JP2014028980A - Polycarbonate resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition including a plant-derived raw material and having excellent mechanical strength, heat resistance, a small refractive index, a fine color tone and excellent transparency.SOLUTION: The polycarbonate resin composition includes a phosphorus-based compound and/or a hindered phenol-based compound (b) and an acidic compound (c) in a polycarbonate resin (a) including at least a constitutional unit derived from a dihydroxy compound represented by the specified general formula (1). The content of the compound (b) is 0.001-10 pts.wt. inclusive based on 100 pts.wt. of the resin (a), and the content of the compound (c) is less than 1.0 equivalent based on the amount of a polymerization catalyst included in the resin (a).

Description

  The present invention contains structural units that can be derived from carbohydrates such as starch, which is a biomass resource, is excellent in heat resistance, moldability, and mechanical strength, has a low refractive index, and is highly transparent. Further, the present invention relates to a polycarbonate resin composition having optical characteristics, a method for producing the composition, and a molded product comprising the composition.

  Polycarbonate is generally produced using raw materials derived from petroleum resources. However, in recent years, there is a concern about the exhaustion of petroleum resources, and there is a demand for providing polycarbonate using raw materials obtained from biomass resources such as plants. In addition, it is feared that global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, etc., so that carbon-neutral plant-derived monomers are used as raw materials even after disposal after use. There is a need to develop polycarbonate.

  Conventionally, it has been proposed to use isosorbide as a plant-derived monomer and obtain a polycarbonate by transesterification with diphenyl carbonate (see, for example, Patent Document 1). However, the polycarbonate obtained is brown and is not satisfactory. Further, as a copolymerized polycarbonate of isosorbide and another dihydroxy compound, a polycarbonate copolymerized with bisphenol A has been proposed (for example, see Patent Document 2), and further, by copolymerizing isosorbide and an aliphatic diol. Attempts have been made to improve the rigidity of homopolycarbonate composed of isosorbide (see, for example, Patent Document 3).

  On the other hand, many polycarbonates obtained by polymerizing 1,4-cyclohexanedimethanol, which is an alicyclic dihydroxy compound, have been proposed (for example, Patent Documents 4 and 5). The molecular weight of these polycarbonates is as low as about 4000 at most. Therefore, many of them have a low glass transition temperature.

  Thus, although a polycarbonate using isosorbide has been proposed, a polycarbonate obtained by copolymerizing isosorbide and an alicyclic dihydroxy compound has not been reported, and optical constants such as a refractive index and an Abbe number are also disclosed. Not done.

GB1079686 Publication JP-A-56-55425 WO 2004/111106 JP-A-6-145336 Japanese Patent Publication No. 63-12896

  The polycarbonates described in Patent Documents 1 to 5 are insufficient in terms of heat resistance and transparency as compared with conventional aromatic polycarbonates derived from petroleum raw materials, and are difficult to use for optical materials and molding materials. It was. For this reason, development of highly transparent polycarbonate with a small refractive index is desired, maintaining the high heat resistance and transparency of aromatic polycarbonate.

  An object of the present invention is to eliminate the above-mentioned conventional problems, and to provide a polycarbonate resin composition containing a plant-derived constituent unit, having excellent mechanical strength, heat resistance, low refractive index and excellent transparency, It is in providing the manufacturing method of a composition.

As a result of intensive studies to solve the above problems, the present inventors have determined that a specific amount of a phosphorus compound is contained in a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound represented by the following general formula (1). And / or the polycarbonate resin composition containing the hindered phenolic compound (b) and the acidic compound (c) has excellent mechanical strength, stable thermal stability, low refractive index, excellent color tone and transparency. The present invention was reached.
That is, the gist of the present invention resides in the following [1] to [10].
[1] The following general formula (1)

A polycarbonate resin composition containing a phosphorus compound and / or a hindered phenol compound (b) and an acidic compound (c) in a polycarbonate resin (a) containing at least a structural unit derived from a dihydroxy compound represented by The content of the compound (b) is 0.001 to 10 parts by weight with respect to 100 parts by weight of the resin (a), and the content of the compound (c) is contained in the resin (a). A polycarbonate resin composition characterized by being less than 1.0 equivalent relative to the amount of polymerization catalyst to be produced.
[2] The resin (a) is an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, the following general formula (12)

(In the formula, Zb represents a single bond, an alkylidene group having 1 to 10 carbon atoms, a cycloalkylidene group having 4 to 15 carbon atoms, a sulfonyl group, a sulfide group, an oxide group or a di (isopropylidene) phenylene group, and R ^4a And R ^4b each independently represents a hydrogen atom, a halogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and p1 and p2 each independently represent an integer of 1 to 4.)
A dihydroxy compound represented by the following general formula (13):

(Wherein R ^5a , R ^5b , R ^6a and R ^6b each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogen atom, and q 1, q 2, s 1 and s 2 are each independently And an integer of 1 to 4 is shown.)
The composition according to [1], further comprising a structural unit derived from at least one selected from the group consisting of a dihydroxy compound represented by the formula: oxyalkylene glycol and a diol having a cyclic acetal structure.
[3] The composition according to [1] or [2], wherein the compound (b) is added and kneaded to the resin (a) at a temperature of 270 ° C. or lower.
[4] The composition according to [3], wherein the oxygen concentration during addition / kneading is 1% or less.
[5] The following general formula (1)

Of a polycarbonate resin composition containing at least a phosphorus compound and / or a hindered phenol compound (b) and an acidic compound (c) in a polycarbonate resin (a) containing at least a structural unit derived from a dihydroxy compound represented by A method for producing a polycarbonate resin composition, which comprises adding and kneading compound (b) to resin (a) at a temperature of 270 ° C. or less and an oxygen concentration of 1% or less.
[6] The method according to [5], wherein the resin (a) is produced using a dihydroxy compound represented by the general formula (1) having a formic acid content of less than 20 ppm as a reaction raw material.
[7] The content of the compound (b) is 0.001 to 10 parts by weight with respect to 100 parts by weight of the resin (a), and the content of the compound (c) is contained in the resin (a). The method according to [5] or [6], which is less than 1.0 equivalent relative to the amount of the polymerization catalyst.
[8] The resin (a) is an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, the following general formula (12)

(In the formula, Zb represents a single bond, an alkylidene group having 1 to 10 carbon atoms, a cycloalkylidene group having 4 to 15 carbon atoms, a sulfonyl group, a sulfide group, an oxide group or a di (isopropylidene) phenylene group, and R ^4a And R ^4b each independently represents a hydrogen atom, a halogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and p1 and p2 each independently represent an integer of 1 to 4.)
A dihydroxy compound represented by the following general formula (13):

(Wherein R ^5a , R ^5b , R ^6a and R ^6b each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogen atom, and q 1, q 2, s 1 and s 2 are each independently And an integer of 1 to 4 is shown.)
The method according to any one of [5] to [7], further comprising a structural unit derived from at least one selected from the group consisting of a dihydroxy compound represented by the formula: oxyalkylene glycol and a diol having a cyclic acetal structure.
[9] A polycarbonate resin composition obtained by the method according to any one of [5] to [8].
[10] A molded article comprising the composition according to any one of [1] to [4] and [9].

  The polycarbonate resin composition of the present invention has high residence heat stability, low refractive index, excellent mechanical strength, color tone and transparency, and the glass transition temperature is adjusted from 45 ° C. to 155 ° C. depending on the application. It can be used for film, sheet field, heat resistance, bottle, container field, camera lens, viewfinder lens, CCD and CMOS lens, liquid crystal display and plasma display. It is possible to provide materials for a wide range of fields such as retardation films, diffusion sheets, polarizing films, and other optical films; sheets, optical disks, optical materials, optical components, dyes, binder applications that fix charge transfer agents, etc. is there. Moreover, according to the manufacturing method of the polycarbonate resin composition of this invention, the composition which has the said characteristic can be manufactured efficiently and stably.

DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.
The polycarbonate resin composition of the present invention has the following general formula (1):

A polycarbonate compound and / or a hindered phenol compound in a polycarbonate resin (a) (hereinafter sometimes referred to as “resin (a)”) containing at least a structural unit derived from a dihydroxy compound represented by the formula: Polycarbonate resin composition containing (b) (hereinafter sometimes abbreviated as “compound (b)”) and acidic compound (c) (hereinafter sometimes abbreviated as “compound (c)”) The content of the compound (b) is 0.001 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the resin (a), and the content of the compound (c) is in the resin (a). The amount is less than 1.0 equivalent relative to the amount of polymerization catalyst contained.

