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

The content of the cyclic carbonate represented by the general formula (II) in the aromatic polycarbonate resin composition is 3000 ppm or less on a mass basis, preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 300 ppm or less, particularly The lower limit of the content of the cyclic polycarbonate, which is preferably 100 ppm or less, is usually a detection lower limit, but is preferably 0.0005 ppm, more preferably 0.005 ppm, and still more preferably 0.05 ppm. Particularly preferably, it is 0.1 ppm. The presence of such a cyclic carbonate may improve the fluidity of the aromatic polycarbonate resin composition. Furthermore, even when various additives such as a stabilizer, an ultraviolet absorber, and a release agent are added, fluidity (moldability), hue (YI value), and impact resistance can be improved. If the cyclic carbonate content is too high, there may be disadvantages such as a decrease in resin strength. If it is too low, the fluidity may deteriorate, or it may be difficult to have sufficient Charpy impact strength. is there.
In addition, the content rate of the cyclic carbonate represented by general formula (II) in an aromatic polycarbonate resin composition is measured using GC-MS.

(3) Additive The aromatic polycarbonate resin composition contains at least one additive selected from the group consisting of a stabilizer, an ultraviolet absorber and a release agent. The content of each additive is not particularly limited, and can be appropriately selected according to the purpose, the type of additive, and the like. The content of each additive contained in the resin composition is, for example, preferably 7% by mass or less, and more preferably 6% by mass or less.
The lower limit value of the additive content is not particularly limited, and can be appropriately selected according to the type of the additive. The lower limit of the additive content is, for example, 0.00001% by mass or more, and preferably 0.0001% by mass or more.

(Stabilizer)
Examples of the stabilizer include hindered phenol compounds, phosphorus compounds, sulfur compounds, epoxy compounds, hindered amine compounds, and the like. Among these, at least one antioxidant selected from the group consisting of hindered phenol compounds and phosphorus compounds is preferably used. One stabilizer may be used alone, or two or more stabilizers may be used in combination.

  Preferable examples of the hindered phenol compound include compounds represented by the following general formula (VI).

In General Formula (VI), R ⁶¹ and R ⁶² are each independently a hydrocarbon group having 1 to 10 carbon atoms. Y is a C1-C20 hydrocarbon group which may contain a functional group selected from an ester group, an ether group and an amide group and / or a phosphorus atom. Z is a C1-C6 hydrocarbon group which may contain an oxygen atom and / or a nitrogen atom, a sulfur atom or a single bond. g shows the integer of 1-4.

Specific examples of the hindered phenol compound include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate], 3,9 -Bis 1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5 ] Undecane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] -3, Di-tert-butyl-4-hydroxybenzyl phosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanate And nurate, N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), and the like.
Among these, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3 ′, 5′-tert) -Butyl-4′-hydroxyphenyl) propionate] and 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] At least one selected from -2,4,8,10-tetraoxaspiro [5.5] undecane is preferred.

  The phosphorus compound is preferably a trivalent phosphorus compound. In particular, at least one ester portion in the phosphite ester is esterified with phenol and / or phenol having at least one alkyl group having 1 to 25 carbon atoms. And at least one selected from phosphites or tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-diphosphonite.

  Specific examples of phosphites include triphenyl phosphite, tricresyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-ditridecyl) phosphite, 1,1, 3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, trisnonylphenyl phosphite, dinonylphenylpentaerythritol diphosphite, tris (2,4-di-tert-butyl Phenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2 '-Ethylidene-bis (4,6-di-tert-butylphenyl) Phosphite fluoride, 2,2'-methylene-bis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, monononylphenol and dinonylphenol And a phosphite ester having a hindered phenol structure represented by the formula (VI).

  Examples of phosphorus compounds include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-diphosphonite, tris (2,4-di-tert-butylphenyl) phosphite, and 2,2′-methylene. At least one selected from the group consisting of -bis (4,6-di-t-butylphenyl) octyl phosphite is preferable.

  Examples of the sulfur compound include stabilizers such as those manufactured by BASF, trade names IRGANOX 1035, IRGANOX 1035FF, IRGANOX 1726, and IRGANOX 565.

  Examples of the epoxy compound include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 1,2-epoxy-4- (2 of 2,2-bis (hydroxymethyl) -1-butanol. -Oxiranyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, a copolymer of styrene and glycidyl methacrylate, and the like.

  Examples of the hindered amine compounds include stabilizers such as those manufactured by BASF Corporation, trade names CHIMASSORB 2020 FDL, CHIMASSORB 944 FDL, TINUVIN 622 SF, TINUVIN PA144, TINUVIN 765, and TINUVIN 770 DF.

  When the resin composition contains a stabilizer, the total content of the stabilizer in the resin composition is, for example, 1 part by mass or less, preferably 0.5 parts by mass or less, with respect to 100 parts by mass of the aromatic polycarbonate resin. Yes, more preferably 0.2 parts by mass or less, still more preferably 0.1 parts by mass or less. When the amount is 1 part by mass or less, hydrolysis resistance tends to be better. Although a lower limit is not specifically limited, It is 0.01 mass part or more.

