JP2014101417A - Polycarbonate copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate copolymer which has high molecular weight and high flowability while keeping excellent essential quality of polycarbonate and has heterogeneous structures at a small ratio.SOLUTION: The polycarbonate copolymer is formed substantially from a structural unit, which is obtained by a method for reacting an aromatic polycarbonate prepolymer with an aliphatic diol compound in the presence of a transesterification catalyst, namely, which is derived from the aliphatic diol compound having an aliphatic hydrocarbon group to be bonded to a terminal hydroxyl group, and another structural unit derived from an aromatic dihydroxy compound. The polycarbonate copolymer further contains 2,000 ppm of a different structural unit shown by general formula (1) as a biphenyl acid conversion value.

Description

  The present invention relates to a novel polycarbonate copolymer. Specifically, the present invention relates to a polycarbonate copolymer that exhibits high fluidity despite having a high molecular weight (high degree of polymerization) and has few heterogeneous structures.

Polycarbonate has been widely used in many fields in recent years because it is excellent in heat resistance, impact resistance and transparency.
Many studies have been made on the production method of this polycarbonate. Among them, polycarbonates derived from aromatic dihydroxy compounds such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol A”) are produced by both the interfacial polymerization method and the melt polymerization method. Industrialized.

  According to this interfacial polymerization method, polycarbonate is produced from bisphenol A and phosgene, but toxic phosgene must be used. In addition, by-product hydrogen chloride and sodium chloride, and chlorine-containing compounds such as methylene chloride used in large quantities as solvents, the equipment is corroded, and impurities such as sodium chloride and residual methylene chloride that affect polymer properties are removed. Difficult things remain as challenges.

  On the other hand, as a method for producing a polycarbonate from an aromatic dihydroxy compound and diaryl carbonate, for example, bisphenol A and diphenyl carbonate can be melted by polymerizing while removing the by-produced aromatic monohydroxy compound by a transesterification reaction in a molten state. Legal has been known for a long time. Unlike the interfacial polymerization method, the melt polymerization method has the advantage of not using a solvent. However, as the polymerization proceeds, the viscosity of the polymer in the system increases rapidly, and the by-product aromatic monohydroxy compound is efficiently produced. It is difficult to remove out of the system well, and there is an essential problem that the reaction rate is extremely lowered and it is difficult to increase the degree of polymerization.

  In order to solve this problem, various devices for extracting an aromatic monohydroxy compound from a polymer in a high viscosity state have been studied. For example, Patent Document 1 (Japanese Patent Publication No. 50-19600) discloses a screw type polymerizer having a vent portion, and Patent Document 2 (Japanese Patent Application Laid-Open No. 2-153923) discloses a combination of a thin film evaporator and a horizontal polymerization apparatus. A method of using is also disclosed.

  Patent Document 3 (U.S. Pat. No. 5,521,275) discloses a method in which the molecular weight conversion of an aromatic polycarbonate is performed under reduced pressure conditions using an extruder having a polymer seal part and a vent part in the presence of a catalyst. Has been.

  However, the methods disclosed in these publications cannot sufficiently increase the molecular weight of polycarbonate. When high molecular weight is applied by using a large amount of the catalyst as described above or by severe conditions that give high shear, there is a problem that the influence on the resin such as the deterioration of the hue of the resin or the progress of the crosslinking reaction is increased. To do.

  Furthermore, it is known to increase the degree of polymerization of polycarbonate by adding a polymerization accelerator to the reaction system in the melt polymerization method. Increasing the molecular weight with a short reaction residence time and low reaction temperature increases polycarbonate production and thus facilitates simple and inexpensive reactor design.

  Patent Document 4 (European Patent No. 0595608) discloses a method of reacting several diaryl carbonates at the time of molecular weight conversion, but a significant increase in molecular weight cannot be obtained. Patent Document 5 (US Pat. No. 5,696,222) discloses certain polymerization accelerators such as bis (2-methoxyphenyl) carbonate, bis (2-ethoxyphenyl) carbonate, bis (2-chlorophenyl). ) Disclosed is a method for producing a polycarbonate having an increased degree of polymerization by adding an aryl ester compound of carbonic acid and dicarboxylic acid such as carbonate, bis (2-methoxyphenyl) terephthalate and bis (2-methoxyphenyl) adipate. . Patent Document 5 teaches that when an ester compound is used as a polymerization accelerator, an ester bond is introduced, resulting in the formation of a polyester carbonate copolymer (instead of a homopolymer) and low hydrolysis stability.

Patent Document 6 (Japanese Patent No. 412979) discloses a method of reacting several salicyl carbonates in order to increase the molecular weight of an aromatic polycarbonate.
Patent Document 7 (Japanese Translation of PCT International Publication No. 2008-514754) discloses a method of increasing the molecular weight by introducing a polycarbonate oligomer, bissalicyl carbonate and the like into an extruder.

  Further, in Patent Document 8 (Japanese Patent No. 4286914), an aromatic polycarbonate having an increased amount of terminal hydroxyl groups by an active hydrogen compound (dihydroxy compound) and then an increased amount of terminal hydroxyl groups by a salicylic acid ester derivative is coupled. A method is disclosed.

  However, the method disclosed in the above publication, which requires increasing the terminal hydroxyl group of polycarbonate, requires a reaction step with an active hydrogen compound and a reaction step with a salicylic acid ester derivative. Many polycarbonates have low thermal stability and risk of deterioration of physical properties. Moreover, the increase in the amount of hydroxyl groups by the active hydrogen compound induces a partial chain breaking reaction as shown in Non-Patent Documents 1 and 2, and is accompanied by an expansion of the molecular weight distribution. Furthermore, in order to obtain a sufficient reaction rate, it is necessary to use a relatively large amount of catalyst, which may cause a decrease in physical properties during molding.

  Several methods for producing a polycarbonate by adding a diol compound to a reaction system have been proposed. For example, Patent Document 9 (Japanese Patent Publication No. 6-94501) discloses a method for producing a polymer polycarbonate by introducing 1,4-cyclohexanediol. However, in the method disclosed here, since 1,4-cyclohexanediol is introduced together with the aromatic dihydroxy compound from the beginning of the polycondensation reaction system, 1,4-cyclohexanediol is consumed in the polycarbonate formation reaction first. (Oligomerization), and then the aromatic dihydroxy compound reacts to increase the molecular weight. For this reason, there are disadvantages that the reaction time is relatively long and appearance physical properties such as hue are likely to be lowered.

  Patent Document 10 (Japanese Patent Application Laid-Open No. 2009-102536) describes a method for producing a polycarbonate by copolymerizing a specific aliphatic diol and an ether diol. However, since the polycarbonate disclosed here has an isosorbide skeleton as the main structure, the excellent impact resistance required for the aromatic polycarbonate does not appear.

  Also, a method of adding a cyclic carbonate compound to the reaction system (Patent Document 11; Japanese Patent No. 3271353), a method of adding a diol having a basicity of hydroxyl group equal to or higher than the dihydroxy compound used (Patent Document 12; Patent) No. 3301453, Patent Document 13; Japanese Patent No. 3317555) have been proposed, but none of them can provide a high-molecular-weight polycarbonate resin having sufficiently satisfactory physical properties.

  As described above, the conventional method for producing a high-molecular-weight aromatic polycarbonate has many problems, and an improved production method capable of maintaining the original good quality of the polycarbonate and achieving sufficient high-molecular weight. The request still exists.

  Polycarbonate has a drawback of poor fluidity, and it is difficult to injection mold precision parts and thin materials. In order to improve the fluidity, it is necessary to raise the molding temperature and the mold temperature. For this reason, there is a problem that the molding cycle becomes long and the molding cost becomes high or the polycarbonate deteriorates during molding.

  In order to improve fluidity, a method of lowering the weight average molecular weight of the polycarbonate can be mentioned. However, the polycarbonate obtained by this method has a drawback that impact resistance and stress cracking resistance are greatly reduced, and solvent resistance is deteriorated. On the other hand, a method for improving flowability by mixing polycarbonates having different molecular weights to widen the molecular weight distribution is provided (Patent Document 14; US Pat. No. 3,166,606, Patent Document 15; No. 56-45945).

  In these methods, a polycarbonate resin composition having non-Newtonian fluidity and a large die swell is obtained. However, in these polycarbonates, the fluidity under high shear stress is similar to that with normal molecular weight distribution, but the fluidity under low shear stress is lower than that with normal molecular weight distribution. Yes. That is, these polycarbonate resin compositions certainly have non-Newtonian fluidity (the ratio of fluidity under high shear stress and low shear stress is large), but the fluidity itself is never superior to the conventional one. There wasn't. In addition, since it becomes a composition with a wide molecular weight distribution, the mechanical strength of a molded product obtained by a low molecular weight component is reduced, or when a polycarbonate having an extremely high molecular weight range is used to obtain a polycarbonate having a desired molecular weight. There is a concern that coloring components derived from a relatively long residence time increase and the hue of the molded product is deteriorated.

  Moreover, although the information of heat resistance and tensile strength is described in the said patent document 9 regarding the manufacturing method of the high molecular polycarbonate by introduction | transduction of 1, 4- cyclohexanediol, the impact resistance and fluidity | liquidity which are the important characteristics of a polycarbonate are described. Information is not disclosed.

  In addition to these, various methods for highly fluidizing polycarbonate have been proposed. For example, as a method of increasing the fluidity by adding a low molecular weight oligomer to a polycarbonate or by specifying the content of the oligomer, methods described in Patent Documents 16 to 18 can be mentioned. Examples of the method for achieving high fluidization by controlling the production conditions include methods described in Patent Documents 19 to 20.

  Examples of a method for increasing the fluidity by adding or copolymerizing another resin to polycarbonate include methods described in Patent Documents 21 to 27. Examples of the method for achieving high fluidization by changing the polymer molecular structure of polycarbonate include methods described in Patent Documents 28 to 30. Examples of a method for increasing the fluidity by changing the terminal structure of the polycarbonate resin and further adding other resins and additives include the methods described in Patent Documents 31 to 33. Patent Documents 34 to 36 can be cited as methods for achieving high fluidization by devising additives. Patent Documents 37 to 39 can be cited as examples of a flow modifier for polycarbonate or a method for improving fluidity using the flow modifier.

  However, it may be possible to achieve high fluidity by any of the above technologies, but at the same time, the original physical properties of the polycarbonate resin are impaired, the process such as kneading operation is added, and the manufacturing process becomes complicated, other than fluidity such as releasability There are drawbacks such as deterioration of the moldability, limitation of the object of use, and the possibility of increased toxicity. Therefore, it is not easy to obtain a polycarbonate resin having high fluidity while maintaining mechanical strength and heat resistance including impact resistance, which is a useful physical property of aromatic polycarbonate.

  The inventors of the present invention have previously proposed a new method in which a high chain polymerization rate is achieved to obtain a good-quality aromatic polycarbonate by connecting the end of the aromatic polycarbonate with an aliphatic diol compound to extend the chain. (Patent document 40; WO2011 / 062220). According to this method, the aromatic polycarbonate resin having a high degree of polymerization having a Mw of about 30,000 to 100,000 can be obtained in a short time by connecting the end of the aromatic polycarbonate with an aliphatic diol compound and extending the chain. Can be manufactured. Since this method produces a polycarbonate by a high-speed polymerization reaction, it can suppress a branching / crosslinking reaction caused by a long-time heat retention or the like, and can avoid resin deterioration such as hue.