In the present invention, examples of the dihydroxy compound represented by the general formula (1) include isosorbide, isomannide, and isoidet, which are related to stereoisomers. These may be used alone or in combination of two kinds. A combination of the above may also be used.
Among these dihydroxy compounds, isosorbide obtained by dehydrating condensation of sorbitol produced from various starches that are abundant as resources and are readily available is easy to obtain and manufacture, optical properties, moldability From the viewpoint of

  Isosorbide is apt to be gradually oxidized by oxygen. Therefore, in order to prevent decomposition by oxygen during storage and handling during production, do not mix moisture, use an oxygen scavenger, or place under a nitrogen atmosphere. It is important to do. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate is produced using isosorbide containing these decomposition products, the resulting polycarbonate is colored or causes a significant deterioration in physical properties. In addition, the polymerization reaction may be affected, and a high molecular weight polymer may not be obtained. In addition, when a stabilizer for preventing the generation of formic acid is added, depending on the type of the stabilizer, coloring may occur in the obtained polycarbonate, or physical properties may be significantly deteriorated. As the stabilizer, a reducing agent or an antacid is used. Among them, examples of the reducing agent include sodium borohydride and lithium borohydride. Examples of the antacid include alkalis such as sodium hydroxide. Addition of such an alkali metal salt also serves as a polymerization catalyst, and if it is excessively added, the polymerization reaction may not be controlled.

  In order to obtain isosorbide containing no oxidative decomposition product, isosorbide may be distilled as necessary. Moreover, also when the stabilizer is mix | blended in order to prevent the oxidation and decomposition | disassembly of isosorbide, you may distill isosorbide as needed. In this case, the distillation of isosorbide may be simple distillation or continuous distillation, and is not particularly limited. After the atmosphere is an inert gas atmosphere such as argon or nitrogen, distillation is performed under reduced pressure.

For example, by performing such distillation for isosorbide, it is possible to achieve a high purity such that the formic acid content is less than 20 ppm, preferably 10 ppm or less, more preferably 5 ppm or less, and even more preferably 3 ppm or less. In the present invention, it is preferable to use these high-purity isosorbides, and it is particularly preferable to use those which do not contain any formic acid derived from the decomposition of the dihydroxy compound represented by the general formula (1). The method for measuring the formic acid content in isosorbide is as described later in the section of [Example].
In the present invention, an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, the following general formula (12)

(In the formula, Zb represents a single bond, an alkylidene group having 1 to 10 carbon atoms, a cycloalkylidene group having 4 to 15 carbon atoms, a sulfonyl group, a sulfide group, an oxide group or a di (isopropylidene) phenylene group, and R ^4a And R ^4b each independently represents a hydrogen atom, a halogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and p1 and p2 each independently represent an integer of 1 to 4.)
A dihydroxy compound represented by the following general formula (13):

(Wherein R ^5a , R ^5b , R ^6a and R ^6b each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogen atom, and q 1, q 2, s 1 and s 2 are each independently And an integer of 1 to 4 is shown.)
The structural unit derived from at least 1 sort (s) chosen from the group which consists of the dihydroxy compound represented by these, oxyalkylene glycol, and the diol which has a cyclic acetal structure can further be included.

The aliphatic dihydroxy compound is not particularly limited as long as it has an alkylene group having 1 to 20 carbon atoms. Specific examples include ethylene glycol, 1,3-propanediol, and 1,2-propanediol. 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-heptanediol, 1,6-hexanediol and the like. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are preferable.
These aliphatic dihydroxy compounds may be used alone or in combination of two or more.

  As said alicyclic dihydroxy compound, the compound normally containing a 5-membered ring structure or a 6-membered ring structure is mentioned. The 6-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. When the alicyclic dihydroxy compound has a 5-membered or 6-membered ring structure, the heat resistance of the obtained polycarbonate can be increased. The number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, more preferably 30 or less. The higher this value, the higher the heat resistance, but the synthesis becomes difficult, the purification becomes difficult, and the price increases. The smaller the number of carbon atoms, the easier the purification and the easier it is to obtain.

Specific examples of the alicyclic dihydroxy compound containing a 5-membered ring structure or a 6-membered ring structure include alicyclic dihydroxy compounds represented by the following general formula (II) or (III).
HOH ₂ C—R ¹ —CH ₂ OH (II) HO—R ² —OH (III) (in the formulas (II) and (III), R ¹ and R ² are cycloalkyl groups having 4 to 20 carbon atoms, Or a C6-C20 cycloalkoxyl group is shown.)

As cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (II), in general formula (II), R ¹ is represented by the following general formula (IIa) (wherein R ³ is a carbon number of 1 to 12 alkyl groups or hydrogen atoms are included). Specific examples thereof include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like.

As tricyclodecane dimethanol and pentacyclopentadecane dimethanol, which are alicyclic dihydroxy compounds represented by the above general formula (II), in general formula (II), R ¹ is represented by the following general formula (IIb) (in the formula: , N represents 0 or 1).

As decalin dimethanol or tricyclotetradecane dimethanol which is an alicyclic dihydroxy compound represented by the above general formula (II), in general formula (II), R ¹ is represented by the following general formula (IIc) (wherein m represents 0 or 1). Specific examples thereof include 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, and the like.

Moreover, as norbornanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (II), various isomers in which R ¹ is represented by the following general formula (IId) in the general formula (II) Include. Specific examples thereof include 2,3-norbornane dimethanol, 2,5-norbornane dimethanol and the like.

The adamantane dimethanol, which is an alicyclic dihydroxy compound represented by the general formula (II), includes various isomers in which R ¹ is represented by the following general formula (IIe) in the general formula (II). Specific examples of such a material include 1,3-adamantane dimethanol.

Further, cyclohexanediol, which is an alicyclic dihydroxy compound represented by the general formula (III), in general formula (III), ^{R 2} is represented by the following general formula (IIIa) (wherein, ^{R 3} is 1 to carbon atoms 12 alkyl groups or hydrogen atoms are included). Specific examples thereof include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.

As tricyclodecanediol and pentacyclopentadecanediol, which are alicyclic dihydroxy compounds represented by the above general formula (III), in general formula (III), R ² represents the following general formula (IIIb) (wherein n Represents 0 or 1).

As decalin diol or tricyclotetradecane diol which is an alicyclic dihydroxy compound represented by the above general formula (III), in general formula (III), R ² is represented by the following general formula (IIIc) (where m is 0 or 1 is represented)). Specifically, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol and the like are used as such.

The norbornanediol which is an alicyclic dihydroxy compound represented by the above general formula (III) includes various isomers in which R ² is represented by the following general formula (IIId) in the general formula (III). Specifically, 2,3-norbornanediol, 2,5-norbornanediol, and the like are used as such.

The adamantanediol which is an alicyclic dihydroxy compound represented by the above general formula (III) includes various isomers in which R ² is represented by the following general formula (IIIe) in the general formula (III). Specifically, 1,3-adamantanediol or the like is used as such.

Among the specific examples of the alicyclic dihydroxy compounds described above, cyclohexane dimethanols, tricyclodecane dimethanols, adamantane diols, and pentacyclopentadecane dimethanols are particularly preferable, and are easily available and easy to handle. From this viewpoint, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecane dimethanol are preferable.
These alicyclic dihydroxy compounds may be used individually by 1 type, and may use 2 or more types together.

  In the dihydroxy compound represented by the general formula (12), Zb is a single bond, an alkylidene group having 1 to 10 carbon atoms, a cycloalkylidene group having 4 to 15 carbon atoms, a sulfonyl group, a sulfide group, an oxide group or di ( An isopropylidene) phenylene group, preferably a single bond, an alkylidene group having 1 to 6 carbon atoms, a cycloalkylidene group having 5 to 10 carbon atoms, a di (isopropylidene) phenylene group, more preferably a single bond or carbon. An alkylidene group having 1 to 4 carbon atoms, a cycloalkylidene group having 6 to 9 carbon atoms, and more preferably an isopropylidene group or a di (isopropylidene) phenylene group.