One stabilizer may be used alone, or two or more stabilizers may be used in combination. The content ratio when two or more stabilizers are used in combination can be arbitrarily determined. Further, which compound is used as a stabilizer or used in combination is appropriately determined depending on the use of the resin composition.
For example, phosphorus compounds are generally highly effective in retention stability at high temperatures when molding resin compositions and heat stability during use of molded products, and phenolic compounds generally mold polycarbonate such as heat aging resistance. Highly effective in heat resistance stability when used after making a product. Moreover, there exists a tendency for the improvement effect of coloring property to increase more by using a phosphorus compound and a phenol compound together.

(UV absorber)
Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as titanium oxide, cerium oxide, and zinc oxide. Of these, organic ultraviolet absorbers are preferred, and in particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H -3,1-benzoxazin-4-one] and [(4-methoxyphenyl) methylene] propanedioic acid-dimethyl ester are preferable.

  Examples of the benzotriazole compound include a compound represented by the following formula (VII) and methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. At least one selected from the group consisting of the condensates is preferred.

In formula (VII), R ^{71 to} R ⁷⁴ represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms, Y ⁷¹ and Y ⁷² represent a hydrogen atom, a nitrogen atom having 1 to 40 carbon atoms, and And / or a hydrocarbon group which may contain an oxygen atom.

  Specific examples of the benzotriazole compound represented by the general formula (VII) include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxy Phenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) ) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, [meth And ru-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. Furthermore, examples of the benzotriazole compound include compounds represented by the following formula (VIII).

  Among these, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl are particularly preferable. ] -2H-benzotriazole, the compound of the above formula (VIII), 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and 2- It is at least one selected from [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol.

  When the resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber in the resin composition is, for example, 5 parts by mass or less, preferably 1 part by mass or less, with respect to 100 parts by mass of the aromatic polycarbonate resin. Preferably it is 0.5 mass part or less. If it is 5% by mass or less, the occurrence of mold contamination tends to be suppressed. Although a lower limit in particular is not restrict | limited, It is 0.01 mass part or more, Preferably it is 0.1 mass part or more.

  The ultraviolet absorbers may be used alone or in combination of two or more. The content ratio when two or more ultraviolet absorbers are used in combination can be arbitrarily determined. Moreover, which compound is used as an ultraviolet absorber or used together is appropriately determined depending on the use of the resin composition.

(Release agent)
Examples of the release agent include aliphatic carboxylic acids, aliphatic carboxylic acid esters, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oil. Among these, at least one selected from the group consisting of aliphatic carboxylic acids and aliphatic carboxylic acid esters is preferably used.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, and montanic acid. , Glutaric acid, adipic acid, azelaic acid and the like.

  Examples of the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester include the same as the aliphatic carboxylic acid. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds. Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

When the resin composition contains a release agent, the content of the release agent in the resin composition is, for example, 5 parts by mass or less, preferably 2 parts by mass or less, with respect to 100 parts by mass of the aromatic polycarbonate resin. Preferably it is 1 mass part or less. When the content is 5% by mass or less, degradation of hydrolysis resistance, occurrence of mold contamination during molding, and the like tend to be suppressed. Although a lower limit in particular is not restrict | limited, It is 0.01 mass% or more, Preferably it is 0.1 mass part or more.
The mold release agent can be used alone or in combination of two or more.

(Coloring agent)
The resin composition may further contain a colorant as necessary. Examples of the colorant include a compound having an anthraquinone skeleton, a compound having a phthalocyanine skeleton, and the like. Among these, a compound having an anthraquinone skeleton is preferably used from the viewpoint of heat resistance. A pigment colorant such as titanium oxide can also be used as the colorant.

  Specific examples of the colorant include MACROLEXBlue RR, MACROLEXViolet 3R, MACROLEXViolet B (manufactured by Bayer), SumilastVioletRR, SumilastVioletB, SumiplastBlueOR (et), Sumitomo Chemical Industries (D) )) And the like.

When the resin composition includes a colorant, the content of the colorant in the resin composition can be appropriately selected according to the purpose, the type of the colorant, and the like. For example, when a compound having an anthraquinone skeleton is used as the colorant, the amount is, for example, 0.01 parts by mass or less, preferably 0.001 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin. Although a lower limit is not specifically limited, For example, it is 0.0001 mass part or more.
For example, when using a compound having a phthalocyanine skeleton as a colorant, for example, 1 part by mass or less, preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, with respect to 100 parts by mass of the aromatic polycarbonate resin. It is. Although a lower limit in particular is not restrict | limited, For example, it is 0.00001 mass part or more, Preferably it is 0.0001 mass part or more.
One colorant can be used alone, or two or more colorants can be used in combination.

(4) Other components The resin composition may further contain other components in addition to the essential components. Other components include, for example, heat stabilizers, hydrolysis stabilizers, pigments, dyes, reinforcing agents, fillers, lubricants, crystal nucleating agents, plasticizers, fluidity improvers, antistatic agents, antibacterial agents, and the like. It may be contained.
As the heat stabilizer, a known one such as triphenylphosphine (P-Ph ₃ ) can be used. When the resin composition contains other components, the content is appropriately selected according to the purpose and the like.

Production method of aromatic polycarbonate resin The production method of the aromatic polycarbonate resin contained in the aromatic polycarbonate resin composition is not particularly limited, but is preferably obtained by the production method shown below. By adopting the production method shown below, 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.