  In addition, the present inventors previously provided a polycarbonate copolymer having a structural unit derived from an aromatic polycarbonate prepolymer and a structural unit derived from an aliphatic diol compound (Patent Document 41; PCT / JP2012 / 070560).

  The method of increasing the molecular weight of polycarbonate using a linking agent composed of these aliphatic diol compounds is a simple and rapid method for producing a polycarbonate resin that maintains the original good quality of polycarbonate and has achieved a sufficiently high molecular weight. There is a need for further improvements in methods of producing high molecular weight polycarbonate resins that can be produced but have better thermal stability.

  One of the factors that impair the thermal stability is a heterogeneous structure present in the polycarbonate resin. In the polycarbonate resin obtained by using the melt polymerization method, there is already known a problem that there are not only a few different structures in the main chain, but it is possible to produce a polycarbonate resin with a small proportion of the different structures by the melt polymerization method. On the contrary, many ideas have been proposed to positively recognize the existence of different structures and improve the melting characteristics and moldability (Patent Documents 42 to 54).

  Although it is important for the development of high-molecular-weight polycarbonate resin with good thermal stability to produce a polycarbonate resin with a high molecular weight but a very small proportion of heterogeneous structure using a melt polymerization method, a method that is fully satisfactory is still proposed It has not been.

Japanese Patent Publication No. 50-19600 Japanese Patent Laid-Open No. 2-153923 US Pat. No. 5,521,275 European Patent No. 0595608 US Pat. No. 5,696,222 Japanese Patent No. 412979 Special table 2008-514754 Japanese Patent No. 4286914 Japanese Examined Patent Publication No. 6-94501 JP 2009-102536 A Japanese Patent No. 3271353 Japanese Patent No. 3301453 Japanese Patent No. 3317555 US Pat. No. 3,166,606 JP 56-45945 Japanese Patent No. 3217862 JP-A-5-186676 Japanese Patent No. 3141297 Japanese Patent No. 3962883 Japanese Patent No. 3785965 JP 2008-037965 A JP 2008-115249 A JP-A-8-003397 JP-T-2006-509862 JP-A-6-157891 JP-A-6-073280 Japanese Patent Laid-Open No. 5-140435 Japanese Patent No. 4030749 JP 2005-060540 A Japanese Patent No. 2521375 Japanese Patent No. 3874671 JP 7-173277 A JP 2003-238790 A Japanese Patent Laid-Open No. 2004-035587 Japanese Patent Publication No. 2007-132596 Japanese Patent Laid-Open No. 2007-039490 Japanese Patent Laid-Open No. 11-181198 JP 61-162520 A Japanese Patent Laid-Open No. 2005-113003 WO2011 / 062220 PCT / JP2012 / 070560 Japanese Patent No. 4267363 Japanese Patent No. 4290472 JP 2004-109162 A Japanese Patent No. 4318346 Japanese Patent No. 4028317 Japanese Patent No. 3249825 JP 2009-235425 A JP 2010-132929 A Japanese Patent No. 3997424 JP 2004-168911 A JP 2010-018819 A Japanese Patent No. 4113781 Japanese Patent No. 4401608

“Polycarbonate Handbook” (Nikkan Kogyo Shimbun), p.344 “Polycarbonate resin” (Nikkan Kogyo Shimbun), Plastic Materials Course 5, p.144

  The problem to be solved by the present invention is a polycarbonate having high flowability while having high molecular weight while maintaining the original good quality of polycarbonate without using other resins or additives, and having a few different structures. It is to provide a copolymer.

  As a result of intensive studies to solve the above problems, the present inventors have a structure formed by an aromatic polycarbonate chain having a certain length or more and a structural unit derived from a specific aliphatic diol compound. The present inventors have found a novel polycarbonate copolymer having the characteristics of having a high fluidity while having a high molecular weight and having a small proportion of different structures.

That is, the present invention relates to the following polycarbonate copolymer.
1) Substantially from a structural unit represented by the following general formula (I) derived from an aliphatic diol compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group and a structural unit represented by the following general formula (II) A polycarbonate copolymer that is formed and satisfies the following conditions (a) to (d).

(In the general formula (I), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain different atoms. R _{1 to} R ₄ each independently represents a hydrogen atom or an aliphatic hydrocarbon having 1 to 30 carbon atoms. And a group selected from the group consisting of an aromatic hydrocarbon group having 1 to 30 carbon atoms, n and m each independently represent an integer of 0 to 10, provided that Q is bonded to the terminal hydroxyl group. When an aliphatic hydrocarbon group is not included, n and m each independently represent an integer of 1 to 10. Further, at least one of R ₁ and R ₂ and at least one of R ₃ and R ₄ are each (Selected from the group consisting of hydrogen atoms and aliphatic hydrocarbon groups.)

(In General Formula (II), R ₁ and R ₂ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or carbon. Represents an aryl group having 6 to 20 carbon atoms, a cycloalkoxyl 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. X is a simple bond or The group selected from the divalent organic group group represented by general formula (II ') is represented.

(In General Formula (II ′), 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, and R ₃ and R ₄ are It may be bonded to form an aliphatic ring.)

(A) It has a structure represented by the following general formula (III).

(In general formula (III), k is an integer of 4 or more, i is an integer of 1 or more, l is an integer of 1 or more, k ′ represents an integer of 0 or 1. R is a linear or branched hydrocarbon group. Represents a phenyl group which may contain fluorine or a hydrogen atom, provided that 70% by weight or more in the total amount of the copolymer is i = 1.)

(B) The ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is 1 to 30:99 to 70 (molar ratio)%.
(C) The weight average molecular weight (Mw) is 30,000 to 100,000.

  (D) The total amount of structural units constituting the polycarbonate copolymer contains at least one of the structural units represented by the following general formulas (1) and (2) in 2000 ppm or less in terms of biphenolic acid.

General formula (1):

General formula (2):

(X in the general formulas (1) and (2) is the same as in the general formula (II).)

2) In the condition (d), the structural unit represented by the general formula (1) is contained at 2000 ppm or less in terms of biphenolic acid, based on the total amount of structural units constituting the polycarbonate copolymer. Polycarbonate copolymer.

3) In the condition (d), the structural units represented by the general formulas (1) and (2) are each contained in 2000 ppm or less in terms of biphenolic acid with respect to the total amount of the structural units constituting the polycarbonate copolymer. 1) The polycarbonate copolymer described in 1).

4) In the condition (d), with respect to the total amount of structural units constituting the polycarbonate copolymer, the structural units represented by the general formulas (1) and (2) are 5000 ppm in terms of biphenolic acid in total. The polycarbonate copolymer according to 1), which is contained below.

5) In the condition (d), the structural unit represented by the following general formula (3) is further contained in an amount of 150 ppm or less in terms of biphenolic acid based on the total amount of structural units constituting the polycarbonate copolymer. Polycarbonate copolymer.

General formula (3):

(X in the general formula (3) is the same as that in the general formula (II).)

6) The polycarbonate copolymer according to 1), wherein a Q value (280 ° C., 160 kg load) which is an index of fluidity is 0.02 to 1.0 ml / s.

7) The polycarbonate copolymer according to 1), wherein an N value (structural viscosity index) represented by the following formula (1) is 1.25 or less.
[Equation 1]
N value = (log (Q160 value) -log (Q10 value)) / (log160−log10) (1)

8) Said Mw and Q value satisfy | fill following numerical formula (2), The polycarbonate copolymer of 1) description characterized by the above-mentioned.
[Equation 2]
4.61 × EXP (-0.0000785 × Mw) <Q (ml / s) (2)

9) The polycarbonate copolymer according to 1), wherein the aliphatic diol compound for deriving the structural unit represented by the general formula (I) is a compound represented by the following general formula (A).

(In the general formula (A), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain different atoms. R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, Represents a group selected from the group consisting of 30 aliphatic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 20 carbon atoms, wherein n and m each independently represent an integer of 0 to 10. However, Q N does not include an aliphatic hydrocarbon group bonded to a terminal hydroxyl group, n and m each independently represent an integer of 1 to 10. In addition, at least one of R ₁ and R ₂ , R ₃ and R ₄ At least one of each is independently selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon group.)

10) The polycarbonate copolymer according to 9), wherein the aliphatic diol compound is a compound represented by the following general formula (i).

(In the general formula (i), _{Q 1} represents a hydrocarbon group having 6 to 40 carbon atoms containing an aromatic ring _{.R 1, R 2,} R ₃ and _{R 4} are each independently a hydrogen atom, 1 to carbon atoms Represents a group selected from the group consisting of 30 aliphatic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 20 carbon atoms, n1 and m1 each independently represents an integer of 1 to 10)

11) The aliphatic diol compound is 4,4′-bis (2-hydroxyethoxy) biphenyl, 2,2′-bis [(2-hydroxyethoxy) phenyl] propane, 9,9-bis [4- (2 -Hydroxyethoxy) phenyl] fluorene, 9,9-bis (hydroxymethyl) fluorene, 9,9-bis (hydroxyethyl) fluorene, fluorene glycol, and fluorene ethanol, a compound selected from 10) The polycarbonate copolymer described.

12) The polycarbonate copolymer according to 9), wherein the aliphatic diol compound is a compound represented by the following general formula (ii).

(In general formula (ii), Q ₂ represents a linear or branched hydrocarbon group having 3 to 40 carbon atoms which may contain a heterocyclic ring. R ₁ , R ₂ , R ₃ and R ₄ are each independently selected. And a group selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and n2 and m2 are each independently 0 to 0. Represents an integer of 10.)

13) The polycarbonate copolymer according to 12), wherein Q ₂ represents a branched aliphatic hydrocarbon group having 6 to 40 carbon atoms having a branch not containing a heterocyclic ring.

14) The aliphatic diol compound is 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3- The polycarbonate copolymer according to 12), selected from the group consisting of diol, 2,2-diethylpropane-1,3-diol, and 2-methyl-2-propylpropane-1,3-diol.

15) The polycarbonate copolymer according to 9), wherein the aliphatic diol compound is a compound represented by the following general formula (iii).

(In general formula (iii), Q ₃ represents a cyclic hydrocarbon group having 6 to 40 carbon atoms. R ₁ , R ₂ , R _3, and R ₄ are each independently a hydrogen atom or a fatty acid having 1 to 30 carbon atoms. Represents a group selected from the group consisting of an aromatic hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and n3 and m3 each independently represents an integer of 0 to 10.)

16) The aliphatic diol compound is selected from the group consisting of pentacyclopentadecane dimethanol, 1,4-cyclohexane dimethanol, 1,3-adamantane dimethanol, decalin-2,6-dimethanol, and tricyclodecane dimethanol. The polycarbonate copolymer according to 15), which is at least one selected compound.

17) The polycarbonate copolymer according to any one of 9) to 16), wherein the aliphatic diol compound has a boiling point of 240 ° C. or higher.
18) A molded product obtained by molding the polycarbonate copolymer according to 1) by a molding method selected from the group consisting of injection molding, blow molding, extrusion molding, injection blow molding, rotational molding, and compression molding.
19) A molded article selected from the group consisting of a sheet and a film, comprising the polycarbonate copolymer according to 1).

  The polycarbonate copolymer of the present invention has a structure formed by an aromatic polycarbonate chain having a certain length or more and a structural unit derived from a specific aliphatic diol compound, and has a high molecular weight. However, it has the characteristics of having high fluidity, almost no branched structure (low N value), and few heterogeneous structures.