R ^4a and R ^4b are each independently a hydrogen atom, a halogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably Is a hydrogen atom. R ^4a and R ^4b may be the same or different from each other, but are usually the same. R ^4a (or R ^4b ) may be different or the same in the same benzene ring.
In addition, the substitution position of R ^4a (or R ^4b ) is not particularly limited, and can be substituted at an appropriate position at the 2-6 position of the phenyl group depending on the number of substitutions m and n.
Preferable substitution numbers p1 and p2 are each independently an integer of 1 to 4, more preferably an integer of 1 or 2.

  Specific examples of the dihydroxy compound represented by the general formula (12) include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1 , 1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2- Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1 -Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, (4-hydroxyphenyl) diphenylmethane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′- Bisphenols such as dimethyldiphenylsulfone, 4,4 ′-(m-phenylenediisopropylidene) diphenol, and 4,4 ′-(p-phenylenediisopropylidene) diphenol are exemplified.

Among these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) or 4,4 ′-(m-phenylenediisopropylidene) diphenol is preferable.
These dihydroxy compounds represented by the general formula (12) may be used alone or in combination of two or more.

In the dihydroxy compound represented by the general formula (13), R ^5a , R ^5b , R ^6a and R ^6b are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogen atom, preferably Is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ^5a (or R ^5b , R ^6a , or R ^6b ) may be substituted alone or in combination of two or more with a benzene ring. R ^5a , R ^5b , R ^6a and R ^6b may be the same as or different from each other. In addition, the substitution position of R ^5a (or R ^5b , R ^6a or R ^6b ) is not particularly limited, and the 2-6 positions of the phenyl group depending on the number of substitutions q1 (or q2, or s1 or s2), etc. Can be substituted at any appropriate position. The substitution numbers q1, q2, s1, and s2 are the same or different integers of 1 to 4, preferably 1 or 2.
The substitution position of the hydroxyl group in the general formula (13) can be selected from the 2-6 positions of the phenyl group substituted at the 9th position of fluorene, preferably 2 or 4 positions, more preferably 4 positions.

Specific examples of the dihydroxy compound represented by the general formula (13) include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9 , 9-bis (2-hydroxy-5-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-propylphenyl) fluorene, 9,9-bis (4-hydroxy-3-isopropylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-isobutylphenyl) ) Fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy) 2,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-diethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dipropylphenyl) fluorene, 9-bis (4-hydroxy-3,5-diisopropylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-di-n-butylphenyl) fluorene, 9,9-bis (4-hydroxy-) 3,5-diisobutylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9,9-bis (4 -Hydroxy-3,5-diphenylphenyl) fluorene, 9,9-bis (4-hydroxy-3-benzylphenyl) fluorene, , 9-bis (4-hydroxy-3,5-dibenzylphenyl) fluorene, 9,9-bis (4-hydroxy-3-propenylphenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) ) 9,9-bis (hydroxyphenyl) fluorenes such as fluorene.

Among these, 9,9-bis (hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene are preferable.
These dihydroxy compounds represented by the general formula (13) may be used alone or in combination of two or more.
In addition, the compound represented by General formula (13) can be obtained by reaction with fluorenones (9-fluorenone etc.) and corresponding phenols. For example, 9,9-bis (4-hydroxyphenyl) fluorene can be obtained by reaction of phenol with 9-fluorenone.

Examples of the oxyalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol. These compounds may be used individually by 1 type, and may use 2 or more types together.
Examples of the diols having a cyclic acetal structure include spiroglycol and dioxane glycol.

  In addition, the said exemplary compound is an example of the dihydroxy compound which can be used as a structural unit of polycarbonate resin by this invention, Comprising: It is not limited to these at all. These compounds can be used alone or in combination with a dihydroxy compound represented by the general formula (1). Hereinafter, these dihydroxy compounds may be referred to as “other dihydroxy compounds”.

  By using these other dihydroxy compounds, effects such as improvement in flexibility, improvement in heat resistance, improvement in moldability, improvement in mechanical strength, and the like can be obtained. The ratio of the dihydroxy compound represented by the general formula (1) to the total dihydroxy compound constituting the polycarbonate resin used in the present invention is not particularly limited, but is usually 10 mol% or more, preferably 40 mol% or more, more preferably 50 mol. % Or more, more preferably 60 mol% or more, preferably 95 mol% or less, more preferably 90 mol% or less. When the content ratio of the structural unit derived from other dihydroxy compounds is too large, the performance of the original optical characteristics may be deteriorated.

  Among the other dihydroxy compounds, when an alicyclic dihydroxy compound is used, the total ratio of the dihydroxy compound represented by the general formula (1) and the alicyclic dihydroxy compound with respect to all the dihydroxy compounds constituting the polycarbonate is particularly limited. However, it is preferably at least 80 mol%, more preferably at least 90 mol%, particularly preferably at least 95 mol%.

  Moreover, about the content rate of the structural unit derived from the dihydroxy compound represented by General formula (1) and the structural unit derived from an alicyclic dihydroxy compound in the polycarbonate obtained by this invention, it can select in arbitrary ratios. Is a structural unit derived from the dihydroxy compound represented by the general formula (1): structural unit derived from the alicyclic dihydroxy compound = 1: 99 to 99: 1 (mol%), particularly represented by the general formula (1). The structural unit derived from the dihydroxy compound to be prepared: The structural unit derived from the alicyclic dihydroxy compound is preferably 10:90 to 90:10 (mol%). If the number of structural units derived from the dihydroxy compound represented by the general formula (1) is larger than the above range and the number of structural units derived from the alicyclic dihydroxy compound is small, it is easy to color, and conversely the general formula (1) When the number of structural units derived from the dihydroxy compound is small and the number of structural units derived from the alicyclic dihydroxy compound is large, the molecular weight tends to be difficult to increase.

Further, when an aliphatic dihydroxy compound, a dihydroxy compound represented by the general formula (12), a dihydroxy compound represented by the general formula (13), an oxyalkylene glycol, and a diol having a cyclic acetal structure are used, all the constituents of the polycarbonate The ratio of the sum total of the dihydroxy compound represented by General formula (1) and each of these dihydroxy compounds with respect to a dihydroxy compound is not specifically limited, It can select in arbitrary ratios.
Moreover, the content rate of the structural unit derived from the dihydroxy compound represented by General formula (1) and the structural unit derived from these each dihydroxy compound is not specifically limited, It can select in arbitrary ratios.

Here, the polymerization degree of the polycarbonate resin used in the present invention having a structural unit derived from the above-mentioned dihydroxy compound is determined by using a mixed solution of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 as a solvent. The reduced viscosity (hereinafter simply referred to as “reduced viscosity of polycarbonate”) measured at a temperature of 30.0 ° C. ± 0.1 ° C. with a polycarbonate concentration adjusted precisely to 1.00 g / dl is preferably 0. The polymerization degree is preferably 40 dl / g or more, more preferably 0.40 dl / g or more, and usually 2.0 dl / g or less, preferably 1.6 dl / g or less. When the polycarbonate reduced viscosity is extremely low, the mechanical strength when molded into a lens or the like is weak. Further, when the reduced viscosity of the polycarbonate is increased, the fluidity at the time of molding is lowered, the cycle characteristics are lowered, the molding cycle is lengthened, and the birefringence of the obtained molded product tends to be increased.
In addition, the specific measuring method of reduced viscosity is as showing in the item of [Example] mentioned later.

The 5% heat loss temperature of the polycarbonate resin or resin composition of the present invention is preferably 340 ° C. or higher, more preferably 345 ° C. or higher. The higher the 5% heat loss temperature, the higher the thermal stability, and the higher the heat resistance, the higher the heat resistance. The lower the temperature, the lower the thermal stability, making it difficult to use at high temperatures. In addition, the allowable control width at the time of manufacture becomes narrow and difficult to make. In addition, the manufacturing temperature can be increased, and the control range at the time of manufacturing can be widened. Therefore, the upper limit of the 5% heat loss temperature is not particularly limited, and the higher the better, the higher the decomposition temperature of the copolymer.

The 5% heat loss temperature is, for example, “TG-DTA” (SSC-5200, TG / DTA220) manufactured by Seiko Electronics, and 10 mg of the sample is placed in an aluminum container and under a nitrogen atmosphere (nitrogen flow rate 200 ml / min) The temperature can be measured from 30 ° C. to 450 ° C. at a heating rate of 10 ° C./min, and the temperature can be measured when the 5% weight is reduced.
The Izod impact strength of the polycarbonate resin or resin composition of the present invention is preferably 30 J / m ² or more. The greater the Izod impact strength, the higher the strength of the molded body and the less likely it will break, so the upper limit is not particularly limited.