  That is, a preferable method for producing an aromatic polycarbonate resin is that an aromatic polycarbonate prepolymer and a diol compound represented by the following general formula (IV) (hereinafter also simply referred to as “diol compound”) are present in the presence of a transesterification catalyst. A high molecular weight process for obtaining a high molecular weight aromatic polycarbonate resin by reaction, and a cyclic carbonate removing process for removing at least a part of the cyclic carbonate by-produced in the high molecular weight process from the reaction system; It is a manufacturing method.

In the general formula (IV), Ra and Rb are each independently a hydrogen atom, a halogen atom, an oxygen atom or a C1-C30 linear or branched alkyl group 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 1 to 6, more preferably 1 to 3, particularly preferably 1.

In 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, an n-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 general formula (IVa), Ra and Rb are respectively synonymous with Ra and Rb in general formula (IV).

  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, an n-butyl group, and an isobutyl group, and preferably an ethyl group, a propyl group, an n-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 diol compound selected from the group consisting of diol, 2,2-diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol.

Aromatic polycarbonate prepolymer An aromatic polycarbonate prepolymer (hereinafter, also simply referred to as “prepolymer” or “PP”) used in the method for producing an aromatic polycarbonate resin is the general formula (I) that constitutes the aromatic polycarbonate resin. Is a polycondensation polymer having a main repeating unit as a structure represented by

  The aromatic polycarbonate prepolymer is prepared by a known transesterification method in which an aromatic dihydroxy compound derived from a structural unit represented by the general formula (I) is reacted with a carbonic diester in the presence of a basic catalyst, or the aromatic dihydroxy It can be easily obtained by any known interfacial polycondensation method in which a compound is reacted with phosgene or the like in the presence of an acid binder.

  As an aromatic dihydroxy compound induced | guided | derived to the structural unit represented by the said general formula (I), the compound represented by the said general formula (V) is mentioned.

  The aromatic polycarbonate prepolymer may be synthesized by an interfacial polymerization method or a melt polymerization method, or may be synthesized by a method such as a solid phase polymerization method or a thin film polymerization method. May be. 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 preferably includes an end-capped aromatic polycarbonate prepolymer satisfying specific conditions.
That is, the aromatic polycarbonate prepolymer is at least partially sealed with an end group derived from an aromatic monohydroxy compound or a terminal phenyl group (hereinafter also referred to as “sealed end 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 blocked end amount to the total end amount of the prepolymer can be analyzed by ¹ H-NMR analysis of the prepolymer.

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. When the terminal hydroxyl group concentration is less than or equal to this range or exceeds the corresponding range, there is a tendency that a sufficient high molecular weight effect is obtained by the transesterification reaction with the diol compound.

  The “total amount of terminal groups of the aromatic polycarbonate prepolymer” as used herein is calculated, for example, when there is 0.5 mol of unbranched polycarbonate (that is, a chain polymer), the total amount of terminal groups is 1 mol. . The same applies to the “total terminal group amount of the aromatic polycarbonate resin”.

  Specific examples of the sealing end group include phenyl end, cresyl end, o-tolyl end, p-tolyl end, pt-butylphenyl end, biphenyl end, o-methoxycarbonylphenyl end, p-cumylphenyl end, etc. There may be mentioned end groups.

  Among these, a capped end group composed of a low-boiling aromatic monohydroxy compound that is easily removed from the reaction system by a transesterification reaction with a diol compound is preferable, and a phenyl end, a p-tert-butylphenyl end, and the like are preferable. 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 p-tert-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 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, the aromatic polycarbonate prepolymer which satisfy | fills the said amount of sealing ends 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 carboxy 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 or more and less than 35,000. More preferably, Mw ranges from 15,000 to less than 35,000, more preferably from 20,000 to less than 35,000, and particularly preferably from 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 carry out the production of the prepolymer at high temperature, high shear, and / or for a long time, and / or There is a tendency that the reaction with the diol compound does not need to be carried out at high temperature, high shear, and for a long time.

Cyclic carbonate In the method for producing an aromatic polycarbonate resin, a diol compound having a specific structure is allowed to act on a terminal-capped aromatic polycarbonate prepolymer in the presence of a transesterification catalyst under reduced pressure conditions to thereby remove the aromatic polycarbonate prepolymer from the aromatic polycarbonate prepolymer. A high molecular weight aromatic polycarbonate resin is produced. This reaction proceeds at high speed under mild conditions, and a high-quality aromatic polycarbonate resin is obtained.

  Here, 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 having a structure corresponding to the structure of the diol compound is added as a secondary substance. To be born. By removing the by-produced cyclic carbonate out of the reaction system, the aromatic polycarbonate prepolymer further increases in molecular weight, and finally finally is almost the same as a conventional homopolycarbonate (eg, a homopolycarbonate resin derived from bisphenol A). An aromatic polycarbonate resin having a structure is obtained.

  The high molecular weight process and the cyclic carbonate removing process do not necessarily need to be physically and temporally separate processes, and are actually preferably performed simultaneously. A preferred production method is to obtain an aromatic polycarbonate resin having a high molecular weight by reacting an aromatic polycarbonate prepolymer and a diol compound in the presence of a transesterification catalyst, and to form a cyclic carbonate by-produced by the high molecular weight reaction. A step of removing at least a part of the reaction solution from the reaction system.