  That is, the polycarbonate copolymer of the present invention is a useful physical property of aromatic polycarbonate without using additives, such as mechanical strength such as impact resistance, abrasion resistance, stress cracking resistance, good hue, optical Polycarbonate resin with high molecular weight and high fluidity while maintaining properties such as properties, low equilibrium water absorption, heat resistance, dimensional stability, transparency, weather resistance, hydrolysis resistance, and flame resistance. is there. Furthermore, it is a polycarbonate resin that not only has a high molecular weight and high fluidity but also has few branched structures and heterogeneous structures.

I. Polycarbonate Copolymer The polycarbonate copolymer of the present invention is substantially formed from the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II).

(1) Structural unit represented by general formula (I) The structural unit represented by general formula (I) is derived from an aliphatic diol compound. Here, the aliphatic diol compound referred to in the present invention is a compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group. A terminal hydroxyl group means the hydroxyl group which contributes to formation of the carbonate bond between aromatic polycarbonate prepolymers by transesterification.

Examples of the aliphatic hydrocarbon group include an alkylene group and a cycloalkylene group, and these may be partially substituted with an aromatic group, a heterocyclic group, or the like.

  In the above general formula (I), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain different atoms. The lower limit of the carbon number of this hydrocarbon group is 3, preferably 6, more preferably 10, and the upper limit is preferably 40, more preferably 30, and even more preferably 25.

Examples of the hetero atom include an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N), a fluorine atom (F), and a silicon atom (Si). Of these, oxygen atoms (O) and sulfur atoms (S) are particularly preferred.
The hydrocarbon group may be linear, branched or cyclic. Q may contain a cyclic structure such as an aromatic ring or a heterocyclic ring.

In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and a carbon number. It represents a group selected from the group consisting of 6 to 20, preferably 6 to 10 carbon atoms.

  Specific examples of the aliphatic hydrocarbon group include linear or branched alkyl groups and cycloalkyl groups. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, i-butyl group, t-butyl group, n-amyl group, isoamyl group, n-hexyl group, and isohexyl group. It is done. A cyclohexyl group is mentioned as a cycloalkyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

However, at least one of R ₁ and R ₂ and at least one of R ₃ and R ₄ are each selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon group.
Particularly preferably, each of R _{1 to} R ₄ independently represents a group selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms.
Particularly preferred aliphatic hydrocarbon groups include linear or branched alkyl groups. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, and an isoamyl group.

R _{1 to} R ₄ are most preferably hydrogen atoms. That is, the aliphatic diol compound capable of deriving the general formula (I) is preferably a primary diol compound, and more preferably a primary diol compound excluding a linear aliphatic diol.

  n and m each independently represents an integer of 0 to 10, preferably 0 to 4. However, when Q does not include an aliphatic hydrocarbon group bonded to a terminal hydroxyl group, n and m each independently represent an integer of 1 to 10, preferably 1 to 4.

The aliphatic diol compound from which the structural unit (I) is derived is a compound having a divalent alcoholic hydroxyl group represented by the following general formula (A). In the general formula (A), Q, R _{1 to} R ₄ , n and m are the same as those in the general formula (I).

Specific examples of the terminal structures “HO— (CR ₁ R ₂ ) _n —” and “— (CR ₃ R ₄ ) _m —OH” include the following structures.

  More preferable examples of the aliphatic diol compound used in the present invention include compounds having a divalent alcoholic hydroxyl group represented by any one of the following general formulas (i) to (iii).

In the general formula (i), Q ₁ represents a hydrocarbon group having 6 to 40 carbon atoms including an aromatic ring, preferably a hydrocarbon group having 6 to 30 carbon atoms including an aromatic ring. Q ₁ contains at least one hetero atom selected from the group consisting of an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N), a fluorine atom (F), and a silicon atom (Si). Also good.

n1 and m1 each independently represent an integer of 1 to 10, preferably an integer of 1 to 4. Examples of the aromatic ring include a phenyl group, a biphenyl group, a fluorenyl group, and a naphthyl group.
Specific examples of Q ₁ include groups represented by the following structural formulas.

In the above general formula (ii), Q ₂ is a linear or branched hydrocarbon group having 3 to 40 carbon atoms which may contain a heterocyclic ring, preferably a linear or branched chain which may contain a heterocyclic ring. Represents a hydrocarbon group having 3 to 30 aliphatic carbon atoms. Q ₂ contains at least one hetero atom selected from the group consisting of an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N), a fluorine atom (F), and a silicon atom (Si). Also good. n2 and m2 each independently represents an integer of 0 to 10, preferably an integer of 0 to 4.

Specific examples of Q ₂ include groups represented by the following structural formulas. In the following structural formulas, in the case of a structural formula group having a molecular weight distribution, it is preferable to select those having an average carbon number based on the average molecular weight in the range of 6 to 40.

In the above general formula (iii), Q ₃ represents a group containing a cyclic hydrocarbon group having 6 to 40 carbon atoms (cycloalkylene group), preferably a cyclic hydrocarbon group having 6 to 30 carbon atoms. n3 and m3 each independently represent an integer of 0 to 10, preferably 1 to 4. Examples of the cycloalkylene group include a cyclohexylene group, a bicyclodecanyl group, and a tricyclodecanyl group.
Specific examples of Q ₃ include groups represented by the following structural formulas.

In the general formulas (i) to (iii), R _{1 to} R ₄ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and 6 carbon atoms. Represents a group selected from the group consisting of ˜20, preferably C 6-10 aromatic hydrocarbon groups. Specific examples thereof are the same as those in the general formula (I).

Of the aliphatic diol compounds represented by any one of the general formulas (i) to (iii), more preferred are the compounds represented by the general formulas (i) and (ii), and particularly preferred are It is a compound represented by general formula (ii).
The aliphatic diol compound represented by the general formula (A) is particularly preferably a primary diol compound, and more preferably a primary diol compound excluding a linear aliphatic diol.

  Specific examples of what can be used as the aliphatic diol compound represented by the general formula (A) include compounds having the following structures.

  Specific examples of those that can be used as the aliphatic diol compound represented by the general formula (A) are classified into primary diols and secondary diols as follows.

(I) Primary diol: 2-hydroxyethoxy group-containing compound The aliphatic diol compound of the present invention is preferably represented by “HO— (CH ₂ ) ₂ —OYO— (CH ₂ ) ₂ —OH”. A hydroxyethoxy group containing compound is mentioned. Here, Y is selected from an organic group (A) having the structure shown below, an organic group (B), an organic group (C) selected from a divalent phenylene group or a naphthylene group, or the following structural formula: A cycloalkylene group (D).

Here, X represents a single bond or a group having the following structure. R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a cycloalkyl group, and they may contain a fluorine atom. R ₁ and R ₂ are preferably a hydrogen atom or a methyl group. p and q each independently represents an integer of 0 to 4 (preferably 0 to 3).

In the above structure, Ra and Rb are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 30, preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 4, carbon atoms, It represents an aryl group having 6 to 12 carbon atoms, or a cycloalkyl group having 6 to 12 carbon atoms, or may be bonded to each other to form a ring. Examples of the ring include an aromatic ring, an alicyclic ring, a heterocyclic ring (including O and / or S), or any combination thereof. When Ra and Rb form an alkyl group or a ring with each other, they may contain a fluorine atom. Rc and Rd each independently represents an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms (particularly preferably a methyl group or an ethyl group), and they may contain a fluorine atom. . e represents an integer of 1 to 20, preferably 1 to 12.
Re and Rf are each independently a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 6 to 12 carbon atoms, or a carbon number. Represents 1-20 alkoxyl groups, which may contain fluorine atoms. Moreover, they may combine with each other to form a ring. The linear or branched alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. The alkoxyl group having 1 to 20 carbon atoms is preferably a methoxy group or an ethoxy group.

The example of a more specific aliphatic diol compound is shown below. In the following formula, n and m each independently represent an integer of 0 to 4. R ₁ and R ₂ each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a phenyl group, or a cyclohexyl group.

<When Y is an organic group (A)>
Preferred compounds when Y is an organic group (A) are shown below.

<When Y is an organic group (B)>
When Y is an organic group (B), X preferably represents -CRaRb- (Ra and Rb are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a methyl group). Specific examples include the following compounds.

<When Y is an organic group (C)>
Preferred compounds when Y is an organic group (C) are shown below.

Among the 2-hydroxyethoxy group-containing compounds, particularly preferable ones are shown below.

(Ii) Primary diol: hydroxyalkyl group-containing compound The aliphatic diol compound of the present invention preferably contains a hydroxyalkyl group represented by “HO— (CH ₂ ) _r —Z— (CH ₂ ) _r —OH”. Compounds. Here, r is 1 or 2. That is, the hydroxyalkyl group includes a hydroxymethyl group and a hydroxyethyl group.

Examples of Z include the organic groups shown below.

  Preferred hydroxyalkyl group-containing compounds are shown below. In the following formula, n and m each independently represent an integer of 0 to 4.

(Iii) Primary diol: carbonate diol compound A preferred example of the aliphatic diol compound of the present invention is a carbonate diol compound represented by the following formula. Here, as R, the organic group which has the structure shown below is mentioned. In the following formula, n is an integer of 1-20, preferably 1-2. m is an integer of 3 to 20, preferably 3 to 10.

  Preferred examples of the polycarbonate diol-based compound include diols (cyclohexanedimethanol or neopentyl glycol dimer) shown below or those having these as a main component.

  As the aliphatic diol compound of the present invention, a primary diol selected from the above (i) 2-hydroxyethoxy group-containing compound, (ii) hydroxyalkyl group-containing compound, and (iii) carbonate diol compound is used. Is preferred.

  The aliphatic diol compound of the present invention is not particularly limited to the above-mentioned specific primary diol, and can be used in primary diol compounds other than the primary diol, or secondary diol compounds. Things exist. Examples of other primary diol compounds or secondary diol compounds that can be used are shown below.

In the following formula, R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, an amino group, a nitro group, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. A cycloalkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkoxyl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, preferably a hydrogen atom, a fluorine atom, a methyl group, Ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, pentyl group, isoamyl group, cyclohexyl group, phenyl group, benzyl group, methoxy group, or An ethoxy group.

R ₅ , R ₆ , R ₇ and R ₈ are a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms. R ₉ and R ₁₀ are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

  Ra and Rb are each independently a hydrogen atom, 1 to 30 carbon atoms, preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 4 linear or branched alkyl group, and 6 to 6 carbon atoms. It represents a 12 aryl group or a cycloalkyl group having 6 to 12 carbon atoms, or may be bonded to each other to form a ring. Examples of the ring include an aromatic ring, an alicyclic ring, a heterocyclic ring (including O and / or S), or any combination thereof. When Ra and Rb form an alkyl group or a ring with each other, they may contain a fluorine atom.

  R 'is an alkylene group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. Re and Rf are each independently a hydrogen atom, halogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, phenyl group, methoxy group or ethoxy group. m 'is an integer of 4 to 20, preferably 4 to 12. m ″ is an integer of 1 to 10, preferably 1 to 5. e is an integer of 1 to 10.