  The Izod impact strength is, for example, a temperature of 240 to 300 ° C., a length of 31.5 mm, a width of 6.1.5 mm using a custom scientific minimax injection molding machine “CS-183MMX”. A test piece of 2 mm and a thickness of 3.2 mm is injection-molded, and a notch with a depth of 1.2 mm is attached with a notching machine to form a test piece. This test piece is a custom scientif. It can be measured as a notched Izod impact strength at 23 ° C. using an Izod impact tester “CS-183TI type”.

  Further, the polycarbonate resin or resin composition of the present invention gives a single glass transition temperature when differential scanning calorimetry (DSC) is performed, but the dihydroxy compound represented by the general formula (1) and other dihydroxy compounds. By adjusting the kind and compounding ratio of the compounds, the glass transition temperature can be obtained as a polymer having an arbitrary glass transition temperature from about 45 ° C. to about 155 ° C. depending on the application.

  For example, in a film application that requires flexibility, the glass transition temperature of the polycarbonate is 45 ° C. or higher, for example, 45 to 100 ° C., and in a molded object such as a bottle or pack that requires a certain degree of heat resistance, The glass transition temperature is preferably adjusted to 90 ° C. or higher, for example, 90 to 130 ° C. Furthermore, when the glass transition temperature is 120 ° C. or higher, it is suitable for lens applications. That is, it is preferable to have such a glass transition temperature because deformation hardly occurs even under a high temperature and high humidity such as a temperature of 85 ° C. and a relative humidity of 85%, and there is little variation in lens surface accuracy.

The polycarbonate resin (a) can be produced by melt polycondensation of the dihydroxy compound and the carbonic acid diester in the presence of a polymerization catalyst.
Examples of the carbonic acid diester used in the melt polymerization method include those represented by the following general formula (2).

(In the formula, A and A ′ are an optionally substituted aliphatic group having 1 to 18 carbon atoms or an optionally substituted aromatic group, and A and A ′ are the same. Or different.)
Examples of the carbonic acid diester represented by the general formula (2) include diphenyl carbonate, substituted diphenyl carbonate represented by ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Particularly preferred are diphenyl carbonate and substituted diphenyl carbonate. These carbonic acid diesters may be used alone or in combination of two or more.

The carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.10, more preferably in a molar ratio of 0.96 to 1.04, with respect to all dihydroxy compounds used in the reaction. When this molar ratio is smaller than 0.90, the terminal OH group of the produced polycarbonate resin is increased, and the thermal stability of the polymer is deteriorated or a desired high molecular weight product cannot be obtained. Further, when this molar ratio is larger than 1.10, the rate of the transesterification reaction decreases under the same conditions, and it becomes difficult to produce a polycarbonate resin having a desired molecular weight. The amount of residual carbonic acid diester increases, and this residual carbonic acid diester may cause odor of the molded product or the molded product.

In addition, the use ratio of the dihydroxy compound represented by the general formula (1) and the other dihydroxy compound is as described above as the ratio of the structural unit derived from each dihydroxy compound constituting the polycarbonate resin used in the present invention. .
Moreover, as a polymerization catalyst (transesterification catalyst) in melt polymerization, an alkali metal compound and / or an alkaline earth metal compound is used. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination with an alkali metal compound and / or an alkaline earth metal compound. It is particularly preferred to use only metal compounds and / or alkaline earth metal compounds.

  Examples of the alkali metal compound used as the polymerization catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate. , Lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, Cesium borohydride, sodium phenyl borohydride, potassium phenyl borohydride, lithium phenyl borohydride, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, benzoic acid Cium, 2 sodium hydrogen phosphate, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, Sodium, potassium, lithium, cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt and the like.

Examples of the alkaline earth metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, Examples thereof include magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.
These alkali metal compounds and / or alkaline earth metal compounds may be used alone or in combination of two or more.

Specific examples of basic boron compounds used in combination with alkali metal compounds and / or alkaline earth metal compounds include, for example, tetramethylboron, tetraethylboron,
Tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyl Examples thereof include sodium salts such as triphenylboron and butyltriphenylboron, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, and strontium salts.

Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.

  Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.

These basic compounds may be used alone or in combination of two or more.
When using an alkali metal compound and / or an alkaline earth metal compound, the amount of the polymerization catalyst used is usually in the range of 0.1 to 100 μmol as a metal conversion amount with respect to 1 mol of all dihydroxy compounds used in the reaction. Is preferably used within the range of 0.5 to 50 μmol, and more preferably within the range of 1 to 25 μmol. If the amount of the polymerization catalyst used is too small, the polymerization activity necessary to produce a polycarbonate resin having a desired molecular weight cannot be obtained. On the other hand, if the amount of the polymerization catalyst used is too large, the hue of the resulting polycarbonate resin deteriorates. However, by-products are generated and fluidity is lowered and gel is generated more frequently, making it difficult to produce a polycarbonate resin having a target quality.

In the present invention, the dihydroxy compound represented by the general formula (1) may be supplied as a solid, heated and supplied in a molten state, or supplied as an aqueous solution.
On the other hand, other dihydroxy compounds may be supplied as a solid, heated and supplied in a molten state, or may be supplied as an aqueous solution as long as it is soluble in water.
When these raw material dihydroxy compounds are supplied in a molten state or in an aqueous solution, there is an advantage that they can be easily measured and transported when industrially produced.

  In the present invention, a method in which a dihydroxy compound containing at least the dihydroxy compound represented by the general formula (1) is reacted with a carbonic acid diester in the presence of a polymerization catalyst is usually a series of a tank reactor and a horizontal reactor. It is carried out in a multi-stage process of two or more stages using a reactor connected to. Specifically, the first stage reaction is carried out at a temperature of 140 to 220 ° C., preferably 150 to 200 ° C. for 0.1 to 10 hours, preferably 0.5 to 3 hours. From the second stage onward, the reaction temperature is raised while gradually reducing the pressure of the reaction system from the pressure of the first stage, and at the same time, the phenol generated at the same time is removed from the reaction system. Is 200 Pa or less and a polycondensation reaction is performed under the temperature range of 210-280 degreeC.

  Here, as described above, the reactor to be used is one in which at least a tank reactor and a horizontal reactor are connected in series. The number of reactors to be connected is not particularly limited, but is 2 or more, preferably 3 to 7, and a multi-tank continuous reaction apparatus in which a plurality of reactors are connected is preferable. In this case, the first-stage reactor is preferably a vertical type and the final-stage reactor is preferably a horizontal type. The reactors may be connected directly or via a preheater or the like, if necessary.

Further, it is important to control the balance between the temperature and the pressure in the reaction system in the pressure reduction in the polycondensation reaction. In particular, if either one of the temperature and the pressure is changed too quickly, unreacted monomers are distilled out, the molar ratio of the dihydroxy compound and the carbonic acid diester may be changed, and the degree of polymerization may be lowered. For example, as a dihydroxy compound, isosorbide and 1,4-
When cyclohexane dimethanol is used, when the molar ratio of 1,4-cyclohexane dimethanol is 50 mol% or more with respect to all dihydroxy compounds, 1,4-cyclohexane dimethanol is easily distilled out as a monomer. The pressure in the reaction system is reduced under a reduced pressure of about 13 kPa while the temperature is increased at a rate of temperature increase of 40 ° C. or less per hour, and further, the pressure is increased up to about 6.67 kPa at a temperature of 40 per hour. When the polycondensation reaction is performed at a temperature of 200 to 250 ° C. at a temperature of 200 Pa or lower at a temperature rising rate of not higher than 200 ° C., a polycarbonate resin having a sufficiently increased degree of polymerization is preferably obtained.

  In addition, when the molar ratio of 1,4-cyclohexanedimethanol is less than 50 mol% with respect to all dihydroxy compounds, particularly when the molar ratio is 30 mol% or less, 1,4-cyclohexanedimethanol Compared with the case where the molar ratio is 50 mol% or more, the viscosity rises rapidly. For example, the temperature is increased at a rate of 40 ° C. or less per hour until the pressure in the reaction system is reduced to about 13 kPa. And the reaction is carried out at a pressure of up to about 6.67 kPa while increasing the temperature at a rate of temperature rise of 40 ° C. or more, preferably at a rate of temperature rise of 50 ° C. or more per hour. When a polycondensation reaction is finally performed at a temperature of 220 to 290 ° C. under a reduced pressure of 200 Pa or less, a polycarbonate resin having a sufficiently increased degree of polymerization is obtained. .

  The polycarbonate resin composition of the present invention is a polycarbonate resin composition containing a phosphorus compound and / or a hindered phenol compound (b) and an acidic compound (c) in the polycarbonate resin (a), wherein the compound ( The content of b) is 0.001 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the resin (a), and the content of the compound (c) is based on the amount of polymerization catalyst contained in the resin (a). Less than 1.0 equivalent.

  The compound (b) is a substance having an antioxidant function of the polycarbonate resin, and the content thereof is 0.001 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the resin (a). 0.005 parts by weight or more, more preferably 0.01 parts by weight or more, and the upper limit is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, and even more preferably 1 part by weight or less. When the content of the compound (b) is more than the upper limit, the surface appearance of the molded article using the polycarbonate resin composition tends to be poor, and when it is less than the lower limit, the antioxidant function tends to be lowered.

The compound (c) is a substance having a deactivation function of the polymerization catalyst, and the content thereof is less than 1.0 equivalent with respect to the polymerization catalyst content contained in the resin (a), but preferably 0. Less than 6 equivalents, more preferably 0.5 equivalents or less. As specifically shown in the examples described later, when the content of the compound (c) is within this range, a composition having no coloration and excellent color tone can be obtained.
The phosphorus compound of the compound (b) is not particularly limited as long as it is a neutral substance and has an antioxidant function. For example, phosphoric acid esters and phosphites are preferable compounds.

Examples of phosphate esters include bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphate, pentaerythrityl (2,4-di-t-butylphenyl) phosphate (2,4-di-). t-butylphenyl) phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythrityl diphosphate, pentaerythrityl (2,6-di-t-butyl-4-methylphenyl) Phosphate (2,6-di-t-butyl-4-methylphenyl) phosphite, bis (nonylphenyl) pentaerythrityl diphosphate, pentaerythrityl (nonylphenyl) phosphate (nonylphenyl) phosphite, diphenyldecyl phosphate, Diphenyl isooctyl phosphate, phenyl diisooctyl phosphate 2-ethylhexyl diphenyl phosphate, tetraphenyl propylene glycol diphosphate, propylene glycol diphenyl phosphate diphenyl phosphite, tetrakis (tridecyl) -4,4'-isopropylidene diphenyl diphosphate, 4,4'-isopropylidenediphenyl bis ( Arylalkyl phosphates such as tridecyl) phosphate bis (tridecyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphate; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, trino Nyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythryl diphosphate , Pentaerythryl stearyl phosphate stearyl phosphite, bis (tridecyl) pentaerythrityl diphosphate, pentaerythritol tridecyl phosphate, tridecyl phosphite, tris (2-chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate Trialkyl phosphates such as tricyclohexyl phosphate; triphenyl phosphate, tricresyl phosphate, tris (ethylphenyl) phosphate, tris (2,4-di-t-butylphenyl) phosphate, tris Triaryl phosphates such as (nonylphenyl) phosphate and tris (hydroxyphenyl) phosphate; hydrogenated bisphenol-A and pentaerythrityl phosphate Polymers such as Feto are go up.

Among these, allyl alkyl phosphates, especially bis (2,4-di-t-butylphenyl) pentaerythrityl phosphate and triaryl phosphates, particularly tris (2,4-di-t-butylphenyl) phosphate, etc. Is preferred.
These phosphate esters may be used alone or in combination of two or more.

  Examples of the phosphite ester include bis (2,4-di-t-butylphenyl) pentaerythrityl diphosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythrate. Lithyl diphosphite, bis (nonylphenyl) pentaerythrityl diphosphite, diphenyldecyl phosphite, diphenylisooctyl phosphite, phenyldiisooctyl phosphite, 2-ethylhexyl diphenyl phosphite, tetraphenylpropylene glycol diphosphite, Tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene diphosphite, tetrakis (tridecyl) -4,4′-isopropylidene diphenyl diphosphite, 2,2-methylenebis (4,6- Di-t-butylphenyl) octi Phosphite, 2-{{2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo {d, f} {1,3,2} dioxaphosphin 6-yl} oxy} -N , N-bis {2-{{2,4,8,10-tetrakis (1,1 dimethylethyl) dibenzo {d, f} {1,3,2} dioxaphosphin 6-yl} oxy}- Aryl} phosphines such as ethyl} ethanamine; trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, trioctadecyl phosphite, distearyl pentaerythryl diphos Phyto, bis (tridecyl) pentaerythrityl diphosphite, tris (2-chloroethyl) phosphite, Trialkyl phosphites such as lith (2,3-dichloropropyl) phosphite; tricycloalkyl phosphites such as tricyclohexyl phosphite; triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite , Triaryl phosphites such as tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (hydroxyphenyl) phosphite; hydrogenated bisphenol-A and pentaerythrityl phos Examples include phytopolymers.

Among these, arylalkyl phosphites, particularly bis (2,4-t-butylphenyl) pentaerythrityl diphosphite, bis (2,6-t-butylphenyl) pentaerythrityl diphosphite, tetrakis ( 2,4-di-tert-butylphenyl) 4,4 ′
-Biphenylene diphosphites and trialkyl phosphites, in particular distearyl pentaerythryl diphosphites, and triaryl phosphites, in particular tris (2,4-di-t-butylphenyl) phosphite, are preferred.
These phosphites may be used alone or in combination of two or more.

  The hindered phenol compound of the compound (b) is not particularly limited as long as it has an antioxidant function. For example, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di) -T-butylphenyl) propionate, tetrakis {methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate} methane, distearyl (4-hydroxy-3-methyl-5-t -Butylbenzyl) malonate, triethyleneglycol-bis {3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4 Hydroxyphenyl) propionate}, 2,2-thiodiethylenebis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 2,2-thiobis (4-methyl-6-tert-butylphenol) ), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxy) Benzyl) -isocyanurate, 2,4-bis {(octylthio) methyl} -o-cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,5,7, 8-tetramethyl-2 (4 ′, 8 ′, 12′-trimethyltridecyl) chroman-6-ol, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl- , A ', a "- (mesitylene-2,4,6-triyl) tri -p- cresol.

Among these, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate}, 3,3 ′, 3 ″, 5,5 ′,
5 "-hexa-t-butyl-a, a ', a'-(mesitylene-2,4,6-triyl) tri-p-cresol, 2,2-thiodiethylenebis {3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate} and the like are preferable.
These hindered phenol compounds may be used alone or in combination of two or more. Further, a phosphorus compound and a hindered phenol compound may be used in combination.

Further, the compound (c) is not particularly limited as long as it is an acidic substance and has a deactivation function of the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetraoctyl sulfonate tetra Phosphonium salts such as butylphosphonium salt, benzenesulfonic acid tetramethylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, P-toluenesulfonic acid tetrabutylphosphonium salt; decylsulfonic acid tetramethylammonium salt Ammonium salts such as tetrabutylammonium dodecylbenzenesulfonate; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, hexade And the like alkyl esters such as Rusuruhon ethyl.
Of these, phosphoric acid and phosphorous acid are preferred.
These acidic compounds may be used alone or in combination of two or more.

In the present invention, the phosphorus compound and / or the hindered phenol compound (b) can be added when the polycarbonate resin is produced by a melt polymerization method, but after the polymerization reaction is completed, the acidic compound (c) or It is preferable to add and knead together with a heat stabilizer and other antioxidants.
Furthermore, in order to prevent a decrease in molecular weight and a deterioration in hue at the time of molding or the like, another antioxidant can be further blended with the polycarbonate resin composition of the present invention at the same time as the above addition and kneading.

  Examples of such antioxidants include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl-3,3′-thiodipropionate, 1-ditridecyl-3,3′-thiopropionate, penta Erythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3- (3-tert-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3 , 5-Di-tert-butyl-4 Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-) tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4- Hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy -5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy} -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2- (3,5-di-t-butyl-4-hydroxy Benzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) and the like.

These antioxidants may be used alone or in combination of two or more.
Further, the blending amount of these antioxidants is preferably 0.0001 to 1 part by weight when the polycarbonate is 100 parts by weight.
Further, the polycarbonate resin composition of the present invention can be blended with a mold release agent within a range that does not impair the object of the present invention in order to further improve the mold release from the mold during melt molding. .

Such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefinic waxes, olefinic waxes containing carboxy groups and / or carboxylic anhydride groups, silicone oils, And organopolysiloxane.

The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include, for example, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, stearyl stearate, behenic acid monoglyceride, behenic acid Behenyl, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphene -To, sorbitan monostearate, 2-ethylhexyl stearate and the like.
Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.
These release agents may be used alone or in combination of two or more.
The amount of the release agent is preferably 0.01 to 5 parts by weight when the polycarbonate resin is 100 parts by weight.
The polycarbonate resin composition of the present invention can be blended with a light stabilizer as long as the object of the present invention is not impaired.

  Examples of such a light stabilizer include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro. Benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2 ′ -Methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazin-4-one) and the like.

These light stabilizers may be used alone or in combination of two or more.
The blending amount of the light stabilizer is preferably 0.01 to 2 parts by weight when the polycarbonate resin is 100 parts by weight.
In addition, the polycarbonate resin composition of the present invention can be blended with a bluing agent in order to counteract the yellowishness of the lens based on the polymer or the ultraviolet absorber. Any bluing agent can be used without any problem as long as it is used in a polycarbonate resin composition. In general, anthraquinone dyes are preferred because they are readily available.

As a specific bluing agent, for example, the general name Solvent Violet 13 [CA. No (color index No) 60725], generic name Solvent Violet 31 [CA. No 68210, generic name Solvent Violet 33 [CA. No. 60725], generic name Solvent Blue 94 [CA. No 61500], generic name Solvent Violet 36 [CA. No. 68210], common name Solvent Blue 97 [manufactured by Bayer "Macrolex Violet RR"] and general name Solvent Blue 45 [CA. No. 61110] is given as a representative example.
These bluing agents may be used individually by 1 type, and may use 2 or more types together.
These blueing agents are usually blended at a ratio of 0.1 × 10 ⁻⁴ to 2 × 10 ⁻⁴ parts by weight when the polycarbonate resin is 100 parts by weight.

  Formulation of the polycarbonate resin composition of the present invention and the above-mentioned various additives is, for example, a method of mixing with a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, extruder, etc., Alternatively, there is a solution blending method in which the above components are mixed in a state of being dissolved in a common good solvent such as methylene chloride. However, this is not particularly limited, and any commonly used polymer blending method may be used. Any method may be used.

  The polycarbonate resin composition thus obtained, or the polycarbonate resin composition obtained by blending various additives and other resins with the polycarbonate resin composition as it is or after being once pelletized with a melt extruder, is then subjected to an injection molding method or an extrusion molding method. Various types of molded articles such as films, sheets, bottles and containers; lenses such as camera lenses, viewfinder lenses, CCD and CMOS lenses; liquid crystals and plasma displays Optical films such as retardation films, diffusion sheets, and polarizing films; other optical materials such as optical disks and optical waveguides, and optical components.

  As described above, there is no particular limitation on the apparatus used for adding and kneading the compound (b) or the compound (c) to the polycarbonate resin, but the moldability of the polycarbonate resin is increased to obtain stable release properties and various physical properties. Therefore, it is preferable to use a single screw extruder or a twin screw extruder in the melt extrusion. A method using a single screw extruder or a twin screw extruder does not use a solvent or the like, has a small environmental load, and can be preferably used from the viewpoint of productivity.

  The upper limit of the addition / kneading temperature in the extruder is 270 ° C. or lower, and the lower limit is not particularly limited as long as the polycarbonate resin can be kneaded and kept in a molten state. The addition / kneading temperature depends on the glass transition temperature of the polycarbonate resin. When the glass transition temperature of the polycarbonate is lower than 90 ° C, the melt kneading temperature of the extruder is usually from 130 ° C to 250 ° C, preferably from 150 to 240 ° C. If the melt kneading temperature is lower than 130 ° C., the melt viscosity of the polycarbonate is high, the load on the extruder is increased, and the productivity is lowered. When it is higher than 250 ° C., the melt viscosity of the polycarbonate becomes low, and it becomes difficult to obtain pellets, and the productivity is lowered.

  When the glass transition temperature of the polycarbonate resin is 90 ° C. or higher, the melt kneading temperature of the extruder is usually 200 to 270 ° C., preferably 220 ° C. to 260 ° C. When the melt kneading temperature is lower than 200 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 270 ° C., the polycarbonate resin is likely to be deteriorated, and the color of the polycarbonate resin is yellowed or the molecular weight is lowered, so that the strength is deteriorated.

The addition / kneading is preferably performed in an atmosphere in which no oxidizing gas such as oxygen is mixed, and is preferably performed at least at an oxygen concentration of 1% or less, and further 0.5% or less.
In order to reduce the oxygen concentration to 1% or less, the oxygen concentration is lowered by sending an inert gas such as nitrogen into the material inlet at the time of addition and kneading.

  When using an extruder, it is desirable to install a filter in order to prevent the polycarbonate resin composition from being burned and mixed with foreign matters during extrusion. The size (opening) of the filter for removing foreign substances depends on the required optical accuracy, but is preferably 100 μm or less. In particular, it is preferably 40 μm or less, more preferably 20 μm or less when foreign matter is disliked, and 10 μm or less when foreign matter is desired.

The extrusion of the polycarbonate resin composition is desirably performed in a clean room in order to prevent foreign matter from being mixed after the extrusion.
Moreover, when cooling the extruded polycarbonate resin composition into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air. When water cooling is used, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. There are various sizes (openings) of filters to be used, but those having a filter of 10 to 0.45 μm are preferable.

  For molding a lens using the polycarbonate resin composition of the present invention, an injection molding machine or an injection compression molding machine is suitable, and the mold surface temperature and the resin temperature are particularly important as molding conditions at this time. These molding conditions cannot be generally defined by the composition and degree of polymerization of the polycarbonate resin, but the mold surface temperature is preferably 30 ° C. or higher and 170 ° C. or lower, and the resin temperature at this time is 220 ° C. or higher and 270 ° C. or lower. It is good to be. When the mold surface temperature is 30 ° C. or lower, both the fluidity and transferability of the resin are poor, stress strain remains during injection molding, and the birefringence tends to increase, and the mold temperature is 170. When it is higher than ° C., the transferability is good, but it is easily deformed at the time of release. On the other hand, when the resin temperature is 270 ° C. or higher, the resin is easily decomposed, which causes a reduction in strength and coloring of the molded product. In addition, the molding cycle is extended, which is not economical.

  When molding optical materials and optical components from the polycarbonate resin composition of the present invention, starting with a raw material charging step, a polymerization step, and a step of extruding the obtained copolymer into a refrigerant to form a pellet or a sheet Then, it is desirable to carry out with care so that dust and the like do not enter. This cleanness is usually class 1000 or less for compact discs and class 100 or less for more advanced information recording.

The polycarbonate resin composition of the present invention is used, for example, for members such as a retardation film represented by a liquid crystal display, a viewing angle widening film, a polarizer protective film, a prism sheet, a diffusion sheet, a reflective sheet, and a surface antireflection film. It can be particularly suitably used for optical films such as films and sheets and release films and protective films used in the production process.
The polycarbonate resin composition of the present invention can also be used as a binder for immobilizing sheets, optical disks, optical materials, optical components, dyes, charge transfer agents and the like.

The polycarbonate resin composition of the present invention includes, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS, and other synthetic resins, polylactic acid, and polybutylene succinate. It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as rubber and rubber. These polymer alloys can also be used as the polycarbonate resin composition of the present invention.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.
In the following, the physical properties and characteristics of the polycarbonate resin were evaluated by the following methods.

(1) Reduced viscosity
Using an Ubbelohde viscometer with a DT-504 automatic viscometer manufactured by Chuo Rika Co., Ltd., using a 1: 1 mixed solvent of phenol and 1,1,2,2-tetrachloroethane as the solvent, and a temperature of 30.0 ° C. ± 0 Measured at 1 ° C. The concentration was precisely adjusted to be 1.00 g / dl.
The sample was dissolved in 30 minutes while stirring at 120 ° C., and used for measurement after cooling.
From the passage time t0 of the solvent and the passage time t of the solution, the relative viscosity ηrel is obtained from the following formula,
ηrel = t / t0 (g · cm ⁻¹ · sec ⁻¹ ) The specific viscosity ηsp was determined from the following formula from the relative viscosity ηrel.
ηsp = (η−η0) / η0 = ηrel−1
The specific viscosity ηsp was divided by the concentration c (g / dl) to obtain a reduced viscosity (converted viscosity) ηred from the following formula.
ηred = ηsp / c
The higher this number, the greater the molecular weight.

(2) Determination of formic acid The amount of formic acid contained in isosorbide was measured by ion chromatography as follows.
About 0.5 g of isosorbide was precisely weighed and collected in a 50 ml volumetric flask, and the volume was adjusted with pure water. An aqueous sodium formate solution was used as the standard sample, and the peak having the same retention time as that of the standard sample was formic acid.
As the ion chromatograph, DX-500 type manufactured by Dionex was used, and an electric conductivity detector was used as a detector. As measurement columns, AG-15 was used as a guard column manufactured by Dionex, and AS-15 was used as a separation column. The measurement sample was injected into a 100 μl sample loop, and 10 mM NaOH was used as an eluent, and the measurement was performed at a flow rate of 1.2 ml / min and a thermostat temperature of 35 ° C. A membrane suppressor was used as the suppressor and 12.5 mM-H was used as the regenerating solution.
_{A 2} SO ₄ aqueous solution was used.
In addition, the formic acid content of isosorbide (distilled by the following method) used for the production of the following polycarbonate resins A and B was 5 ppm.
Here, the distillation method of isosorbide used for the production of the following polycarbonate resins A and B is as follows.

<Distillation of isosorbide>
About 1.3 kg of isosorbide was placed in a 2 L flask under an argon stream, a Claisen tube was attached to the flask, and a receiver was attached through a fraction cutter. Heat was kept so that it did not solidify in each part such as piping. After gradually starting to reduce the pressure, the solution was heated and dissolved at an internal temperature of about 100 ° C. Thereafter, distillation started at an internal temperature of 160 ° C. The pressure at this time was 133-266 Pa. After the initial distillation, distillation was performed at an internal temperature of 160 to 170 ° C., a tower top temperature of 150 to 157 ° C., and 133 Pa. After completion of distillation, argon was added to return to normal pressure. The obtained distilled product was cooled and pulverized under an argon stream to obtain distilled and purified isosorbide. This product was sealed and stored at room temperature with AGELESS (Mitsubishi Gas Chemical Co., Ltd.) enclosed in an aluminum laminate bag under a nitrogen stream.

[Polycarbonate resin A]
13.0 parts by weight (0.246 moles) of 1,4-cyclohexanedimethanol (hereinafter abbreviated as “1,4-CHDM”) and 27.7 parts by weight of isosorbide (0.516 moles) Carbonate (hereinafter abbreviated as “DPC”) 59.2 parts by weight (0.752 mol) and 2.21 × 10 ⁻⁴ parts by weight (1.84 × 10 ⁻⁶ mol) of cesium carbonate as a catalyst were reacted. In a nitrogen atmosphere, as a first step of the reaction, the heating bath temperature was heated to 150 ° C., and the raw materials were dissolved while stirring as necessary (about 15 minutes).
Subsequently, the pressure was changed from normal pressure to 13.3 kPa, and the generated phenol was extracted out of the reaction vessel while the heating bath temperature was increased to 190 ° C. over 1 hour.

  After maintaining the entire reaction vessel at 190 ° C. for 15 minutes, as a second step, the pressure in the reaction vessel is set to 6.67 kPa, the heating bath temperature is increased to 230 ° C. in 15 minutes, and the generated phenol is removed. It was extracted out of the reaction vessel. Since the stirring torque of the stirrer increased, the temperature was raised to 250 ° C. in 8 minutes, and the pressure in the reaction vessel was allowed to reach 0.200 kPa or less in order to remove the generated phenol. After reaching a predetermined stirring torque, the reaction was terminated, and the produced reaction product was extruded into water to obtain polycarbonate copolymer pellets. The reduced viscosity of the obtained polycarbonate copolymer was 0.616 dl / g.

[Polycarbonate resin B]
15.8 parts by weight (0.211 moles) of tricyclodecane dimethanol (hereinafter abbreviated as “TCDDM”) and 57.4 parts by weight of DPC (0 parts by weight) with respect to 26.9 parts by weight (0.483 moles) of isosorbide. 709 moles) and 2.14 × 10 ⁻⁴ parts by weight (1.73 × 10 ⁻⁶ moles) of cesium carbonate as a catalyst are placed in a reaction vessel, and the first stage of the reaction is carried out in a nitrogen atmosphere. As a process, the heating bath temperature was heated to 150 ° C., and the raw materials were dissolved while stirring as necessary (about 15 minutes).
Subsequently, the pressure was reduced from normal pressure to 13.3 kPa over 40 minutes, and the generated phenol was extracted out of the reaction vessel while raising the heating bath temperature to 190 ° C. over 40 minutes.

  After maintaining the entire reaction vessel at 190 ° C. for 15 minutes, as the second step, the heating bath temperature was increased to 220 ° C. in 30 minutes. Ten minutes after entering the temperature rise, the pressure in the reaction vessel was reduced to 0.200 kPa or less in 30 minutes, and the generated phenol was distilled off. After reaching a predetermined stirring torque, the reaction was terminated, and the produced reaction product was extruded into water to obtain polycarbonate copolymer pellets. The reduced viscosity of the obtained polycarbonate copolymer was 0.464 dl / g.

[Example 1]
Adekastab PEP-36 (produced by Asahi Denka Co., Ltd., compound name: bis (2,6-t-butylphenyl) pentaerythrityl diphosphite), which is a phosphorus-based antioxidant, with respect to 100 parts by weight of the polycarbonate resin A A weight part was added and kneaded at 240 ° C. using a custom scientific mini-max injection molding machine “CS-183MMX” and allowed to stay in the molding machine at 240 ° C. for 30 minutes. Thereafter, injection molding was performed, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Example 2]
Example 1 0.5 parts by weight of ADK STAB PEP-36 (manufactured by Asahi Denka Co., Ltd., compound name: bis (2,6-t-butylphenyl) pentaerythrityl diphosphite) with respect to 100 parts by weight of the polycarbonate resin A The mixture was added and kneaded in the same manner as described above, and retained in a molding machine at 240 ° C. for 30 minutes, then injection molded, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Example 3]
Example 1 was carried out using 1.0 part by weight of ADK STAB PEP-36 (manufactured by Asahi Denka Co., Ltd., compound name: bis (2,6-t-butylphenyl) pentaerythrityl diphosphite) based on 100 parts by weight of the polycarbonate resin A. The mixture was added and kneaded in the same manner as described above, and retained in a molding machine at 240 ° C. for 30 minutes, then injection molded, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Example 4]
In the same manner as in Example 1, 0.01 parts by weight of Adekastab PEP-8 (produced by Asahi Denka Co., Ltd., compound name: distearyl pentaerythryl diphosphite), which is a phosphorus-based antioxidant, is added to 100 parts by weight of the polycarbonate resin A. The mixture was added and kneaded by the above method, retained in a molding machine at 240 ° C. for 30 minutes, then injection molded, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Example 5]
0.05 parts by weight of ADK STAB PEP-8 (manufactured by Asahi Denka Co., Ltd., compound name: distearyl pentaerythryl diphosphite) is added and mixed in the same manner as in Example 1 with respect to 100 parts by weight of the polycarbonate resin A. After smelting and retaining in a molding machine at 240 ° C. for 30 minutes, injection molding was performed, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Example 6]
In the same manner as in Example 1, 0.1 part by weight of ADK STAB PEP-8 (manufactured by Asahi Denka Co., Ltd., compound name: distearyl pentaerythryl diphosphite) was added and mixed with 100 parts by weight of the polycarbonate resin A. After smelting and retaining in a molding machine at 240 ° C. for 30 minutes, injection molding was performed, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Example 7]
In the same manner as in Example 1, 0.2 parts by weight of ADK STAB PEP-8 (manufactured by Asahi Denka Co., Ltd., compound name: distearyl pentaerythryl diphosphite) was added and mixed with 100 parts by weight of the polycarbonate resin A. After smelting and retaining in a molding machine at 240 ° C. for 30 minutes, injection molding was performed, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Example 8]
Sandstub P-EPQ (manufactured by Clariant Japan, compound name: tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenyl, which is a phosphorus-based antioxidant, with respect to 100 parts by weight of the polycarbonate resin A (Range phosphite) 0.2 parts by weight was added and kneaded in the same manner as in Example 1, and retained in a molding machine for 30 minutes at 240 ° C., then injection molded, and the reduced viscosity of the molded piece. The color tone was visually observed. The results are shown in Table 1.

[Example 9]
For 100 parts by weight of the polycarbonate resin A, 0.01 parts by weight of Adekastab PEP-8 (manufactured by Asahi Denka), which is a phosphorus antioxidant, and phosphorous acid (manufactured by Wako Pure Chemical Industries, Ltd.), which is an acidic compound, are polycarbonate resins. 0.5 equivalent to the amount of catalyst contained in the catalyst is added and kneaded in the same manner as in Example 1, and retained in a molding machine for 30 minutes at 240 ° C., then injection molded, and molded. The reduced viscosity of the piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Comparative Example 1]
Polycarbonate resin A alone was added and kneaded in the same manner as in Example 1, and was retained in a molding machine at 240 ° C. for 30 minutes, then injection molded, and the reduced viscosity of the molded piece was measured. The color tone was visually observed. The results are shown in Table 1.

[Comparative Example 2]
In the same manner as in Example 1, 1.0 equivalent to the amount of catalyst containing butyl p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is an acidic compound, is added to the polycarbonate resin A. -After kneading and retaining in a molding machine at 240 ° C for 30 minutes, injection molding was performed, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Comparative Example 3]
For polycarbonate resin A, 5.0 equivalents of p-toluenesulfonic acid butyl (manufactured by Tokyo Chemical Industry Co., Ltd.), which is an acidic compound, is added in the same manner as in Example 1 with respect to the amount of catalyst contained in the polycarbonate resin. -After kneading and retaining in a molding machine at 240 ° C for 30 minutes, injection molding was performed, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 1.

[Example 10]
Irganox 1010, a hindered phenol-based antioxidant (compound name: pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-), manufactured by Ciba Japan, based on 100 parts by weight of polycarbonate resin B 4-hydroxyphenyl) propionate}
) 0.1 part by weight was added and kneaded in the same manner as in Example 1, and was retained in the molding machine for 30 minutes at 240 ° C., then injection molded, and the reduced viscosity of the molded piece was measured. The color tone was observed visually. The results are shown in Table 2.

[Example 11]
Irganox 1010 (manufactured by Ciba Japan, compound name: pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}) 0 with respect to 100 parts by weight of polycarbonate resin B .2 parts by weight were added and kneaded in the same manner as in Example 1 and retained in a molding machine at 240 ° C. for 30 minutes, then injection molded, and the reduced viscosity of the molded piece was measured. The color tone was observed visually. The results are shown in Table 2.

[Example 12]
Irganox 1010 (manufactured by Ciba Japan, compound name: pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}) 0 with respect to 100 parts by weight of polycarbonate resin B .5 parts by weight were added and kneaded in the same manner as in Example 1 and retained in a molding machine for 30 minutes at 240 ° C., then injection molded, and the reduced viscosity of the molded piece was measured. The color tone was observed visually. The results are shown in Table 2.

[Example 13]
Irganox 1010 (manufactured by Ciba Japan, compound name: pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}) 1 with respect to 100 parts by weight of polycarbonate resin B 0.0 part by weight was added and kneaded in the same manner as in Example 1, and was retained in a molding machine at 240 ° C. for 30 minutes, then injection molded, and the reduced viscosity of the molded piece was measured. The color tone was observed visually. The results are shown in Table 2.

[Comparative Example 4]
Polycarbonate resin B alone was added and kneaded in the same manner as in Example 1 and retained in a molding machine for 30 minutes at 240 ° C., then injection molded, and the reduced viscosity of the molded piece was measured. The color tone was visually observed. The results are shown in Table 2.

[Comparative Example 5]
In the same manner as in Example 1, 1.0 equivalent to the amount of catalyst containing butyl p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is an acidic compound, is added to the polycarbonate resin B. -After kneading and retaining in a molding machine at 240 ° C for 30 minutes, injection molding was performed, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 2.

[Comparative Example 6]
To the polycarbonate resin B, 5.0 equivalents of the acidic compound p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) in the polycarbonate resin is added in the same manner as in Example 1. -After kneading and retaining in a molding machine at 240 ° C for 30 minutes, injection molding was performed, the reduced viscosity of the molded piece was measured, and the color tone was visually observed. The results are shown in Table 2.

In addition, the symbol of the compound in Table 1 and Table 2 is as follows.
PEP-36: ADK STAB PEP-36
P-EPQ: Sandstub P-EPQ
PEP-8: ADK STAB PEP-8
PTSB: butyl p-toluenesulfonate Irg1010: Irganox 1010

  The polycarbonate resin composition of the present invention is a film that requires flexibility, a sheet field, a bottle that requires heat resistance, a container field, various structural materials that require impact strength, a camera lens, a finder lens, and a CCD. Films such as lenses for CMOS and CMOS, retardation films used for liquid crystals and plasma displays, diffusion sheets, polarizing films, films, sheets, optical disks, films, sheets, optical materials, optical components, dyes and charge transfer agents It is suitable for use in applications such as a binder that immobilizes etc.

Claims (10)

The following general formula (1)

A polycarbonate resin composition containing a phosphorus compound and / or a hindered phenol compound (b) and an acidic compound (c) in a polycarbonate resin (a) containing at least a structural unit derived from a dihydroxy compound represented by The content of the compound (b) is 0.001 to 10 parts by weight with respect to 100 parts by weight of the resin (a), and the content of the compound (c) is contained in the resin (a). A polycarbonate resin composition characterized by being less than 1.0 equivalent relative to the amount of polymerization catalyst to be produced. Resin (a) is an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, the following general formula (12)

(In the formula, Zb represents a single bond, an alkylidene group having 1 to 10 carbon atoms, a cycloalkylidene group having 4 to 15 carbon atoms, a sulfonyl group, a sulfide group, an oxide group or a di (isopropylidene) phenylene group, and R ^4a And R ^4b each independently represents a hydrogen atom, a halogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and p1 and p2 each independently represent an integer of 1 to 4.)
A dihydroxy compound represented by the following general formula (13):

(Wherein R ^5a , R ^5b , R ^6a and R ^6b each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogen atom, and q 1, q 2, s 1 and s 2 are each independently And an integer of 1 to 4 is shown.)
The composition of Claim 1 which further contains the structural unit derived from at least 1 sort (s) chosen from the group which consists of the dihydroxy compound represented by these, oxyalkylene glycol, and the diol which has a cyclic acetal structure.   The composition according to claim 1 or 2, wherein the compound (b) is added and kneaded to the resin (a) at a temperature of 270 ° C or lower.   The composition according to claim 3, wherein the oxygen concentration during addition and kneading is 1% or less. The following general formula (1)

Of a polycarbonate resin composition containing at least a phosphorus compound and / or a hindered phenol compound (b) and an acidic compound (c) in a polycarbonate resin (a) containing at least a structural unit derived from a dihydroxy compound represented by A method for producing a polycarbonate resin composition, which comprises adding and kneading compound (b) to resin (a) at a temperature of 270 ° C. or less and an oxygen concentration of 1% or less.   The method according to claim 5, wherein the resin (a) is produced using a dihydroxy compound represented by the general formula (1) having a formic acid content of less than 20 ppm as a reaction raw material.   The content of the compound (b) is 0.001 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the resin (a), and the content of the compound (c) is the polymerization catalyst amount contained in the resin (a). The method according to claim 5 or 6, wherein the amount is less than 1.0 equivalent. Resin (a) is an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, the following general formula (12)

(In the formula, Zb represents a single bond, an alkylidene group having 1 to 10 carbon atoms, a cycloalkylidene group having 4 to 15 carbon atoms, a sulfonyl group, a sulfide group, an oxide group or a di (isopropylidene) phenylene group, and R ^4a And R ^4b each independently represents a hydrogen atom, a halogen atom, a phenyl group or an alkyl group having 1 to 4 carbon atoms, and p1 and p2 each independently represent an integer of 1 to 4.)
A dihydroxy compound represented by the following general formula (13):

(Wherein R ^5a , R ^5b , R ^6a and R ^6b each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a halogen atom, and q 1, q 2, s 1 and s 2 are each independently And an integer of 1 to 4 is shown.)
The method according to any one of claims 5 to 7, further comprising a structural unit derived from at least one selected from the group consisting of a dihydroxy compound represented by the formula: oxyalkylene glycol and a diol having a cyclic acetal structure.   A polycarbonate resin composition obtained by the method according to claim 5.   A molded article comprising the composition according to any one of claims 1 to 4 and claim 9.