The cyclic carbonate by-produced is a compound having a structure represented by the general formula (II). The details of the structure of the cyclic carbonate produced as a by-product are as described above.
The cyclic carbonate produced as a by-product has a structure corresponding to the diol compound to be used, and is considered to be a cyclic product derived from the diol compound. , Not necessarily obvious.

  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 represented by the general formula (IV), the aromatic polycarbonate prepolymer is reacted with a diol compound as a linking agent to increase the molecular weight of the aromatic polycarbonate prepolymer. The cyclic carbonate having a structure corresponding to the structure of the diol compound to be removed is removed, and is not limited to a specific reaction mechanism as long as it is within the range.

Scheme (1):

Scheme (2):

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

  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 structural units having a different structure, and excellent color tone.

Below, the detailed conditions of the manufacturing method of aromatic polycarbonate resin are demonstrated.
(I) Addition of diol compound The diol compound represented by the general formula (IV) is added to and mixed with the aromatic polycarbonate prepolymer, and a high molecular weight reaction (transesterification reaction) is performed in the high molecular weight reactor.

  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 diol compound having a relatively low boiling point is used, an excessive amount can be added in advance depending on the reaction conditions in consideration of the possibility that a part of the diol compound will be not involved in the reaction due to volatilization or the like. . 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 vacuum when supplying the diol compound to the high molecular weight reactor is insufficient, the cleavage reaction of the prepolymer main chain by the byproduct (phenol) proceeds, and the reaction time for increasing the molecular weight is reduced. It may be necessary to lengthen it.

  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 for the transesterification reaction (polymerization 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, more preferably Is 280 ° C to 310 ° C.

  Further, the degree of vacuum is preferably 13 kPa (100 torr) or less, more preferably 1.3 kPa (10 torr) or less, more preferably 0.67 to 0.013 kPa (5 to 0.1 torr).

  Examples of the transesterification catalyst (hereinafter, also simply referred to as “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.

  As such compounds, organic acid salts such as alkali metals and alkaline earth metals, inorganic salts, oxides, hydroxides, hydrides and alkoxides; quaternary ammonium hydroxides and salts thereof; amines and the like are preferable. 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, zinc, tin, zirconium and lead salts 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, dibutyltin dilaurate, Examples include dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, and lead (IV) acetate.

These catalysts, the total 1 mol of aromatic dihydroxy compounds constituting the prepolymer, at a ratio of 1 × ¹⁰ -9 ~1 × ^{10 -3} mol, preferably 1 × ¹⁰ -7 ~1 × ^{10 -} Used in a ratio of ⁵ moles.

(Iii) Cyclic carbonate removal step At the same time, the aromatic polycarbonate prepolymer having a high molecular weight is obtained by a high molecular weight reaction to obtain an aromatic polycarbonate resin having a desired molecular weight, and at least a part of the cyclic carbonate by-produced in the reaction. Is removed from 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 when distilling from the reaction system is preferably in the range of 240 ° C to 320 ° C, more preferably 260 ° C to 310 ° C, more preferably 280 ° C to 310 ° C.

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 fat 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. In the following, an aromatic polycarbonate resin containing 500 ppm or less, particularly preferably 300 ppm or less is obtained. 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 Due to the ester exchange reaction between the aromatic polycarbonate prepolymer and the diol compound, the weight average molecular weight (Mw) of the aromatic polycarbonate resin after the reaction is more than the weight average molecular weight (Mw) of the aromatic polycarbonate prepolymer. Is preferably increased by 5,000 or more, more preferably by 10,000 or more, and further preferably by 15,000 or more.

Any known apparatus may be used in the transesterification reaction with the diol compound, the material of the kettle, etc., and the process may be performed continuously or batchwise. The reaction apparatus used for carrying out the reaction may be a vertical type equipped with paddle blades, lattice blades, glasses blades, etc. Alternatively, an extruder type equipped with a screw may be used, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer. Preferably, it has a rotary blade with good horizontal stirring efficiency and a unit that can be under reduced pressure conditions.
More preferably, it is a twin screw extruder or a horizontal reactor having a polymer seal and having a devolatilization structure.

  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 (hereinafter, also simply referred to as “deactivator”) may be applied to the high molecular weight aromatic polycarbonate resin. In general, examples of the deactivator include known acidic substances, and the deactivation of the catalyst by the addition of these deactivators is preferably performed. Specific examples of these deactivators include aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl paratoluenesulfonic acid, tetrabutylphosphonium salt of dodecylbenzenesulfonic acid, and paratoluenesulfonic acid. Aromatic sulfonates such as tetrabutylammonium salt, stearic acid chloride, butyric acid chloride, benzoyl chloride, toluenesulfonic acid chloride, organic halides such as benzyl chloride, alkyl sulfates such as dimethyl sulfate, phosphoric acids, phosphorous acids, etc. Is mentioned.