<Other primary diols>

<Secondary diol>

More specifically, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol, tricyclo (5.2.1.0 ^2.6 ) decanedimethanol, decalin-2, Aliphatic diols containing a cyclic structure such as 6-dimethanol, pentacyclopentadecane dimethanol, isosorbide, isomannide, 1,3-adamantane dimethanol; p-xylylene glycol, m-xylylene glycol, naphthalene diethanol, biphenyl Dimethanol, 1,4-bis (2-hydroxyethoxy) phenyl, 4,4′-bis (2-hydroxyethoxy) biphenyl, 2,2′-bis [(2-hydroxyethoxy) phenyl] propane, 9,9 -Bis [4- (2-hydroxyethoxy) phenyl] fluorene (BP F), aliphatic diols containing an aromatic ring such as 9,9-bis (hydroxymethyl) fluorene, 9,9-bis (hydroxyethyl) fluorene, fluorene glycol, fluorene ethanol; polycaprolactone diol, poly (1 , 4-butanediol adipate) diol, poly (1,4-butanediol succinate) diol, and other aliphatic polyester diols; 2-butyl-2-ethylpropane-1,3-diol (butylethylpropane glycol), 2 , 2-diethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol, 2-methyl-2-propylpropanediol, Branched aliphatic di such as 2-methyl-propane-1,3-diol Lumpur; bis (3-hydroxy-2,2-dimethylpropyl) carbonate diol-based compounds such as carbonate, and the like.

  You may use the said aliphatic diol compound individually or in combination of 2 or more types. In addition, the aliphatic diol compound actually used may vary depending on the reaction conditions and the like, and may be appropriately selected depending on the reaction conditions to be employed.

  The boiling point of the aliphatic diol compound used in the present invention is not particularly limited, but the aromatic monohydroxy compound by-produced by the reaction between the aromatic polycarbonate prepolymer and the aliphatic diol compound is distilled off. In view of this, it is preferable that the aliphatic diol compound to be used has a boiling point higher than that of the aromatic monohydroxy compound. In addition, it is often desirable to use an aliphatic diol compound having a higher boiling point because it is necessary to ensure that the reaction proceeds without volatilization under a certain temperature and pressure. In that case, it is desirable to use an aliphatic diol compound having a boiling point at normal pressure of 240 ° C. or higher, preferably 250 ° C. or higher.

  Specific examples of such aliphatic diol compounds include 1,4-cyclohexanedimethanol, 1,6-cyclohexanedimethanol (boiling point: 283 ° C.), decalin-2,6-dimethanol (341 ° C.), pentacyclo Pentadecalin dimethanol, 4,4′-bis (2-hydroxyethoxy) biphenyl, 2,2′-bis [(2-hydroxyethoxy) phenyl] propane, 9,9-bis [4- (2-hydroxyethoxy) Phenyl] fluorene (BPEF), 9,9-bis (hydroxymethyl) fluorene, 9,9-bis (hydroxyethyl) fluorene, fluorene glycol, fluoreneethanol, 2-butyl-2-ethylpropane-1,3-diol (271 ° C), 2,2-diethylpropane-1,3-diol (250 ° C), 2,2 -Diisobutylpropane-1,3-diol (280 ° C.), bis (3-hydroxy-2,2-dimethylpropyl) carbonate and the like.

On the other hand, even an aliphatic diol compound having a boiling point of less than 240 ° C. at normal pressure can be sufficiently preferably used in the present invention by devising an addition method. Specific examples of such aliphatic diol compounds include 2-ethyl-2-methylpropane-1,3-diol (226 ° C.) and 2-methyl-2-propylpropane-1,3-diol (230 ° C.). And propane-1,2-diol (188 ° C.).
Although there is no restriction | limiting in particular about the upper limit of the boiling point of the aliphatic diol compound used by this invention, 700 degrees C or less is enough.

(2) Structural unit represented by general formula (II) The aromatic polycarbonate-forming unit of the polycarbonate copolymer of the present invention is a structural unit represented by general formula (II).

In general formula (II), R ₁ and R ₂ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon number. A 6-20 aryl group, a C6-C20 cycloalkoxyl group, or a C6-C20 aryloxy group is represented. p and q represent the integer of 0-4. X represents a simple bond or a group selected from a divalent organic group represented by the following general formula (II ′).

In General Formula (II ′), 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, and R ₃ and R ₄ are bonded to each other. Thus, an aliphatic ring may be formed.

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

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

  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′-dimethylphenyl ether, 4,4′-dihydroxyphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy 3,3'-dimethyl diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 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 a monomer and the fact that it can be easily obtained with a small amount of impurities contained therein.

  As the aromatic polycarbonate forming unit in the present invention, various monomers (aromatic dihydroxy) are used for the purpose of controlling optical properties such as control of glass transition temperature, improvement of fluidity, improvement of refractive index, reduction of birefringence, etc. The structural units derived from a plurality of types of the compound) may be combined as necessary.

(3) Requirements (a)
The polycarbonate copolymer of the present invention has a structure represented by the following general formula (III). Here, in general formula (III), (I) represents the structural unit represented by general formula (I), and (II) represents the structural unit represented by general formula (II).

  In the general formula (III), R represents a linear or branched hydrocarbon group, a phenyl group which may contain fluorine, or a hydrogen atom. Specifically, methyl group, propyl group, isopropyl group, ethyl group, butyl group, isobutyl group, pentyl group, isoamyl group, hexyl group, tetrafluoropropyl group, t-butyl-phenyl group, pentafluorophenyl group, etc. Can be mentioned.

In the general formula (III), k represents an average chain length of a chain composed of an aromatic polycarbonate forming unit (aromatic polycarbonate chain). The aromatic polycarbonate forming unit is a structural unit which is the main component of the polycarbonate copolymer of the present invention, and the aromatic polycarbonate chain formed from this unit forms the main polymer structure of the polycarbonate copolymer. k is 4 or more, preferably 4 to 100, more preferably 5 to 70. If this chain length does not have a certain length or more, the structural portion represented by “— (I) _i —” relatively increases, and as a result, the random copolymerizability of the polycarbonate copolymer of the present invention is increased. In addition, the heat resistance and other characteristics inherent in polycarbonate resin tend to be lost.

The structural unit “— (II) _k —” (aromatic polycarbonate chain) is a structural unit derived from an aromatic polycarbonate prepolymer, and its weight average molecular weight (Mw) is preferably 5,000 to 60,000, More preferably, it is 10,000-50,000, More preferably, it is 10,000-40,000, Most preferably, it is 15,000-35,000.

  If the molecular weight of the aromatic polycarbonate chain is too low, the polycarbonate copolymer of the present invention may be more greatly affected by the physical properties of the copolymer component. Although this makes it possible to improve the physical properties, the effect of maintaining the useful physical properties of the aromatic polycarbonate may be insufficient.

  If the molecular weight of the aromatic polycarbonate chain is too high, the polycarbonate copolymer of the present invention may not be a polycarbonate copolymer having high fluidity while maintaining useful physical properties of the aromatic polycarbonate.

i represents the average chain length of the site “— (I) _i —” composed of a structural unit derived from an aliphatic diol compound. i is 1 or more, preferably 1 to 5, more preferably 1 to 3, particularly preferably 1 to 2, and most preferably 1. The average chain length is preferably as close to 1. If the average chain length of the aliphatic diol moiety “— (I) _i —” is too long, the heat resistance and mechanical strength are lowered, and the effects of the present invention cannot be obtained.

l represents the average chain length of the structural unit “-[-(II) _k- (I) _i- ] _l- ” composed of an aromatic polycarbonate chain and an aliphatic diol moiety. l is 1 or more, preferably 1 to 30, more preferably 1 to 20, and particularly preferably 1 to 10.
k ′ is an integer of 0 or 1. That is, the aliphatic diol part “-(I) _i- ” has an aromatic polycarbonate chain on both sides of the aliphatic diol moiety “-(I) _i- ” and sometimes has an aromatic polycarbonate chain on only one side. Has a chain.

In the polycarbonate copolymer, the ratio (molar ratio) between the aromatic polycarbonate chain “— (II) _k —” and the aliphatic diol moiety “— (I) _i —” is not particularly limited, but the entire polycarbonate copolymer is not limited. The average value is preferably “− (II) _k −” / “− (I) _i −” = 0.1 to 3, more preferably 0.6 to 2.5, and particularly preferably 2. Further, k / l is not particularly limited, but is preferably 2 to 200, more preferably 4 to 100.

However, in the polycarbonate copolymer of the present invention, 70% by weight or more, preferably 80% by weight or more, more preferably 90% or more, particularly preferably 95% or more, of the total amount of polymer molecules constituting the polycarbonate copolymer. I = 1. That is, the resin is usually an aggregate of polymer compounds (polymer molecules) having various structures and molecular weights, but the polycarbonate copolymer of the present invention has a long-chain aromatic polycarbonate chain (-(II) k- ) Is an aggregate containing 70% by weight or more of a polymer compound having a structure bonded to one structural unit (-(I)-) derived from an aliphatic diol compound. When the polymer compound of i = 1 is less than 70% by weight, the proportion of the copolymer component is high, and therefore, it is easily affected by the physical properties of the copolymer component, and the original physical properties of the aromatic polycarbonate cannot be maintained.
The proportion of the polymer compound with i = 1 in the polycarbonate copolymer of the present invention can be analyzed by ¹ H-NMR analysis of the polycarbonate copolymer.

(4) Requirements (b)
In the polycarbonate copolymer of the present invention, the ratio of the structural unit represented by the general formula (I) to the structural unit represented by the general formula (II) is 1 to 30:99 to 70 (molar ratio)%. ,
Preferably it is 1-25: 99-75 (molar ratio), Most preferably, it is 1-20: 99-80 (molar ratio).

  When the proportion of the structural unit represented by the general formula (I) is too small, the high molecular weight and high fluidity conditions that are characteristic of the polycarbonate copolymer are not satisfied, and when it is too large, aromaticity such as mechanical strength and heat resistance is obtained. The excellent physical properties inherent to the polycarbonate resin are impaired.

  The polycarbonate copolymer of the present invention may contain a structure derived from another copolymer component without departing from the gist of the present invention. Preferably, the polycarbonate copolymer of the present invention has the general formula ( The structural unit represented by I) is contained in an amount of 1 to 30 mol%, preferably 1 to 25 mol%, particularly preferably 1 to 20 mol%, based on the total amount of structural units.

(5) Requirements (c)
The polycarbonate copolymer of the present invention has a weight average molecular weight (Mw) of 30,000 to 100,000, preferably 30,000 to 80,000, more preferably 35,000 to 75,000, and a high molecular weight. However, it also has high fluidity.

  When the weight average molecular weight of the polycarbonate copolymer is too low, when it is used for blow molding, extrusion molding or the like, the melt tension becomes low and a draw-down is liable to occur and a satisfactory molded product cannot be obtained. In addition, when used in applications such as injection molding, satisfactory molded products cannot be obtained due to stringing or the like. Furthermore, physical properties such as mechanical properties and heat resistance of the obtained molded product are lowered. In addition, the oligomer region increases, and physical properties such as organic solvent resistance also decrease.

  If the weight average molecular weight of the polycarbonate copolymer is too high, injection molding of precision parts and thin materials becomes difficult, resulting in a long molding cycle time and adversely affecting production costs. For this reason, measures such as increasing the molding temperature are required. However, at high temperatures, there is a possibility of gelation, the appearance of heterogeneous structures, an increase in N value, and the like.

(6) Requirements (d)
In the polycarbonate copolymer of the present invention, the structural units include structural units represented by the following general formulas (1) and (2) as heterogeneous structures (hereinafter referred to as “structural units (1)”, “structural units ( 2) ”) is included. X in the following general formulas (1) and (2) is the same as in the above general formula (II).