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 deactivation of the catalyst, a step of devolatilizing and removing the low boiling point compound in the aromatic polycarbonate resin at a pressure of 0.013 to 0.13 kPa (0.1 to 1 torr) and a temperature of 200 to 350 ° C. may be provided. For this purpose, a horizontal apparatus equipped with a stirring blade excellent in surface renewability, such as a paddle blade, a lattice blade, or a glasses blade, or a thin film evaporator is preferably used. Preferably, it is a twin screw extruder or a horizontal reactor having a polymer seal and having a vent structure.

Production method of aromatic polycarbonate resin composition The production method of the aromatic polycarbonate resin composition is not particularly limited as long as a resin composition in which a desired additive is mixed is obtained. For example, the catalyst used in the polymerization reaction for producing the aromatic polycarbonate resin having the structural unit represented by the general formula (I) (for example, the high molecular weight reaction) or at the end of the polymerization reaction or the polymerization reaction is used. The resin composition can be produced by adding an additive at any time after deactivation with the catalyst deactivator and before pelletization, and mixing with the aromatic polycarbonate resin. Preferably, for example, at least one additive selected from the group consisting of a stabilizer, an ultraviolet absorber and a release agent is added to the aromatic polycarbonate resin containing a cyclic carbonate obtained by the method for producing an aromatic polycarbonate resin. A resin composition can be manufactured by mixing. In this case, the mixing of the additive may be performed simultaneously with the mixing of the catalyst deactivator in the method for producing the aromatic polycarbonate resin, or may be performed separately.

  The aromatic polycarbonate resin composition of the present invention can be preferably used for various molded articles and various members obtained by injection molding, blow molding, extrusion molding, rotational molding, compression molding and the like. When used in these applications, the 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 household appliances such as TVs and microwave ovens, electronic parts applications such as connectors and IC trays, protective gear members such as helmets, protectors, protective surfaces, members for different medical devices, etc. However, it is not limited to these. As described above, particularly preferred uses of the aromatic polycarbonate resin composition of the present invention include molded products that require particularly high strength (high Charpy strength) and precision moldability.

    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 analysis and physical-property evaluation of the obtained aromatic polycarbonate prepolymer or aromatic polycarbonate resin (Hereinafter, when it is common to both, it is also called "polycarbonate.") Measured using method or apparatus.

(1) Weight average molecular weight (Mw) and 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 determined as polystyrene converted values by the following calculation formula.

[a formula]
Mw = Σ (W _i × M _i ) ÷ Σ (W _i )
Mn = Σ (N _i × M _i ) ÷ Σ (N _i )
Here, i is the i-th dividing point when the molecular weight M is divided, W _i is the i-th weight, N _i is the number of i-th molecules, and M _i 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)
It 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.
Measurement nucleus: ¹ H
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 amount; mol%)
^It calculated | required by the following numerical formula from the analysis result of < ¹ > H-NMR.

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.

(5) Cyclic carbonate content 10 g of the aromatic polycarbonate resin as a sample 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, 30 m × 0.25 mmI. D. , Film thickness 0.5μm
Temperature rising conditions: 50 ° C. (5 min hold) −300 ° C. (15 min hold), 10 ° C./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

(6) Content 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 high temperature was measured using a nuclear magnetic resonance analyzer ¹ H-NMR at 23 ° C. The content of heterogeneous structures in the molecular weighted polycarbonate (PC) was measured. The content (ppm) of heterostructure (PSA) shown below was measured by assignment of ¹ H-NMR of Ha and Hb described in P.7659 in the document Polymer 42 (2001) 7653-7661. The measurement conditions for ¹ H-NMR are the same as described above.

(7) N value Using an elevated flow tester CFT-500D (manufactured by Shimadzu Corporation), an aromatic polycarbonate (sample) dried at 120 ° C. for 5 hours has a hole diameter of 1.0 mmφ and a length of 10 mm. Using a die, the melt flow volume per unit time measured at 280 ° C. and a load of 160 kg is set as a Q160 value, and similarly the melt flow volume per unit time measured at 280 ° C. and a load of 10 kg is set as a Q10 value. It calculated | required by the following Formula (1). The Q value is the outflow amount (ml / sec) of the molten resin.
N value = (log (Q160 value) −log (Q10 value)) / (log160−log10) (1)

(8) Fluidity (Q value)
The flow value (Q value) of the pellets of the aromatic polycarbonate resin composition was evaluated by the method described in JIS K7210 Appendix C. Measurement was performed using a flow tester CFD500D manufactured by Shimadzu Corporation using a die with a hole diameter of 1.0 mmφ and a length of 10 mm, and the amount of molten resin discharged under the conditions of a test temperature of 280 ° C., a test force of 160 kg / cm 2 and a preheating time of 420 sec. (× 0.01 cm ³ / sec) was measured.

(9) MVR value MVR is in accordance with the method described in JIS K7210, pellets melt volume rate of an aromatic polycarbonate resin composition ^was evaluated as (MVR, the unit cm 3 / 10min). Specifically, it was carried out under the conditions of a test temperature of 300 ° C. and a test load of 1.2 kgf using a melt indexer F-W01 manufactured by Toyo Seiki Seisakusho.

(10) YI (Yellow Index)
After drying the pellets of the aromatic polycarbonate resin composition at 120 ° C. for 5 hours, the injection molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) was used under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 40 seconds. Injection molding was performed to form a flat plate having a width of 60 mm, a length of 90 mm, and a thickness of 3 mm.The obtained flat plate was subjected to a color difference meter (“SE6000” manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS K7105. Used to measure YI.

(11) Impact resistance After the pellets of the aromatic polycarbonate resin composition are dried at 120 ° C. for 5 hours, the cylinder temperature is 280 ° C. and the mold is used with an injection molding machine (“SG75Mk-II” manufactured by Sumitomo Heavy Industries, Ltd.). Injection molding is performed under conditions of a temperature of 80 ° C. and a molding cycle of 50 seconds to produce an ISO multipurpose test piece (3 mm thickness), and each of the conditions of room temperature (23 ° C.), 0 ° C., and −30 ° C. Based on this, a Charpy impact test (notched) was carried out. The number of ductile fractures / number of tests was shown as the ductility rate.

[Production Example 1 of aromatic polycarbonate resin composition: PC-1]
(Prepolymer production process)
64.662 kg (283.245 mol) of 2,2-bis (4-hydroxyphenyl) propane, 68.260 kg (318.651 mol) of diphenyl carbonate and 0.17 μmol / mol (2,2-bis) of cesium carbonate as a catalyst (The number of moles relative to (4-hydroxyphenyl) propane) was put into a 300 L reaction with a stirrer and a distillation apparatus, and 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 the system was further maintained for 1 hour to obtain an aromatic polycarbonate prepolymer (hereinafter sometimes abbreviated as “PP-1”). It was.

The obtained aromatic polycarbonate prepolymer (PP-1) had a polystyrene-reduced weight average molecular weight (Mw) of 26500, a terminal hydroxyl group concentration of 200 ppm, and a terminal phenyl group concentration of 6.0 mol%.
The terminal hydroxyl group concentration is a value calculated from ¹ H-NMR and indicates the terminal hydroxyl group concentration contained in the entire polymer. The terminal phenyl group concentration is a value calculated from ¹ H-NMR, and indicates the concentration of all phenylene groups and terminal phenyl groups (including phenyl groups substituted with hydroxyl groups) in the phenyl terminals.

(High molecular weight process)
The resin temperature of the aromatic polycarbonate prepolymer (PP-1) 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 310 ° 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, was heated and melted at 75 to 80 ° C. in a binder preparation tank equipped with anchor blades, and 0.005 mol / L 66 ml of an aqueous solution of cesium carbonate (Cs ₂ CO ₃ ) was added and stirred, followed by dehydration treatment (the final water content was below the detection limit) at 0.1 torr for 1 hour. BEPG containing the obtained catalyst was continuously fed together with PP-1 to the kneader at a rate of 155 g / hr (0.30 mol relative to 1 mol of the total terminal amount of PP-1).

The catalyst, cesium carbonate (Cs ₂ CO ₃ ), was continuously fed so as to have a ratio of 0.33 × 10 ⁻⁶ mol to 1 mol of BPA.

  Subsequently, the mixture of PP-1 and BEPG added with cesium carbonate was supplied to the horizontal stirring reactor at a flow rate of 13455 g / hr through a transport pipe kept at 280 ° C. from the kneader outlet to carry out a high molecular weight reaction. went. 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-toluenesulfonate (p-TSB) as a catalyst deactivator and n-octadecyl-as an antioxidant are obtained with respect to the polycarbonate resin obtained after conducting a linked high molecular weight reaction in a horizontal stirring reactor. Aromatic polycarbonate resin obtained by kneading 1000 ppm of 3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate (Irganox 1076, manufactured by BASF) with a biaxial kneader It was set as the composition (PC-1).

  The polystyrene equivalent weight average molecular weight (Mw) of the aromatic polycarbonate resin in the obtained aromatic polycarbonate resin composition (PC-1) is 47200, and the N value of the obtained aromatic polycarbonate resin is 1.19, the terminal hydroxyl group. The concentration was 400 ppm, the amount of dissimilar structure (PSA) was 500 ppm, and the amount of cyclic polycarbonate was 7 ppm.

[Production Example 2 of aromatic polycarbonate resin composition: PC-2]
In Production Example 1 of the polycarbonate resin (PC-1), the reaction time during the production of the aromatic polycarbonate prepolymer was extended by 1 hour, the polystyrene equivalent weight average molecular weight (Mw) was 28500, the terminal hydroxyl group concentration was 300 ppm, and the terminal phenyl group An aromatic polycarbonate prepolymer (PP-2) having a concentration of 5.8 mol% was obtained, BEPG containing the catalyst was added at a rate of 124 g / hr (0.25 mol based on 1 mol of the total terminal amount of PP-2). The polycarbonate resin (PC-2) was obtained in the same manner except that it was continuously supplied to the kneader together with PP-2 and the resin temperature in the horizontal reactor was changed to 310 ° C.

  The polystyrene equivalent weight average molecular weight (Mw) of the aromatic polycarbonate resin in the obtained aromatic polycarbonate resin composition (PC-2) is 57300, and the N value of the obtained aromatic polycarbonate resin is 1.19, and the terminal hydroxyl group. The concentration was 320 ppm, the amount of heterogeneous structure (PSA) was 310 ppm, and the amount of cyclic polycarbonate was 13 ppm.