Structural unit (1):

Structural unit (2):

  Note that the two structural formulas (i) and (ii) in the above structural formula (2) are isomers of each other and are indistinguishable analytically, and are treated as the same structure in the present invention. Therefore, in the present invention, the structural formula (2) means one or both of the structural formulas (i) and (ii). Moreover, content of the structural unit (2) in this invention means the total amount of said two structural formula (i) and (ii).

  In the present invention, the content of at least one structural unit among the structural units (1) and (2) is 2000 ppm or less in terms of biphenolic acid, preferably in terms of biphenolic acid, based on the total amount of structural units constituting the aromatic polycarbonate resin. 1500 ppm, more preferably 1000 ppm or less, particularly preferably 500 ppm or less, and most preferably 300 ppm or less. When the contents of the structural units (1) and (2) both exceed 2000 ppm, the degree of branching tends to increase and the thermal stability tends to decrease. In addition, since these structural units are naturally occurring branches, it is difficult to easily control the degree of branching depending on the amount of branching agent added, or the fluidity is lowered and the moldability is deteriorated. There is.

  As described above, in the present invention, it is necessary that the content ratio of at least one of the structural units (1) and (2) is 2000 ppm or less in terms of biphenolic acid, which is the structural units (1) and ( It means that any one of 2) may be 2000 ppm, but as a preferred embodiment, at least the structural unit (1) is 2000 ppm or less, more preferably 1500 ppm or less, further preferably 1000 ppm or less, particularly preferably 500 ppm or less, Most preferably, the content is 300 ppm or less. In particular, the structural unit (1) has a great influence on the retention stability and hue, and if the proportion of the structural unit (1) is small, the thermal stability and hue are remarkably improved.

  Next, it is desirable that both of the structural units (1) and (2) are each 2000 ppm or less, more preferably 1000 ppm or less, further preferably 1000 ppm or less, particularly preferably 500 ppm or less, most preferably 300 ppm in terms of biphenolic acid. It is the following.

  Moreover, the ratio of the structural units represented by the structural units (1) and (2) is a total, 5000 ppm or less, more preferably 3000 ppm or less, more preferably 2000 ppm or less, particularly preferably 1000 ppm or less, in terms of biphenolic acid. Most preferably, it is 600 ppm or less.

  Furthermore, in addition to the structural units (1) and (2), the structural unit constituting the aromatic polycarbonate resin of the present invention further includes a structural unit represented by the following general formula (3) (hereinafter referred to as “structural unit ( 3) ") in terms of biphenolic acid is 150 ppm or less, preferably 100 ppm or less, and more preferably 70 ppm or less. X in the following general formula (3) is the same as in the above general formula (II).

Structural unit (3):

  Note that the two structural formulas (iii), (iv), and (v) in the structural formula (3) are isomers of each other and cannot be distinguished from each other in the analysis, and therefore are treated as the same structure in the present invention. Therefore, in the present invention, the structural formula (3) means at least one of the structural formulas (iii), (iv), and (v). Moreover, content of the structural unit (3) in this invention means the total amount of said three structural formula (iii), (iv), and (v).

  That is, as will be described later, the polycarbonate copolymer of the present invention is a high molecular weight polymerized at high speed using an aliphatic diol compound, and has not only extremely high thermal stability and excellent heat resistance, but also N Excellent quality such as a low value, a small percentage of units having different structures, and excellent color tone can be provided.

  Here, the unit having a heterogeneous structure refers to a unit having a structure that may cause an undesirable effect, and includes a branch point unit that is contained in a large amount in a polycarbonate obtained by a conventional melting method. The invention is characterized in that the proportion of the structural unit (1) and / or (2) is extremely small, and the proportion of the structural unit (3) can also be reduced.

  In addition, since it is desirable that the content ratio of the structural units (1) to (3) is small, the lower limit thereof is not particularly limited and may be a detection limit (the detection lower limit is usually about 1 ppm). It is allowed that 1)-(3) is contained in an amount of 1 ppm or more (lower detection limit) in terms of biphenolic acid, and in some cases 5 ppm or more, or 10 ppm or more.

  The content ratio of the structural units (1) to (3) in the present invention is a biphenolic acid conversion value. The biphenolic acid converted value is obtained by subjecting the resulting aromatic polycarbonate resin composition to alkaline hydrolysis to the monomer level, and then the compound (1)-() having the following structure corresponding to the structural units (1)-(3) in the monomer. It is the value calculated | required by measuring the content rate of 3) by LC-MS analysis, respectively.

Compound (1) corresponding to structural unit (1):

Compound (2) corresponding to structural unit (2):

Compound (3) corresponding to structural unit (3):

(7) Q value The polycarbonate copolymer of the present invention has a Q value (280 ° C., 160 kg load) which is an index of fluidity, preferably 0.02 to 1.0 ml / s, more preferably 0.03 to 3. 0.5 ml / s and high fluidity. In general, the melting characteristics of the polycarbonate resin can be displayed by Q = K · P ^N. Here, the Q value in the formula is the flow rate of the molten resin (ml / sec), K is the regression equation intercept and is an independent variable (derived from the molecular weight and structure of the polycarbonate resin), and P is an elevated flow tester. Pressure measured at 280 ° C. (load: 10 to 160 kgf) (kg / cm ² ), N represents a structural viscous finger. If the Q value is too low, injection molding of precision parts and thin objects becomes difficult. In that case, measures such as raising the molding temperature are required, but at high temperatures, there is a possibility of gelation, the appearance of a heterogeneous structure, an increase in the N value, and the like. If the Q value is too high, when used for blow molding, extrusion molding or the like, the melt tension becomes low, and a draw-down is likely to occur, and a satisfactory molded product cannot be obtained. In addition, when used in applications such as injection molding, satisfactory molded products cannot be obtained due to stringing or the like.

(8) N value (structural viscosity index)
In the polycarbonate copolymer of the present invention, the N value (structural viscosity index) represented by the following formula (1) is preferably 1.3 or less, more preferably 1.28 or less, and even more preferably 1.25 or less. Especially preferably, it is 1.23 or less.
[Equation 5]
N value = (log (Q160 value) -log (Q10 value)) / (log160−log10) (1)

  In the above formula (1), Q160 value is 280 ° C., melt flow volume per unit time measured at 160 kg load (ml / sec) (Shimadzu Corporation: measured using CFT-500D type, and so on) The Q10 value is 280 ° C. and the melt flow volume per unit time (ml / sec) measured at a load of 10 kg (stroke = 7.0 to 10.0 mm). Calculated). (Nozzle diameter 1mm x Nozzle length 10mm)

  The structural viscosity index “N value” is an index of the degree of branching of the aromatic polycarbonate resin. In the polycarbonate copolymer of the present invention, the N value is low, the content of the branched structure is small, and the proportion of the linear structure is high. Polycarbonate resins generally tend to have higher fluidity (higher Q value) when the proportion of the branched structure is increased (with higher N value) in the same Mw. High fluidity (high Q value) is achieved while keeping the N value low.

(9) Relationship between Mw and Q value In the polycarbonate copolymer of the present invention, the Mw and Q value preferably satisfy the following mathematical formula (2), and more preferably satisfy the following mathematical formula (3). In other words, the polycarbonate copolymer of the present invention can have high molecular weight (high Mw) and high fluidity (Q value) at the same time. A polycarbonate copolymer satisfying the following mathematical formula (2), preferably (3) has not been known so far.

[Equation 6]
4.61 × EXP (-0.0000785 × Mw) <Q (ml / s) (2)
4.61 × EXP (-0.0000785 × Mw) <Q (ml / s) <2.30 × EXP (-0.0000310 × Mw) (3)

(10) Hue The polycarbonate copolymer of the present invention is excellent in hue. The hue evaluation of the polycarbonate copolymer is generally represented by a YI value. Usually, the YI value of the aromatic polycarbonate resin obtained from the interfacial polymerization method is generally 0.8 to 1.0. On the other hand, the conventional high molecular weight polymer of an aromatic polycarbonate obtained by the melt polymerization method generally has a YI value of 1.7 to 2.0 due to a decrease in quality accompanying the production process. However, the YI value of the polycarbonate copolymer obtained by the present invention shows the same YI value as that of the aromatic polycarbonate obtained by the interfacial polymerization method, and the hue is not deteriorated.

2. Production Method of Polycarbonate Copolymer The polycarbonate copolymer of the present invention may be referred to as a polycondensation polymer (hereinafter referred to as “aromatic polycarbonate prepolymer”) having the structure represented by the general formula (II) as a main repeating unit. And an aliphatic diol compound that induces the structure represented by the general formula (I) can be produced by transesterification under reduced pressure conditions. The polycarbonate copolymer thus obtained gives high fluidity while maintaining a high molecular weight while maintaining the original properties of the polycarbonate resin such as impact resistance.
In particular, as the aromatic polycarbonate prepolymer, it is preferable to use an end-capped one that satisfies the specific conditions described later.

(1) Aromatic polycarbonate prepolymer The aromatic polycarbonate prepolymer used in the production of the polycarbonate copolymer of the present invention mainly repeats the structure represented by the general formula (II) constituting the aromatic polycarbonate resin of the present invention. A polycondensation polymer as a unit.

  Such an aromatic polycarbonate prepolymer is prepared by a known transesterification method in which an aromatic dihydroxy compound that induces a structural unit represented by the general formula (II) is reacted with a carbonic acid diester in the presence of a basic catalyst, or the aromatic dihydroxy compound. 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. Moreover, what was synthesize | combined by methods, such as a solid-phase polymerization method and a thin film polymerization method, may be used. Further, it is also possible to use polycarbonate recovered from used products such as used disk molded products.

  These polycarbonates may be mixed and used. 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.

  Examples of the aromatic dihydroxy compound for deriving the structural unit represented by the general formula (II) include compounds represented by the general formula (II ″) and specific examples thereof.

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

As the ratio of the capped end groups, the effect is particularly remarkable when the ratio is 60 mol% or more with respect to the total amount of terminals. 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 aliphatic diol compound proceeds rapidly, and the effects unique to the present invention are particularly prominent. The ratio of the amount of capped ends to the total amount of ends of the polymer can be analyzed by ¹ H-NMR analysis of the polymer.

  Further, the terminal hydroxyl group concentration can be measured by spectroscopic measurement using a Ti complex. 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 hydroxyl group terminal exceeds this range or the amount of the sealed terminal is less than this range, there is a possibility that a sufficient high molecular weight effect cannot be obtained by the transesterification reaction with the aliphatic diol compound.

  As used herein, “total amount of terminal groups of polycarbonate” or “total amount of terminal groups of aromatic polycarbonate prepolymer” is, for example, if there is 0.5 mol of unbranched polycarbonate (or chain polymer), Calculated as 1 mole.

  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 terminal group composed of a low-boiling aromatic monohydroxy compound that is easily removed from the reaction system by transesterification with an aliphatic diol compound is preferable, and a phenyl terminal, a p-tert-butylphenyl terminal, 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 acid diester such as diphenyl carbonate with respect to the aromatic dihydroxy compound during the production of the aromatic polycarbonate prepolymer. Although it depends on the apparatus and reaction conditions used for the reaction, specifically, 1.00 to 1.30 mol, more preferably 1.02 to 1.20 mol of carbonic acid diester is used per 1 mol of the aromatic dihydroxy compound. . Thereby, the aromatic polycarbonate prepolymer which satisfy | fills the said amount of terminal sealing is obtained.