[Production Example 3 of aromatic polycarbonate resin composition: PC-3]
In Production Example 1 of the aromatic polycarbonate resin composition (PC-1), 62.844 kg (275.281 mol) of 2,2-bis (4-hydroxyphenyl) propane, 64.750 kg (302.265 mol) of diphenyl carbonate As a catalyst, cesium carbonate 0.25 μmol / mol (number of moles relative to 2,2-bis (4-hydroxyphenyl) propane) and tetramethylammonium hydroxide 20 μmol / mol (2,2-bis (4- Hydroxyphenyl) Aromatic polycarbonate prepolymer (PP) having a polystyrene equivalent weight average molecular weight (Mw) of 26000, a terminal hydroxyl group concentration of 120 ppm, and a terminal phenyl group concentration of 7.2 mol%. -3), BEPG containing catalyst was 158 g / hr. The same except that it was continuously fed to the kneader with PP-2 at a speed (0.25 mol relative to the total terminal amount of PP-3) and the resin temperature in the horizontal reactor was changed to 300 ° C. Thus, an aromatic polycarbonate resin composition (PC-3) was obtained.

  The polystyrene equivalent weight average molecular weight (Mw) of the aromatic polycarbonate resin in the obtained aromatic polycarbonate resin composition (PC-3) is 41000, and the N value of the obtained aromatic polycarbonate resin is 1.20, the terminal hydroxyl group. The concentration was 500 ppm, the amount of different structure (PSA) was 150 ppm, and the amount of cyclic polycarbonate was 2 ppm.

[Production Example 4 of aromatic polycarbonate resin composition: PC-7]
2,2-bis (4-hydroxyphenyl) propane 64.662 kg (283.245 mol), diphenyl carbonate 63.71 kg (297.410 mol) and cesium carbonate 0.5 μmol / mol (2,2-bis) as a catalyst (The number of moles relative to (4-hydroxyphenyl) propane) was put into a 300 L reaction with a stirrer and a distillation apparatus, and 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 is 260 ° C., the degree of vacuum is 0.05 kPa (0.38 torr) or less, and is further maintained for 1 hour to obtain an aromatic polycarbonate prepolymer (hereinafter sometimes abbreviated as “PP-D”). It was.

  The obtained aromatic polycarbonate prepolymer (PP-D) 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-D) was melted to 280 ° C. by a melter (double-screw extruder), and continuously supplied to a kneader having a rotation speed of 140 rpm heated to 300 ° C. at a speed of 13300 kg / hr. .

  Subsequently, an aromatic polycarbonate prepolymer (PP-D) was supplied to the horizontal stirring reactor at a flow rate of 13300 g / hr via 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-toluenesulfonate (p-TSB) as a catalyst deactivator and n-octadecyl-3 as an antioxidant for a polycarbonate resin obtained after conducting a linked high molecular weight reaction in a horizontal stirring reactor. 1000 ppm of-(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate (Irganox 1076, manufactured by BASF) was kneaded with a twin-screw kneader. The polystyrene equivalent weight average molecular weight (Mw) of the aromatic polycarbonate resin in the obtained aromatic polycarbonate resin composition is 47000, the N value of the obtained aromatic polycarbonate resin is 1.27, the terminal hydroxyl group concentration is 1100 ppm, the heterogeneous structure ( The amount of PSA) was 2000 ppm, and the amount of cyclic polycarbonate was below the detection limit.

[Production Example 5 of aromatic polycarbonate resin composition: PC-5]
In the production example 4 of the aromatic polycarbonate resin composition (PC-7), the aromatic polycarbonate resin composition (PC-5) was similarly obtained except that the amount of diphenyl carbonate was changed to 62.00 kg (289.427 mol). )

  The polystyrene equivalent weight average molecular weight (Mw) of the aromatic polycarbonate resin in the obtained aromatic polycarbonate resin composition (PC-5) is 57900, and the N value of the obtained aromatic polycarbonate resin is 1.32. The concentration was 1050 ppm, the amount of different structure (PSA) was 2100 ppm, and the amount of cyclic polycarbonate was below the detection limit.

[Production Example 6 of aromatic polycarbonate resin composition: PC-6]
In Production Example 4 of the polycarbonate resin composition (PC-7), the aromatic polycarbonate resin composition (PC-6) was similarly obtained except that the amount of diphenyl carbonate was changed to 64.500 kg (301.098 mol). Obtained.

  The polystyrene equivalent weight average molecular weight (Mw) of the aromatic polycarbonate resin in the obtained aromatic polycarbonate resin composition (PC-6) is 40500, and the N value of the obtained aromatic polycarbonate resin is 1.26, the terminal hydroxyl group. The concentration was 1020 ppm, the amount of different structure (PSA) was 2000 ppm, and the amount of cyclic polycarbonate was below the detection limit.

The evaluation results of the obtained aromatic polycarbonate resin composition are shown in the following table.