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

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

  Further, when an aromatic polycarbonate prepolymer is produced, a dicarboxylic acid compound may be used in combination with the aromatic dihydroxy compound to form 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 employed as an acid chloride or ester compound. Moreover, when manufacturing polyester carbonate resin, it is preferable to use dicarboxylic acid in 0.5-45 mol% when the sum total of the said dihydroxy component and dicarboxylic acid component is 100 mol%. It is more preferable to use in the range of ˜40 mol%.

  The molecular weight of the aromatic polycarbonate prepolymer is preferably Mw of 5,000 to 60,000. An aromatic polycarbonate prepolymer having a Mw of 10,000 to 50,000, more preferably 10,000 to 40,000, and particularly preferably 15,000 to 35,000 is desirable.

  When an aromatic polycarbonate prepolymer having an Mw within this range is used, the resulting polycarbonate copolymer does not have an excessive effect on the physical properties of the copolymer component, and more sufficiently maintains the useful physical properties of the aromatic polycarbonate. be able to. In addition, since the viscosity of the aromatic polycarbonate prepolymer itself is not too high, the prepolymer is produced at a high temperature / high shear / long time, or the reaction with the aliphatic diol compound is performed at a high temperature / high shear / It is not necessary to carry out for a long time, and it is preferable because a polycarbonate copolymer having high fluidity can be easily obtained while maintaining useful physical properties of the aromatic polycarbonate.

  In the present invention, an aliphatic diol compound is allowed to act on the end-capped aromatic polycarbonate prepolymer in the presence of a transesterification catalyst under reduced pressure conditions, thereby achieving high molecular weight at high speed under mild conditions. That is, the reaction between the aliphatic diol compound and the aromatic polycarbonate prepolymer proceeds faster than the reaction in which the aliphatic polycarbonate unit is generated by the transesterification after the aromatic polycarbonate prepolymer is cleaved by the aliphatic diol. .

  As a result, the polymer compound in which the chain length (i value) of the structural unit derived from the aliphatic diol compound in the general formula (III) is 1, the polymer compound having an aliphatic polycarbonate unit having an i value of 2 or more. The polycarbonate copolymer of the present invention in which the ratio of the polymer compound having an i value of 1 is extremely high can be obtained.

  Even if a polycarbonate copolymer containing the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) at the same ratio as in the present invention has existed conventionally, By the method of reacting the dihydroxy compound, the aliphatic diol compound, and the carbonate bond-forming compound all together, a polycarbonate copolymer in which the ratio of the high molecular compound having an i value of 1 in the general formula (III) is extremely high can be obtained. I can't. The polycarbonate copolymer having a low ratio of the high molecular compound having an i value of 1 in the general formula (III) retains the original physical properties of the polycarbonate resin, has a high molecular weight and high fluidity. However, it may become a polymer with many branches (branching degree N value is large), and it may become gelled or tend to decrease in mechanical strength such as hue, impact resistance, and stress cracking resistance.

  A polycarbonate copolymer obtained by a method in which an aliphatic diol compound is allowed to act on an end-capped aromatic polycarbonate prepolymer in the presence of a transesterification catalyst in a reduced pressure condition as in the present invention is high in molecular weight but high in molecular weight. The proportion of units having a heterogeneous structure that exhibits a Q value, more preferably a low N value, and that may necessarily lead to undesirable effects in the present invention is extremely small. Here, the unit having a heterogeneous structure refers to a branch point unit contained in a large amount of polycarbonate obtained by a conventional melting method. The polycarbonate copolymer of the present invention is characterized in that the proportion of units having a structure represented by the above general formulas (1) to (3) is extremely small as units having a different structure.

  The aromatic polycarbonate prepolymer used in the present invention preferably has a residual carbonate monomer amount of 3000 ppm or less, more preferably a residual carbonate monomer amount of 2000 ppm or less, and particularly preferably 1000 ppm or less.

  The method of setting the amount of residual carbonate monomer to 3000 ppm or less is not particularly limited, but the amount of carbonic acid diester charged at the time of production is adjusted (for example, an amount not exceeding 1.3 mol relative to 1 mol of the aromatic dihydroxy compound in total) Preferably, the amount does not exceed 1.2 mol), or an appropriate reaction temperature (for example, 180 ° C. to 320 ° C.) and a reduced pressure (for example, 150 torr or less) can be used.

  The aromatic polycarbonate prepolymer used in the present invention preferably has a structural viscosity index (N value) of 1.25 or less. In that case, since the content ratio of the branched structure of the prepolymer is small and the ratio of the linear structure is high, when the prepolymer and the aliphatic diol compound are reacted to increase the molecular weight, the low molecular weight is maintained while maintaining a low N value. A polycarbonate copolymer having good fluidity (high Q value) can be obtained. The polycarbonate copolymer obtained has an N value (structural viscosity index) of preferably 1.3 or less, more preferably 1.28 or less, particularly preferably 1.25 or less, and most preferably 1.23 or less. There is no large variation in N value between the polycarbonate prepolymer.

(2) Aliphatic diol compound What can be used as the aliphatic diol compound that induces the structure represented by the general formula (I) to be transesterified with the aromatic polycarbonate prepolymer is represented by the general formula (A). The compound having a divalent alcoholic hydroxyl group is preferable as described above.

  In the present invention, the addition amount of the aliphatic diol compound is preferably 0.01 to 1.0 mole, more preferably 0.1 to 1 mole relative to 1 mole of the total terminal group amount of the aromatic polycarbonate prepolymer. 0.0 mol, and more preferably 0.2 to 0.7 mol. However, when a product having a relatively low boiling point is used, an excessive amount may be added in advance in consideration of the possibility that a part of the reaction may go out of the system without being involved in the reaction due to volatilization or the like depending on the reaction conditions. For example, about 1,4-cyclohexanedimethanol (boiling point 283 ° C.), p-xylylene glycol (boiling point 288 ° C.), m-xylylene glycol (boiling point 290 ° C.), polycarbonate diol, etc., in the obtained polycarbonate copolymer In order to make the amount of the structural unit derived from the aliphatic diol compound within a desired range, it is possible to add about 50 mol at the maximum with respect to 1 mol of all terminal groups of the aromatic polycarbonate prepolymer.

  When the amount of the aliphatic diol compound used exceeds this range, the copolymerization ratio increases, and the physical properties of the structural unit derived from the aliphatic diol compound represented by the general formula (I), which is a copolymerization component, are large. There is a case. Although it is possible to improve the physical properties by this, it may not be preferable as an effect of maintaining the useful physical properties of the aromatic polycarbonate. On the other hand, if the amount of the aliphatic diol compound used is less than this range, the effect of increasing the molecular weight and increasing the fluidity may be small, which may not be preferable.

(3) Purity of raw material In addition, it is preferable that the chemical purity of raw material compounds, such as an aromatic dihydroxy compound used for manufacture of the polycarbonate copolymer of this invention, an aliphatic diol compound, and a carbonate bond-forming compound, is high. Although it is possible to manufacture with commercially available chemical purity at an industrial level, if a low-purity product is used, it will contain impurities by-products and heterogeneous skeletal structures, so the resulting resin and molded product will be colored. May become stronger, or various physical properties such as thermal stability and strength may be lowered, making it difficult to maintain the original physical properties of the polycarbonate resin.

  The preferable chemical purity of the aliphatic diol compound is 70% or more, more preferably 80% or more, and particularly preferably 90% or more. The preferable chemical purity of the carbonate bond-forming compound such as diphenyl carbonate is 80% or more, more preferably 90% or more, and particularly preferably 95% or more. The preferable chemical purity of the aromatic dihydroxy compound is 90% or more, more preferably 95% or more, and particularly preferably 99% or more.

  In the case where the aliphatic diol compound is a compound represented by the following formula (BPEF or the like), an impurity that may be a factor in reducing the chemical purity contained in the raw material compound mainly composed of the aliphatic diol compound will be described.

  Examples of impurities contained in the raw material compound mainly composed of the aliphatic diol compound that can lower the chemical purity include the following compounds.

  The content of impurities having these structures is desirably 30% or less, preferably 20% or less, particularly preferably 10% or less, in the raw material compound mainly composed of the aliphatic diol compound.

  In addition to impurities that lower the chemical purity, the above raw material compounds may contain chlorine, nitrogen, boron, alkali metals, alkaline earth metals, light metals, heavy metals, etc. as impurities, but the amount of chlorine contained in the raw material compounds The amount of nitrogen, boron, alkali metal, alkaline earth metal, light metal, and heavy metal are preferably low.

  Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, and salts and derivatives thereof. Alkaline earth metals include beryllium, magnesium, calcium, strontium, barium and their salts and derivatives. Examples of the light metal include titanium, aluminum, and salts and derivatives thereof.

Specific examples of heavy metals include vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tantalum, Examples thereof include tungsten, osmium, iridium, platinum, gold, thallium, lead, bismuth, arsenic, selenium, tellurium, and salts and derivatives thereof.
These impurities are preferably low in all raw material compounds.

  The content of impurities contained in the aliphatic diol compound is 3 ppm or less, preferably 2 ppm or less, more preferably 1 ppm or less as chlorine, 100 ppm or less as nitrogen, alkali metal, alkaline earth metal content, titanium and heavy metals (among others). (Iron, nickel, chromium, zinc, copper, manganese, cobalt, molybdenum, tin) is preferably 10 ppm or less, preferably 5 ppm, more preferably 1 ppm or less.

  The content of impurities contained in other raw materials (aromatic dihydroxy compound and carbonate bond-forming compound) is 2 ppm or less, preferably 1 ppm or less, more preferably 0.8 ppm or less as nitrogen, 100 ppm or less as nitrogen, and alkali. The amount of metal, alkaline earth metal, titanium and heavy metal (among others iron, nickel, chromium, zinc, copper, manganese, cobalt, molybdenum, tin) is preferably 10 ppm or less, preferably 5 ppm, more preferably 1 ppm or less.

  When the metal content is large, the reaction may be faster due to the catalytic action, or conversely, the reactivity may deteriorate. As a result, the progress of the assumed reaction is hindered and the side reaction proceeds, resulting in spontaneous occurrence. There are cases where the branching structure to be increased increases or the N value increases unexpectedly. Furthermore, in the obtained resin and molded body, coloring may become strong and various physical properties such as thermal stability may be deteriorated.

(4) Production conditions The temperature used for the transesterification reaction between the aromatic polycarbonate prepolymer and the aliphatic diol compound is preferably in the range of 240 ° C to 320 ° C, more preferably 260 ° C to 310 ° C, more preferably 270. ° C to 300 ° C.

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

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

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

  Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, acetic acid. Cesium, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, hydrogen phosphate Disodium, 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, phenolic sodium Potassium 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 the nitrogen-containing compound include an alkyl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide, and / or an aryl group. 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, or ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride Ride, tetrabutylammonium tetraphenylborate, basic or basic salts such as tetraphenyl ammonium tetraphenylborate, or the like is used.

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

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

These catalysts are used in a ratio of 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻⁵ mol, relative to a total of 1 mol of the aromatic dihydroxy compound. Used.

  In the present invention, the weight average molecular weight (Mw) of the polycarbonate copolymer after the reaction is changed by the transesterification reaction between the aromatic polycarbonate prepolymer and the aliphatic diol compound. It is preferable to increase more than 5,000, more preferably 10,000 or more, and still more preferably 15,000 or more.

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

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

  In the present invention, a catalyst deactivator can be used for the polymer having an increased molecular weight. In general, a method of deactivating a catalyst by adding a known acidic substance is preferably performed. Specific examples of these substances include aromatic sulfonic acid esters such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl paratoluenesulfonate, stearic acid chloride, butyric acid chloride, benzoyl chloride, and toluenesulfonic acid chloride. An organic halide such as dimethyl sulfate, an alkyl sulfate such as dimethyl sulfate, and an organic halide such as benzyl chloride are preferably used.

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

  Furthermore, in the present invention, in addition to the above heat stabilizer and hydrolysis stabilizer, antioxidants, pigments, dyes, reinforcing agents and fillers, ultraviolet absorbers, lubricants, mold release agents, crystal nucleating agents, Plasticizers, fluidity improvers, antistatic agents, and the like can be added.

  These additives can be mixed with the polycarbonate copolymer by a conventionally known method. For example, a method in which each component is dispersed and mixed with a high-speed mixer represented by a turnbull mixer, a Henschel mixer, a ribbon blender, or a super mixer, and then melt-kneaded with an extruder, a Banbury mixer, a roll, or the like is appropriately selected.

3. Example of Use The polycarbonate copolymer of the present invention is preferably used for various molded articles, sheets, films and the like obtained by injection molding, blow molding (hollow molding), extrusion molding, injection blow molding, rotational molding, compression molding and the like. Can be used. When used in these applications, the resin of the present invention alone or a blend with another polymer may be used. Depending on the application, processing such as hard coating and laminating can be preferably used.

  Particularly preferably, the polycarbonate copolymer of the present invention is used for extrusion molding, blow molding, injection molding and the like. Examples of the molded product obtained include extrusion molded products, hollow molded products, precision parts, and thin injection molded products. Precision parts and thin injection molded articles preferably have a thickness of 1 μm to 3 mm.

  Specific examples of molded products include optical media products such as compact discs, digital video discs, mini-discs, magneto-optical discs, optical communication media such as optical fibers, optical components such as headlamp lenses for cars and lens bodies for cameras, etc. , Optical equipment parts such as siren light covers and lighting lamp covers, vehicle window glass substitutes such as trains and automobiles, household window glass substitutes, daylighting parts such as sunroofs and greenhouse roofs, goggles and sunglasses, eyeglass lenses , Housings for OA equipment such as copiers, facsimiles and personal computers, housings for home appliances such as TVs and microwave ovens, electronic parts such as connectors and IC trays, helmets, protectors, protective equipment such as protective surfaces, feeding Household items such as bottles, tableware, trays, medical supplies such as artificial dialysis cases and dentures, packaging Material, writing instruments, but can be and the like miscellaneous goods such as stationery but are not limited to these.

Particularly preferably, the use of the polycarbonate copolymer of the present invention includes the following molded products requiring high strength and precision moldability.
・ Automotive materials such as headlamp lenses, meter panels, sunroofs, glass window substitutes, outer panel parts, various films such as liquid crystal displays, light guide plates, and optical disk substrates.
・ Cases such as personal computers, printers, and LCD TVs as building materials and structural members such as transparent sheets

  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 was measured using the following method or apparatus.

1) Polystyrene-converted weight average molecular weight (Mw): A calibration curve was prepared using standard polystyrene having a known molecular weight (molecular weight distribution = 1) using GPC and chloroform as a developing solvent. Based on this calibration curve, it was calculated from the retention time of GPC.

2) Measurement of the proportion of different structures (structural units (1) to (3)):
After alkali hydrolysis of the polycarbonate resin to the monomer level, the content ratio of the compounds (1)-(3) having the following structure corresponding to the structural units (1)-(3) in the monomer was measured by LC-MS analysis. Asked. Specifically, 0.1 g of a sample was collected in an Erlenmeyer flask and dissolved in 10 ml of dichloromethane, and then 1.8 ml of 28% sodium methoxide methanol solution, 8 ml of methanol, and 2.6 ml of water were added and stirred for 1 hour. Further, 12 ml of 1N hydrochloric acid was added to make the pH acidic, and the mixture was stirred for 10 minutes and allowed to stand. The dichloromethane layer was collected and made up to 10 ml. 2 ml of this dichloromethane solution was extracted and dried under a nitrogen stream. What added 2 ml of acetonitrile to this sample was analyzed by LC-MS.

[LC-MS analysis conditions]
LC: Waters Acquity UPLC
Column: Waters BEH C18 (2.1 mm × 100 mm, 1.7 μm)
Eluent: A; 0.1% -HCO ₂ Haq. B; MeCN
B = 25-100% (0-8min), B = 100% (8-10min)
Flow rate: 0.5 ml / min
Temperature: 40 ° C
Detection: UV220nm
MS: Waters, MALDI-Synapt HDMS
Scan range, speed: 100-1500 / 0.3sec
Ionization method: ESI (-)
Measurement mode: MS
Resolution: 8500 (Vmode)
Capillary voltage: 3kV
Cone voltage: 30V
Trap collision energy: 6V
Transfer collision energy: 4V
Source temperature: 150 ° C
Desolvation temperature: 500 ° C
Injection volume: 1 μl
Internal standard (mass correction): Leucine Enkephalin (m / z554.2615)
Internal standard flow rate: 0.1 ml / min

[Target compound of LC-MS analysis]
Compound (1) corresponding to structural unit (1):

Compound (2) corresponding to structural unit (2):

Compound (3) corresponding to structural unit (3):

  The standard samples of the different structural components were quantified using biphenolic acid having a structure represented by the following formula as a standard substance. Therefore, the obtained value is a biphenolic acid conversion value. Specifically, 26.1 mg of biphenolic acid was diluted with 25 ml of acetonitrile to prepare a standard solution. This solution was diluted to make a standard solution of 1.0 to 250 mg / l.

3) Total amount of terminal groups (number of moles) of polymer: 0.25 g of a resin sample was dissolved in 5 ml of deuterium-substituted chloroform, and nuclear magnetic resonance analyzer ¹ H-NMR (trade name, manufactured by JEOL Ltd.) at 23 ° C. The end groups were measured using “LA-500”) and expressed in moles per ton of polymer.

4) Hydroxyl terminal concentration (ppm): Measured by UV / visible spectroscopic analysis (546 nm) of a complex formed from a polymer and titanium tetrachloride in a methylene chloride solution. Or it measured by observing a terminal hydroxyl group from the analysis result of < ¹ > H-NMR.

5) Terminal phenyl group concentration (terminal Ph concentration; mol%): Obtained from the analysis result of ¹ H-NMR by the following mathematical formula.

6) Resin hue (YI value): 6 g of a resin sample was dissolved in 60 ml of methylene chloride, and a spectroscopic color difference meter (trade name “SE-2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) was used in a cell having an optical path length of 5 cm. Used to measure the YI value.

7) Fluidity (Q value): Q value is the flow rate of molten resin (ml / sec), and it is 5 hours at 130 ° C. using Koka-type flow tester CFT-500D (manufactured by Shimadzu Corporation). After drying, the melt flow volume per unit time measured at 280 ° C. and a load of 160 kg was evaluated.

8) N value: unit time measured at 280 ° C. under a load of 160 kg for an aromatic polycarbonate (sample) dried at 130 ° C. for 5 hours using a Koka type flow tester CFT-500D (manufactured by Shimadzu Corporation) The melt flow volume per unit was defined as Q160 value, and the melt flow volume per unit time measured at 280 ° C. and a load of 10 kg was defined as Q10 value.

[Equation 10]
N value = (log (Q160 value) -log (Q10 value)) / (log160−log10) (1)

9) Ratio of polymer compound having i value = 1: Ratio of polymer compound having i value (chain length of structural unit derived from aliphatic diol compound) in general formula (III) of 1 is the polycarbonate obtained It calculated | required from the < ¹ > H-NMR analysis result of the copolymer.

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

<Example 1>
1,2-bis (4-hydroxyphenyl) propane 10000.0 g (43.804 mol), diphenyl carbonate 10558.0 g (49.286 mol) and sodium hydrogen carbonate as a catalyst at 1.0 μmol / mol-BPA (the catalyst is (Calculated as the number of moles relative to 2,2-bis (4-hydroxyphenyl) propane) was placed in a 50 L SUS reactor equipped with a stirrer and a distillation apparatus, and the system was replaced with a nitrogen atmosphere. The degree of vacuum was adjusted to 27 kPaA (200 torr), the heating medium was set to 205 ° C., the raw material was heated and melted, and then stirred.

  Thereafter, the temperature of the heating medium was gradually raised, and at the same time, the degree of reduced pressure was lowered, and phenol distilled from the reaction system was aggregated and removed by a cooling tube to conduct a transesterification reaction. It took about 4 hours, and finally the inside of the system was 260 ° C., the degree of vacuum was 0.13 kPaA (1 torr) or less, and the system was further maintained for 1 hour. At this time, the partially sampled polycarbonate prepolymer had a weight average molecular weight (Mw) of 21,500, a terminal hydroxyl group concentration of 150 ppm, and a phenyl terminal concentration (Ph terminal concentration) of 7.4 mol%.

  The terminal hydroxyl group concentration is a value calculated from NMR, and indicates the concentration of terminal hydroxyl groups 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.

  Subsequently, the pressure reduction degree of the reaction system was set to 0.13 kPaA (1 torr) or less, and at 285 ° C., 326.89 g (1.033 mol) of 2,2′-bis [(2-hydroxyethoxy) phenyl] propane as an aliphatic diol compound. ) Was added to the reaction system. Further, the degree of vacuum was kept at 0.13 kPaA (1 torr) or less, and stirring was continued for 1 hour and 20 minutes. The obtained polycarbonate resin has a weight average molecular weight (Mw) = 63,000, N value = 1.24, terminal hydroxyl group concentration = 290 ppm, YI value = 1.1, heterogeneous structural formula (1) = 1300 ppm, heterogeneous Structural formula (2) = 370 ppm and different structural formula (3) = 5 ppm were contained.

<Example 2>
The same operation as in Example 1 was carried out except that 256.94 g (0.979 mol) of pentacyclopentadecanedimethanol as an aliphatic diol compound was added to the reaction system. The obtained polycarbonate resin has weight average molecular weight (Mw) = 46,400, N value = 1.23, terminal hydroxyl group concentration = 430 ppm, YI value = 1.2, heterogeneous structural formula (1) = 920 ppm, heterogeneous. Structural formula (2) = 230 ppm and different structural formula (3) = 1 ppm were contained.

<Example 3>
10,000.6 g (43.807 mol) of 2,2-bis (4-hydroxyphenyl) propane, 10,560.0 g (49.295 mol) of diphenyl carbonate and 0.5 μmol / mol-BPA of cesium carbonate as a catalyst (The catalyst is calculated as the number of moles relative to 2,2-bis (4-hydroxyphenyl) propane) in a 50 L SUS reactor equipped with a stirrer and a distiller, and the system is replaced with a nitrogen atmosphere. did. The degree of vacuum was adjusted to 27 kPaA (200 torr), the heating medium was set to 205 ° C., the raw material was heated and melted, and then stirred.

  Thereafter, the temperature of the heating medium was gradually raised, and at the same time, the degree of reduced pressure was lowered, and phenol distilled from the reaction system was aggregated and removed by a cooling tube to conduct a transesterification reaction. It took about 4 hours, and finally the inside of the system was 260 ° C., the degree of vacuum was 0.13 kPaA (1 torr) or less, and the system was further maintained for 1 hour. The obtained polycarbonate prepolymer had a weight average molecular weight (Mw) of 22,000, a terminal hydroxyl group concentration of 60 ppm, and a phenyl terminal concentration (Ph terminal concentration) of 5.0 mol%.

  The terminal hydroxyl group concentration is a value calculated from NMR, and indicates the concentration of terminal hydroxyl groups 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.

  30.0664 g of the above polycarbonate prepolymer was put into a 300 cc four-necked flask equipped with a stirrer and a distiller and heated and melted at 280 ° C. As an aliphatic diol compound, 0.7085 g (0.001616 mol) of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene was added, and the mixture was added at a jacket temperature of 280 ° C. at normal pressure and kneaded for 15 minutes. did.

Subsequently, at 280 ° C., the pressure was adjusted to 0.04 kPaA (0.3 torr), and the mixture was stirred and kneaded for 40 minutes to conduct a transesterification reaction.
The obtained polycarbonate resin has weight average molecular weight (Mw) = 59,000, N value = 1.22, terminal hydroxyl group concentration = 700 ppm, YI value = 1.2, heterogeneous structural formula (1) = 60 ppm, heterogeneous. Structural formula (2) = 60 ppm and heterogeneous structural formula (3) = 1 ppm.

<Example 4>
The same operation as in Example 3 was performed except that 0.2379 g (0.001650 mol) of 1,4-cyclohexanedimethanol as an aliphatic diol compound was added to the reaction system. The obtained polycarbonate resin has weight average molecular weight (Mw) = 56,700, N value = 1.20, terminal hydroxyl group concentration = 700 ppm, YI value = 1.20, heterogeneous structural formula (1) = 70 ppm, heterogeneous Structural formula (2) = 30 ppm and heterogeneous structural formula (3) = 10 ppm were contained.

<Comparative Example 1>
2,2-bis (4-hydroxyphenyl) propane 10,000.0 g (43.804 mol), diphenyl carbonate 9,618.0 g (44.898 mol) and cesium carbonate as a catalyst at 0.5 μmol / mol-BPA (The catalyst is calculated as the number of moles relative to 2,2-bis (4-hydroxyphenyl) propane) in a 50 L SUS reactor equipped with a stirrer and a distiller, and the system is replaced with a nitrogen atmosphere. did. The degree of vacuum was adjusted to 27 kPaA (200 torr), the heating medium was set to 205 ° C., the raw material was heated and melted, and then stirred.

  Thereafter, the temperature of the heating medium was gradually raised, and at the same time, the degree of reduced pressure was lowered, and phenol distilled from the reaction system was aggregated and removed by a cooling tube to conduct a transesterification reaction. It took about 4 hours, and finally the inside of the system was 260 ° C., the degree of vacuum was 0.13 kPaA (1 torr) or less, and the system was further maintained for 4 hours. The weight average molecular weight (Mw) of the obtained polycarbonate is 59,000, the terminal hydroxyl group concentration is 800 ppm, the N value = 1.32, the YI value = 3.0, the heterogeneous structural formula (1) = 2100 ppm, the heterogeneous structural formula (2) = 3100 ppm and different structural formula (3) = 170 ppm.

  The terminal hydroxyl group concentration is a value calculated from NMR, and indicates the concentration of terminal hydroxyl groups 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 polycarbonate copolymer of the present invention is characterized in that the fluidity is improved in spite of the high molecular weight while maintaining the physical properties of the polycarbonate by the conventional interface method without using other resins and additives. Have Further, it can be produced by a simple production method without requiring limited production conditions.

  Such a high fluidity polycarbonate copolymer of the present invention, when used as a substitute for a conventional general-purpose polycarbonate resin or composition, has advantages such as a faster molding cycle and a lower molding temperature. It can be preferably used for various molded products, sheets, films and the like obtained by injection molding, blow molding, extrusion molding, injection blow molding, rotational molding, compression molding and the like. In addition, due to the reduction of power consumption and the like, it is expected that the load on the natural environment and the manufacturing cost of the molded body will be reduced.

Claims (19)

It is formed substantially from a structural unit represented by the following general formula (I) derived from an aliphatic diol compound having an aliphatic hydrocarbon group bonded to a terminal hydroxyl group and a structural unit represented by the following general formula (II). And a polycarbonate copolymer satisfying the following conditions (a) to (d).

(In the general formula (I), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain different atoms. R _{1 to} R ₄ each independently represents a hydrogen atom or an aliphatic hydrocarbon having 1 to 30 carbon atoms. And a group selected from the group consisting of an aromatic hydrocarbon group having 1 to 30 carbon atoms, n and m each independently represent an integer of 0 to 10, provided that Q is bonded to the terminal hydroxyl group. When an aliphatic hydrocarbon group is not included, n and m each independently represent an integer of 1 to 10. Further, at least one of R ₁ and R ₂ and at least one of R ₃ and R ₄ are each (Selected from the group consisting of hydrogen atoms and aliphatic hydrocarbon groups.)

(In General Formula (II), R ₁ and R ₂ are each independently a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or carbon. Represents an aryl group having 6 to 20 carbon atoms, a cycloalkoxyl 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. X is a simple bond or The group selected from the divalent organic group group represented by general formula (II ') is represented.

(In General Formula (II ′), 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, and R ₃ and R ₄ are It may be bonded to form an aliphatic ring.)
(A) It has a structure represented by the following general formula (III).

(In general formula (III), k is an integer of 4 or more, i is an integer of 1 or more, l is an integer of 1 or more, k ′ represents an integer of 0 or 1. R is a linear or branched hydrocarbon group. Represents a phenyl group which may contain fluorine or a hydrogen atom, provided that 70% by weight or more in the total amount of the copolymer is i = 1.)
(B) The ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is 1 to 30:99 to 70 (molar ratio)%.
(C) The weight average molecular weight (Mw) is 30,000 to 100,000.
(D) The total amount of structural units constituting the polycarbonate copolymer contains at least one of the structural units represented by the following general formulas (1) and (2) in 2000 ppm or less in terms of biphenolic acid.
General formula (1):

General formula (2):

(X in the general formulas (1) and (2) is the same as in the general formula (II).)   In the said condition (d), the structural unit represented by the said General formula (1) is contained at 2000 ppm or less in biphenolic acid conversion value with respect to the structural unit whole quantity which comprises the said polycarbonate copolymer. Polycarbonate copolymer.   In the condition (d), the structural unit represented by the general formulas (1) and (2) is contained in an amount of 2000 ppm or less in terms of biphenolic acid, based on the total amount of structural units constituting the polycarbonate copolymer. The polycarbonate copolymer according to claim 1.   In the condition (d), the total of structural units represented by the general formulas (1) and (2) with respect to the total amount of structural units constituting the polycarbonate copolymer is 5000 ppm or less in terms of biphenolic acid. The polycarbonate copolymer according to claim 1. The said condition (d) WHEREIN: The structural unit represented by following General formula (3) is further contained 150 ppm or less in conversion value of biphenolic acid with respect to the structural unit whole quantity which comprises the said polycarbonate copolymer. Polycarbonate copolymer.
General formula (3):

(X in the general formula (3) is the same as that in the general formula (II).)   The polycarbonate copolymer of Claim 1 whose Q value (280 degreeC, 160 kg load) which is a flowability parameter | index is 0.02-1.0 ml / s. The polycarbonate copolymer according to claim 1, wherein an N value (structural viscosity index) represented by the following formula (1) is 1.25 or less.
[Equation 1]
N value = (log (Q160 value) -log (Q10 value)) / (log160−log10) (1) The polycarbonate copolymer according to claim 1, wherein the Mw and the Q value satisfy the following formula (2).
[Equation 2]
4.61 × EXP (-0.0000785 × Mw) <Q (ml / s) (2) The polycarbonate copolymer according to claim 1, wherein the aliphatic diol compound for deriving the structural unit represented by the general formula (I) is a compound represented by the following general formula (A).

(In the general formula (A), Q represents a hydrocarbon group having 3 or more carbon atoms which may contain different atoms. R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, Represents a group selected from the group consisting of 30 aliphatic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 20 carbon atoms, wherein n and m each independently represent an integer of 0 to 10. However, Q N does not include an aliphatic hydrocarbon group bonded to a terminal hydroxyl group, n and m each independently represent an integer of 1 to 10. In addition, at least one of R ₁ and R ₂ , R ₃ and R ₄ At least one of each is independently selected from the group consisting of a hydrogen atom and an aliphatic hydrocarbon group.) The polycarbonate copolymer of Claim 9 whose said aliphatic diol compound is a compound represented by the following general formula (i).

(In the general formula (i), _{Q 1} represents a hydrocarbon group having 6 to 40 carbon atoms containing an aromatic ring _{.R 1, R 2,} R ₃ and _{R 4} are each independently a hydrogen atom, 1 to carbon atoms Represents a group selected from the group consisting of 30 aliphatic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 20 carbon atoms, n1 and m1 each independently represents an integer of 1 to 10)   The aliphatic diol compound is 4,4′-bis (2-hydroxyethoxy) biphenyl, 2,2′-bis [(2-hydroxyethoxy) phenyl] propane, 9,9-bis [4- (2-hydroxy). 11. A compound selected from the group consisting of ethoxy) phenyl] fluorene, 9,9-bis (hydroxymethyl) fluorene, 9,9-bis (hydroxyethyl) fluorene, fluorene glycol, and fluorene ethanol. Polycarbonate copolymer. The polycarbonate copolymer of Claim 9 whose said aliphatic diol compound is a compound represented by the following general formula (ii).

(In general formula (ii), Q ₂ represents a linear or branched hydrocarbon group having 3 to 40 carbon atoms which may contain a heterocyclic ring. R ₁ , R ₂ , R ₃ and R ₄ are each independently selected. And a group selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and n2 and m2 are each independently 0 to 0. Represents an integer of 10.) The polycarbonate copolymer according to claim 12, wherein Q ₂ represents a branched aliphatic hydrocarbon group having 6 to 40 carbon atoms and having a branch not containing a heterocyclic ring.   The aliphatic diol compound is 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol, The polycarbonate copolymer according to claim 12, selected from the group consisting of 2,2-diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol. The polycarbonate copolymer according to claim 9, wherein the aliphatic diol compound is a compound represented by the following general formula (iii).

(In general formula (iii), Q ₃ represents a cyclic hydrocarbon group having 6 to 40 carbon atoms. R ₁ , R ₂ , R _3, and R ₄ are each independently a hydrogen atom or a fatty acid having 1 to 30 carbon atoms. Represents a group selected from the group consisting of an aromatic hydrocarbon group and an aromatic hydrocarbon group having 6 to 20 carbon atoms, and n3 and m3 each independently represents an integer of 0 to 10.)   The aliphatic diol compound is selected from the group consisting of pentacyclopentadecane dimethanol, 1,4-cyclohexanedimethanol, 1,3-adamantane dimethanol, decalin-2,6-dimethanol, and tricyclodecane dimethanol. The polycarbonate copolymer according to claim 15, which is at least one compound.   The polycarbonate copolymer in any one of Claims 9-16 whose boiling point of the said aliphatic diol compound is 240 degreeC or more.   A molded article obtained by molding the polycarbonate copolymer according to claim 1 by a molding method selected from the group consisting of injection molding, blow molding, extrusion molding, injection blow molding, rotational molding, and compression molding. The molded object selected from the group which consists of a sheet | seat and a film which consists of a polycarbonate copolymer of Claim 1.