[Example 1]
Nippon Steel Works Co., Ltd. equipped with 1 vent after blending the aromatic polycarbonate resin composition PC-1 obtained in Production Example 1 and various additives in the mass ratio shown in the table below and mixing for 20 minutes with a tumbler. Supplied (TEX30HSST), 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 and pelletized using a pelletizer. The pellet of the aromatic polycarbonate resin composition PC-1A was obtained.
About the pellet of the obtained aromatic polycarbonate resin composition PC-1A, the flow value (Q value), MVR value, YI value, and impact resistance were evaluated. The evaluation results are shown in the table below.

[Examples 2 to 5, Comparative Examples 1 to 5]
In Example 1, an aromatic polycarbonate resin composition was prepared in the same manner as in Example 1, except that the types and amounts of the aromatic polycarbonate resin composition and various additives were changed as shown in the table below. The evaluation was made in the same manner. In Example 5 and Comparative Examples 3 to 5, the aromatic polycarbonate resin compositions obtained in Production Examples 1 and 4 to 6 were pelletized and evaluated without adding further additives.

The abbreviations in the table are as follows.
PTS: Pentaerythritol tetrastearate (Roxyol VPG861, manufactured by Cognis Japan Co., Ltd.) / Mold release agent Manufactured / stabilizer / TINUVIN329: 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole (TINUVIN329, manufactured by BASF Japan) / ultraviolet absorber All polycarbonate resin compositions of Examples and Comparative Examples In addition, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate (Irganox 1076), which is an antioxidant, is contained as a stabilizer at a concentration of 1000 ppm.

  From the table, the aromatic polycarbonate resin composition of the present invention is an aromatic polycarbonate resin composition to which an additive has been added, and the fluidity, hue and mechanical strength are maintained without impairing the original properties of the aromatic polycarbonate resin. It is understood that it is excellent.

Claims (13)

An aromatic polycarbonate resin having a structural unit represented by the following general formula (I), at least one additive selected from the group consisting of a stabilizer, an ultraviolet absorber and a release agent, and the following general formula (II) A cyclic carbonate represented by
The aromatic polycarbonate resin composition whose cyclic carbonate content rate represented by the following general formula (II) is 3000 ppm or less with respect to the aromatic polycarbonate resin which has a structural unit represented by the following general 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)

(In the formula, each of Ra and Rb independently represents 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, an aryl group having 6 to 30 carbon atoms that may contain an oxygen atom or a halogen atom, or a carbon number that 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 1, wherein the terminal hydroxyl group concentration of the aromatic polycarbonate resin having the structural unit represented by the general formula (I) is 1000 ppm or less.   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the weight average molecular weight of the aromatic polycarbonate resin having the structural unit represented by the general formula (I) is in the range of 35,000 to 100,000. object.   The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the stabilizer is at least one antioxidant selected from the group consisting of a hindered phenol compound and a phosphorus compound.   The UV absorber is a benzotriazole compound, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis. (2,4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine The compound according to any one of claims 1 to 4, which is at least one compound selected from the group consisting of -4-one] and [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester. Aromatic polycarbonate resin composition.   The aromatic polycarbonate resin composition according to any one of claims 1 to 5, wherein the release agent is at least one compound selected from the group consisting of aliphatic carboxylic acids and aliphatic carboxylic acid esters.   The additive is deactivated with a catalyst deactivator during or at the end of the polymerization reaction for producing the aromatic polycarbonate resin having the structural unit represented by the general formula (I) or at the end of the polymerization reaction. The aromatic polycarbonate resin composition according to any one of claims 1 to 6, which is added at any time later and before pelletization. The aromatic polycarbonate resin composition according to any one of claims 1 to 7, wherein the cyclic carbonate represented by the general formula (II) is a compound represented by the following general formula (IIa).

(In the formula, Ra and Rb are respectively synonymous with Ra and Rb in the general formula (II)). The N value (structural viscosity index) of the aromatic polycarbonate resin having the structural unit represented by the general formula (I) is 1.25 or less when represented by the following mathematical formula (1). The aromatic polycarbonate resin composition according to any one of 8.
N value = (log (Q160 value) −log (Q10 value)) / (log160−log10) (1) The aromatic polycarbonate resin having the structural unit represented by the general formula (I) includes a structural unit represented by the following general formula (III), and the content thereof is represented by the general formula (I). The aromatic polycarbonate resin composition according to any one of claims 1 to 9, which is less than 2000 ppm in the aromatic polycarbonate resin having a structural unit.

(In the formula, X has the same meaning as X in formula (I).) The aromatic polycarbonate resin having the structural unit represented by the general formula (I) and the cyclic carbonate represented by the general formula (II) are an aromatic polycarbonate prepolymer and a diol represented by the following general formula (IV). Reacting the compound in the presence of a transesterification catalyst to obtain a high molecular weight aromatic polycarbonate resin, and at least part of the cyclic carbonate by-produced in the high molecular weight process is removed from the reaction system. The aromatic polycarbonate resin composition according to any one of claims 1 to 10, which is obtained by a method comprising a step of removing a cyclic carbonate.

(Wherein, Ra, Rb and _R 5 to R ₈ are the same meanings Ra, and Rb and _R 5 to R ₈ in the general formula (II)). The aromatic polycarbonate resin composition according to claim 11, wherein 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 respectively synonymous with Ra and Rb in the general formula (IV)).   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 11 or 12, selected from the group consisting of 2-diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol.