JP5418166B2 - Polycarbonate resin composition and polycarbonate resin molded product - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a polycarbonate resin molded article.

  In recent years, it has been described that isosorbide, which is a plant-derived monomer, is used as a polycarbonate resin using raw materials obtained from biomass resources, and a polycarbonate resin is obtained by transesterification with diphenyl carbonate (see Patent Document 1). Patent Document 2 describes a polycarbonate resin obtained by copolymerizing isosorbide and bisphenol A. Patent Document 3 describes that the rigidity of a polycarbonate resin is improved by copolymerizing isosorbide and an aliphatic diol. Patent Document 4 describes that a polycarbonate resin obtained by homopolymerizing isosorbide is added with at least one heat stabilizer selected from the group consisting of a phosphorus heat stabilizer and a hindered phenol heat stabilizer.

British Patent 1,079,686 JP-A-56-055425 International Publication No. 2004/111106 Pamphlet International Publication No. 2008/133342

By the way, the polycarbonate resin obtained by using isosorbide as a plant-derived monomer is insufficient in terms of heat resistance, transparency, and mechanical strength as compared with a conventional aromatic polycarbonate derived from petroleum raw materials. Moreover, there exists a problem that it yellows at the time of melt molding and it is difficult to use as a transparent member or an optical member. In the prior art, a certain amount of yellowing can be suppressed, but the effect is not sufficient.
An object of the present invention is to provide a polycarbonate resin composition having at least a structural unit derived from a dihydroxy compound such as isosorbide, having excellent heat resistance, transparency, mechanical strength, and excellent color tone, and a molded product thereof. is there.

According to the present invention, a polycarbonate resin composition and a polycarbonate resin molded product according to the following claims are provided.
The invention according to claim 1 is a polycarbonate resin (a) 100 parts by weight containing at least a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure, and a phosphite antioxidant A polycarbonate resin composition comprising: (b) 0.0001 part by weight to 1 part by weight and sulfur-based antioxidant (c) 0.0001 part by weight to 1 part by weight.

(Unless moiety represented by the above general formula (1) is part of _-CH 2 -O-H.
)

  The invention according to claim 2 is the polycarbonate resin composition according to claim 1, wherein the dihydroxy compound having a portion represented by the general formula (1) in a part of the structure has a heterocyclic group. It is.

The invention according to claim 3 is characterized in that the dihydroxy compound having a site represented by the general formula (1) in a part of the structure is a compound represented by the following general formula (2). The polycarbonate resin composition according to 1 or 2.

  According to a fourth aspect of the present invention, the polycarbonate resin (a) further includes a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and an oxyalkylene glycol. It is a polycarbonate resin composition of any one of Claim 1 thru | or 3 characterized by the above-mentioned.

  The invention according to claim 5 includes 0.0001 parts by weight or more and 1 part by weight or less of phenolic antioxidant (d) with respect to 100 parts by weight of the polycarbonate resin (a). 4. The polycarbonate resin composition according to any one of 4 above.

  The invention according to claim 6 includes the release agent (e) in an amount of 0.0001 part by weight to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin (a). The polycarbonate resin composition according to item 1.

  The invention according to claim 7 is the polycarbonate resin composition according to any one of claims 1 to 6, wherein the glass transition temperature of the polycarbonate resin composition is 90 ° C or higher.

  The invention according to an eighth aspect is a molded article obtained by molding the polycarbonate resin composition according to any one of the first to seventh aspects.

  According to the present invention, a polycarbonate resin composition excellent in heat resistance, transparency and mechanical strength and excellent in color tone and a molded article comprising the same can be obtained.

  Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention. The drawings used are for explaining the present embodiment and do not represent the actual size.

[1] Polycarbonate resin (a)
The polycarbonate resin (a) used in the present invention is a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure.

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)

<Dihydroxy compound having a site represented by the general formula (1) in a part of the structure>
The dihydroxy compound having a site represented by the general formula (1) in a part of the structure is particularly limited as long as the part represented by the general formula (1) is included in a part of the molecular structure. Specifically, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9 , 9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4 -(2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis ( 4- (2-hydroxyethoxy) -3-tert-butyl-6-methylphenyl) fluorene, 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene, etc. in the side chain The dihydroxy compound which has an aromatic group and the ether group couple | bonded with the aromatic group in the principal chain is a site | part represented by the said General formula (1) is mentioned. Moreover, a part of heterocyclic groups, such as an anhydrosugar alcohol represented by the dihydroxy compound represented by the following general formula (2), a compound having a cyclic ether structure such as a spiroglycol represented by the following general formula (3) Is a dihydroxy compound which is a moiety represented by the general formula (1), and a dihydroxy compound in which a part of the heterocyclic group is a moiety represented by the general formula (1) is preferable. Examples of the dihydroxy compound represented by the following general formula (2) include isosorbide, isomannide, and isoide which are in a stereoisomeric relationship. Moreover, as a dihydroxy compound represented by the following general formula (3), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) ) Undecane (common name: spiroglycol), 3,9-bis (1,1-diethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 3,9- Bis (1,1-dipropyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, dioxane glycol and the like can be mentioned.
These may be used alone or in combination of two or more.
Of these dihydroxy compounds, compounds of the following general formula (2) which are abundant as resources and are readily available are particularly preferred, and isosorbide obtained by dehydrating condensation of sorbitol produced from various starches is available In view of ease of production, optical characteristics, and moldability, it is most preferable.

(In the general formula (3), R _{1 to} R ₄ are each independently an alkyl group having 1 to 3 carbon atoms.)

  Isosorbide is easily oxidized gradually by oxygen. For this reason, when storing or handling during production, it is important to prevent moisture from being mixed, to use an oxygen scavenger, or to be in a nitrogen atmosphere in order to prevent decomposition by oxygen. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate resin is produced using isosorbide containing these decomposition products, the resulting polycarbonate resin is colored or causes a significant deterioration in physical properties. Moreover, it may affect the polymerization reaction, 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 resin, or the physical properties may be significantly deteriorated. A reducing agent or an antacid is used as the stabilizer. Among these, examples of the reducing agent include sodium borohydride and lithium borohydride, and examples of the antacid include alkalis such as sodium hydroxide. The addition of such an alkali metal salt is not preferable because the alkali metal also serves as a polymerization catalyst, and if it is excessively added, the polymerization reaction cannot 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. Distillation is carried out under reduced pressure in an inert gas atmosphere such as argon or nitrogen. By performing such distillation of isosorbide, it is possible to use high purity isosorbide having a formic acid content of 20 ppm or less, particularly 5 ppm or less.

In addition, the measuring method of formic acid content in isosorbide is performed according to the following procedures using an ion chromatograph.
About 0.5 g of isosorbide is precisely weighed and collected in a 50 ml volumetric flask and made up to volume with pure water. A sodium formate aqueous solution is used as a standard sample, and the peak having the same retention time as that of the standard sample is defined as formic acid, and quantified by an absolute calibration curve method from the peak area.
As the ion chromatograph, DX-500 type manufactured by Dionex was used, and an electric conductivity detector was used as a detector. As a measurement column, AG-15 is used for a guard column manufactured by Dionex, and AS-15 is used for a separation column. A measurement sample is injected into a 100 μl sample loop, and 10 mM NaOH is used as an eluent, and measurement is performed at a flow rate of 1.2 ml / min and a thermostat temperature of 35 ° C. A membrane suppressor is used as the suppressor, and a 12.5 mM-H ₂ SO ₄ aqueous solution is used as the regenerating solution.

  The polycarbonate resin (a) used in the present invention has an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and a structural unit derived from a dihydroxy compound having a site represented by the general formula (1) in a part of the structure. It preferably has a structure containing a structural unit derived from at least one compound selected from the group consisting of oxyalkylene glycols. The polycarbonate resin (a) includes a structural unit derived from at least one compound selected from the group consisting of an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and an oxyalkylene glycol. It has a low water absorption and may be a useful material.

<Alicyclic dihydroxy compound>
Although it does not specifically limit as an alicyclic dihydroxy compound, Usually, the compound containing a 5-membered ring structure or a 6-membered ring structure is mentioned. When the alicyclic dihydroxy compound has a 5-membered or 6-membered ring structure, the heat resistance of the obtained polycarbonate resin can be increased. The six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond.
Carbon number contained in an alicyclic dihydroxy compound is 70 or less normally, Preferably it is 50 or less, More preferably, it is 30 or less. When the number of carbon atoms is excessively large, the heat resistance becomes high, but synthesis tends to be difficult, purification becomes difficult, and cost tends to be high. The smaller the carbon number, the easier it is to purify 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 (I) or (II).
_{HOCH 2 -R 5 -CH 2 OH (} I)
HO—R ₆ —OH (II)
(However, in formula (I) and formula (II), R ₅ and R ₆ each independently represent a divalent group containing a substituted or unsubstituted cycloalkyl structure having 4 to 20 carbon atoms. )

As cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I), in general formula (I), R ₅ is the following general formula (Ia) (wherein R ³ is a hydrogen atom, or Represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.). Specific examples thereof include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like.

Examples of tricyclodecane dimethanol and pentacyclopentadecane dimethanol, which are alicyclic dihydroxy compounds represented by the above general formula (I), include R ₅ in general formula (I).
Includes various isomers represented by the following general formula (Ib) (wherein n is 0 or 1).

As decalin dimethanol or tricyclotetradecane dimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I), in general formula (I), R ₅ is represented by the following general formula (Ic) (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.

Further, as norbornanedimethanol which is an alicyclic dihydroxy compound represented by the above general formula (I), various isomers in which R ₅ is represented by the following general formula (Id) in the general formula (I) 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 (I), includes various isomers in which R ₅ is represented by the following general formula (Ie) in the general formula (I). Specific examples of such a material include 1,3-adamantane dimethanol.

Further, cyclohexanediol, which is an alicyclic dihydroxy compound represented by the above general formula (II), has the following general formula (II), wherein R ₆ is the following general formula (IIa) (wherein R ³ is a hydrogen atom, or , Represented by a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.). 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 (II), in general formula (II), R ₆ represents the following general formula (IIb) (wherein n Is represented by 0 or 1).

As decalin diol or tricyclotetradecane diol which is an alicyclic dihydroxy compound represented by the above general formula (II), in general formula (II), R ₆ represents the following general formula (IIc) (where m is It represents 0 or 1). 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 general formula (II) includes various isomers in which R ₆ is represented by the following general formula (IId) in the general formula (II). 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 (II) includes various isomers in which R ₆ is represented by the following general formula (IIe) in the general formula (II). Specifically, 1,3-adamantanediol etc. are 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.

  In addition, the said exemplary compound is an example of the alicyclic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. These alicyclic dihydroxy compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

<Aliphatic dihydroxy compound>
The aliphatic dihydroxy compound is not particularly limited, and examples thereof include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, and 1,2-butane. Examples include diol, 1,5-heptanediol, 1,6-hexanediol, and the like.

<Oxyalkylene glycol>
Examples of the oxyalkylene glycol include diethylene glycol, triethylene glycol, and tetraethylene glycol.

  The polycarbonate resin (a) in the present invention is a polycarbonate resin containing at least a structural unit derived from a dihydroxy compound having a site represented by the general formula (1) in a part of the structure. It is preferable to include a structural unit derived from at least one compound selected from the group consisting of an alicyclic dihydroxy compound and an oxyalkylene glycol, and a structural unit derived from an alicyclic dihydroxy compound and / or an aliphatic dihydroxy compound. More preferably, it contains a structural unit derived from an alicyclic dihydroxy compound.

  In addition to the dihydroxy compound, the polycarbonate resin (a) used in the present invention may further contain structural units derived from other dihydroxy compounds.

<Other dihydroxy compounds>
Examples of other dihydroxy compounds include bisphenols.

  Examples of bisphenols include 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis ( 4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) ) Propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1 -Bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxy) Rokishifeniru) cyclohexane.

  Further, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichloro Examples include diphenyl ether, 4,4′-dihydroxy-2,5-diethoxydiphenyl ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene, and the like. .

When the polycarbonate resin composition of the present invention contains structural units derived from other dihydroxy compounds, effects such as improvement in flexibility, improvement in heat resistance, improvement in moldability, etc. can also be obtained. However, if the content ratio of structural units derived from other dihydroxy compounds is excessively large, the performance of the original optical characteristics may be deteriorated.
For this reason, in the polycarbonate resin (a) used by this invention, the ratio of the structural unit derived from the other dihydroxy compound with respect to all the structural units derived from the dihydroxy compound which comprises polycarbonate resin (a) is 10 mol% or less. It is preferable that
In particular, the polycarbonate resin (a) used in the present invention includes only a structural unit derived from a dihydroxy compound having a site represented by the general formula (1) in a part of the structure and a structural unit derived from an alicyclic dihydroxy compound. It is preferable that it is comprised.

The polymerization degree of the polycarbonate resin (a) used in the present invention is such that a mixed solvent of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 is used as a solvent, and the polycarbonate resin concentration is 1.00 g / It is expressed as a reduced viscosity (hereinafter sometimes simply referred to as “reduced viscosity of a polycarbonate resin”) of a polycarbonate solution precisely adjusted to dl measured at a temperature of 20.0 ° C. ± 0.1 ° C. The reduced viscosity of the polycarbonate resin (a) used in the present invention is preferably 0.40 dl / g or more, more preferably 0.40 dl / g to 2.0 dl / g, and more preferably 0.45 dl / g to 1.5 dl / g. Particularly preferred is g or less.
If the reduced viscosity is excessively small, the mechanical strength when molded into a lens or the like tends to decrease. On the other hand, if the reduced viscosity is excessively high, the fluidity during molding is lowered, the cycle characteristics are lowered, and the birefringence of the molded product tends to increase.

  The Abbe number of the polycarbonate resin (a) used in the present invention is preferably 50 or more, particularly preferably 55 or more. The larger this value, the smaller the chromatic dispersion of the refractive index. For example, the chromatic aberration when used with a single lens is reduced, and a clearer image can be easily obtained. As the Abbe number decreases, the chromatic dispersion of the refractive index increases, and when used with a single lens, chromatic aberration increases and the degree of image blur increases.

  The 5% heat loss temperature of the polycarbonate resin (a) used in the present invention is preferably 340 ° C or higher, particularly preferably 345 ° C or higher. The higher the 5% heat loss temperature, the better the thermal stability, the higher the temperature resistance, the higher the temperature, the higher the manufacturing temperature, and the wider the control range during manufacturing, making it easier to manufacture. There is sex. The lower the 5% heat loss 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 may become narrow and difficult to make.

The photoelastic coefficient of the polycarbonate resin (a) used in the present invention is preferably 40 × 10 ⁻¹² Pa ⁻¹ or less, more preferably 20 × 10 ⁻¹² Pa ⁻¹ or less. When the photoelastic coefficient is high, the retardation value of the film formed by melt extrusion, solution casting method, etc. becomes large. The variation becomes even larger. Moreover, when bonding such a phase difference film, not only the desired phase difference is shifted due to the tension during the bonding, but also the phase difference value is likely to change due to shrinkage of the polarizing plate after the bonding. The smaller the photoelastic coefficient, the smaller the variation in phase difference.

<Production method of polycarbonate resin (a)>
The polycarbonate resin (a) used in the present invention can be produced by a conventionally known polymerization method. As a polymerization method, any of a solution polymerization method using phosgene and a melt polymerization method in which a carbonic acid diester and a dihydroxy compound are reacted may be used.
Among these, a melt polymerization method is preferred in which a dihydroxy compound containing at least a dihydroxy compound having a site represented by the general formula (1) in a part of the structure described above is reacted with a carbonic acid diester in the presence of a polymerization catalyst. .

(Carbonated diester)
Examples of the carbonic acid diester used in the melt polymerization method include those represented by the following general formula (4). These carbonic acid diesters may be used alone or in combination of two or more.

(In General Formula (4), A ₁ and A ₂ are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted 6 to 18 carbon atoms. It is an aromatic group.)

Examples of the carbonic acid diester represented by the general formula (4) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate; dimethyl carbonate, diethyl carbonate and di-t-butyl carbonate.
Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.

In the above-described melt polymerization method, the carbonic acid diester represented by the general formula (4) is 0 with respect to all dihydroxy compounds including a dihydroxy compound having a site represented by the general formula (1) in a part of the structure. It is preferably used in a molar ratio of .90 to 1.10, more preferably in a molar ratio of 0.96 to 1.04.
If the molar ratio of the carbonic acid diester used in the melt polymerization method is too small, the terminal hydroxyl group of the produced polycarbonate resin increases, the thermal stability of the polymer deteriorates, and the desired high molecular weight product tends not to be obtained. is there. On the other hand, if the molar ratio of the carbonic acid diester used is excessively large, the rate of the transesterification reaction decreases under the same polymerization conditions, and it tends to be difficult to produce a polycarbonate resin having a desired molecular weight. Furthermore, the amount of carbonic acid diester remaining in the produced polycarbonate resin tends to increase, and the residual carbonic acid diester tends to cause an odor during molding or a molded product.

From such a viewpoint, the polycarbonate resin (a) used in the present invention preferably has a residual content of the dihydroxy compound having a site represented by the general formula (1) in a part of the structure of 60 ppm or less. 50 ppm or less is more preferable, and 30 ppm or less is particularly preferable.
If the residual content of the dihydroxy compound having a site represented by the general formula (1) in a part of the structure in the polycarbonate resin is excessively large, the thermal stability of the polymer is deteriorated and the gold at the time of injection molding When the amount of deposits on the mold increases or when a sheet or film is extruded, the surface appearance may be impaired due to an increase in the amount of roll deposits.

Further, in the polycarbonate resin (a) used in the present invention, the content of the carbonic acid diester represented by the general formula (4) is preferably 0.1 ppm or more and 60 ppm or less, and is 0.1 ppm or more and 50 ppm or less. More preferably, it is 0.1 ppm or more and 30 ppm or less.
When the content of the carbonic acid diester represented by the general formula (4) in the polycarbonate resin is excessively large, when a material attached to the mold at the time of injection molding, a sheet or a film is extruded, a roll is attached. There is a possibility that the surface appearance may be impaired by increasing the amount of kimono.

(End group structure of polycarbonate resin (a))
As described above, in the method for producing the polycarbonate resin (a) used in the present invention, it is preferable to use diphenyl carbonate as the carbonic acid diester. In this case, all of the terminal groups (A) of the terminal group represented by the following general formula (5) (hereinafter sometimes referred to as “phenyl group terminal”) of the polycarbonate resin (a) to be produced are present. It is preferable that the ratio (A / B) with respect to the existence number (B) is in the range of 20% or more.
Further, the ratio (A / B) of the number of phenyl group terminals (A) to the number of all terminal groups (B) in the polycarbonate resin (a) is more preferably 25% or more, and 30% The above range is particularly preferable.
When the ratio (A / B) of the number of phenyl group terminals (A) to the number of all terminal groups (B) is excessively small, coloring occurs under conditions where the polymerization reaction temperature, injection molding temperature, etc. are high. May become large.

A method for adjusting the ratio (A / B) of the number of phenyl group terminals (A) to the number of all terminal groups (B) in the polycarbonate resin (a) to the above-mentioned range is not particularly limited. The amount ratio of carbonic acid diester to the total dihydroxy compound used is adjusted within a range where a desired high molecular weight product can be obtained, or the residual monomer is removed from the reaction system by degassing at the latter stage of the polymerization reaction, or the reactor at the latter stage of the polymerization reaction. The ratio (A / B) of the number of phenyl group terminals (A) to the number of all terminal groups (B) is adjusted to the above-mentioned range by increasing the reaction rate by increasing the stirring efficiency of be able to.
The proportion of the phenyl group terminal in the polycarbonate resin can be calculated by measurement of 1H-NMR spectrum using deuterated chloroform to which TMS is added as a measurement solvent with an NMR spectrometer.

  In addition, a dihydroxy compound having a portion represented by the general formula (1) in a part of the structure, an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, an oxyalkylene glycol, and other dihydroxy compounds used as necessary The use ratio with the compound is appropriately adjusted according to the ratio of the structural unit derived from each dihydroxy compound constituting the polycarbonate resin used in the present invention.

(Polymerization catalyst)
As a polymerization catalyst (transesterification catalyst) in melt polymerization, an alkali metal compound and / or an alkaline earth metal compound is used. It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound together with an alkali metal compound and / or an alkaline earth metal compound. It is particularly preferred to use only alkali 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 bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate. Strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like. These alkali metal compounds and / or alkaline earth metal compounds may be used alone or in combination of two or more. In this specification, the terms “alkali metal” and “alkaline earth metal” are respectively referred to as “Group 1 metal” and “Group 2 metal” in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). As a synonym.

  Specific examples of basic boron compounds used in combination with alkali metal compounds and / or alkaline earth metal compounds include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl Boron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, sodium salt, potassium salt, lithium salt , Calcium salt, barium salt, magnesium salt, or strontium salt.

  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 polymerization catalyst is usually used in an amount of 0.1 to 100 μmol as a metal conversion amount with respect to 1 mol of all dihydroxy compounds used in the reaction. It is used within the range, preferably within the range of 0.5 μmol to 50 μmol, and more preferably within the range of 1 μmol to 25 μmol. When the amount of the polymerization catalyst used is excessively small, there is a tendency that the polymerization activity necessary for producing a polycarbonate resin having a desired molecular weight cannot be obtained. On the other hand, if the amount of the polymerization catalyst used is excessive, the hue of the resulting polycarbonate resin deteriorates, and by-products are generated, resulting in a decrease in fluidity and the generation of gels. Resin production tends to be difficult.

  In the production of the polycarbonate resin (a) used in the present invention, the dihydroxy compound having a site represented by the general formula (1) in a part of the structure described above may be supplied as a solid or heated. You may supply as a molten state and may supply as aqueous solution.

  A dihydroxy compound such as an alicyclic dihydroxy compound 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. . The same applies to other dihydroxy compounds. 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, at least one selected from the group consisting of a dihydroxy compound having a site represented by the general formula (1) and an aliphatic dihydroxy compound, an alicyclic dihydroxy compound, and an oxyalkylene glycol in a part of the structure. The method of reacting a compound and another dihydroxy compound used as necessary with a carbonic acid diester in the presence of a polymerization catalyst is usually carried out in a multistage process of two or more stages.
Specifically, the first stage reaction is carried out at a temperature of 140 ° C. to 220 ° C., preferably 150 ° C. to 200 ° C. for 0.1 hour to 10 hours, preferably 0.5 hour to 3 hours. In the second and subsequent stages, the reaction temperature is raised while gradually reducing the pressure of the reaction system from the pressure in the first stage, and the aromatic monohydroxy compound such as phenol that is generated at the same time is removed from the reaction system. Specifically, the pressure of the reaction system is 200 Pa or less, and the polycondensation reaction is performed under a temperature range of 210 to 280 ° C.

In this polycondensation reaction, it is important to control the balance between temperature and pressure in the reaction system. In particular, if either one of the temperature and the pressure changes too quickly, the unreacted monomer is distilled off, the molar ratio of the dihydroxy compound and the carbonic acid diester is changed, and the degree of polymerization may be lowered.
For example, when isosorbide and 1,4-cyclohexanedimethanol are used as the dihydroxy compound, 1,4-cyclohexanedimethanol is used when the molar ratio of 1,4-cyclohexanedimethanol is 50 mol% or more based on the total dihydroxy compound. Since methanol easily distills out of the reaction system as a monomer, the reaction is performed while the temperature in the reaction system is increased at a rate of temperature increase of 40 ° C. or less under a reduced pressure of about 13 kPa. When the temperature is increased at a rate of temperature increase of 40 ° C. or less per hour under a pressure up to about .67 kPa and finally a polycondensation reaction is performed at a temperature of 200 to 250 ° C. at a pressure of 200 Pa or less, This is preferable because a polycarbonate resin having an increased degree of polymerization can be obtained.

  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, the mole of 1,4-cyclohexanedimethanol Compared with the case where the ratio is 50 mol% or more, the viscosity increases rapidly. For example, until the pressure in the reaction system is about 13 kPa, the temperature is increased at a rate of temperature increase of 40 ° C. or less per hour. The reaction is further performed at a pressure up to about 6.67 kPa at a temperature rising rate of 40 ° C. or more per hour, preferably 50 ° C. or more per hour. In particular, when a polycondensation reaction is performed at a temperature of 220 ° C. to 290 ° C. under a reduced pressure of 200 Pa or less, a polycarbonate resin having a sufficiently increased degree of polymerization can be obtained. There. The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.

(Aromatic monohydroxy compound content)
In the polycondensation reaction between the dihydroxy compound and the carbonic acid diester described above, an aromatic monohydroxy compound that may have an alkyl group having 5 or less carbon atoms is generated as a by-product.
In the present embodiment, the content of the aromatic monohydroxy compound which may have an alkyl group having 5 or less carbon atoms contained in the polycarbonate resin (a) is preferably 700 ppm or less, and the content is 500 ppm. More preferably, the content is more preferably 300 ppm or less.
However, the polycarbonate resin (a) used in the present invention contains about 10 ppm of the aromatic monohydroxy compound as an unavoidable remaining amount.

Here, the aromatic monohydroxy compound which may have an alkyl group having 5 or less carbon atoms excludes an antioxidant such as hindered phenol, which is added to the polycarbonate resin, as will be described later. Is meant to do.
Specific examples of the aromatic monohydroxy compound which may have an alkyl group having 5 or less carbon atoms include, for example, phenol, cresol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn -Pentylphenol, 2,6-di-t-butylphenol, 2,5-di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol and the like.

The method for adjusting the content of the aromatic monohydroxy compound, which may have an alkyl group having 5 or less carbon atoms, contained in the polycarbonate resin (a) to 700 ppm or less is not particularly limited. Is mentioned.
For example, in the polycondensation reaction, the charge ratio of the dihydroxy compound and the carbonic acid diester is brought close to 1, the polycondensation reaction is increased, and the aromatic monohydroxy compound is efficiently discharged out of the reactor in which the polycondensation reaction is performed. In the latter half of the polycondensation reaction, devolatilization is performed while applying a predetermined shearing force to the high-viscosity reaction solution using a horizontal reactor, and water and the aromatic monohydroxy compound are azeotroped by water injection and devolatilization. .

  In the polycarbonate resin (a) used in the present invention, when the content of the aromatic monohydroxy compound which may have an alkyl group having 5 or less carbon atoms is excessively large, the color tone and transparency are impaired, for example, The optical material tends to be an inappropriate material. Moreover, heat resistance falls and there exists a tendency for a color tone to deteriorate over time.

[2] Polycarbonate resin composition The polycarbonate resin composition of the present invention comprises a polycarbonate resin (a) and an antioxidant, and phosphite-based antioxidant (b) and sulfur-based antioxidant as antioxidants. (C).

<Phosphite Antioxidant (b)>
Examples of the phosphite antioxidant (b) include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite. , Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaeryth Diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.

Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferably used. These compounds can be used alone or in combination of two or more.
Here, the content of the phosphite-based antioxidant (c) is 0.0001 part by weight or more and 1 part by weight or less, preferably 0.0001 part by weight or more and 0.1 part by weight or more with respect to 100 parts by weight of the polycarbonate resin (a). 1 part by weight or less, more preferably 0.0002 part by weight or more and 0.01 part by weight or less.
If the content is too small, the effect of suppressing coloring during molding may be insufficient. Moreover, if the content is excessively large, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be impaired.

<Sulfur-based antioxidant (c)>
Examples of the sulfur-based antioxidant (c) include dilauryl-3,3′-thiodipropionic acid ester, ditridecyl-3,3′-thiodipropionic acid ester, and dimyristyl-3,3′-thiodipropionic acid. Ester, distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4 -(3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. be able to. Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

Here, the content of the sulfur-based antioxidant (c) is 0.0001 parts by weight or more and 1 part by weight or less, preferably 0.0001 parts by weight or more and 0.1 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin (a). Parts by weight or less, more preferably 0.0002 parts by weight or more and 0.01 parts by weight or less.
If the content is too small, the effect of suppressing coloring during molding may be insufficient. Moreover, if the content is excessively large, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be impaired.

  Even if the polycarbonate resin composition of the present invention contains each of the phosphite antioxidant (b) and the sulfur antioxidant (c) alone, the effect of suppressing coloration is poor. There is a possibility of exerting a great effect on coloring suppression at the time.

  The polycarbonate resin composition of the present invention preferably further contains a phenolic antioxidant (d).

<Phenolic antioxidant (d)>
Examples of the phenolic antioxidant (d) include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, and 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-hydrocinna Mido), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphine Acid tetrakis (2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] Compounds such as ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane.

  Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. Specifically, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis [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 and the like, preferably pentaerythris Lithyl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is more preferred.

Here, the content of the phenol-based antioxidant (d) is preferably 0.0001 part by weight or more and 1 part by weight or less, more preferably 0.0001 part by weight or more with respect to 100 parts by weight of the polycarbonate resin (a). 0.1 parts by weight or less, more preferably 0.0002 parts by weight or more and 0.01 parts by weight or less.
If the content is too small, the effect of suppressing coloring during molding may be insufficient. Moreover, if the content is excessively large, the amount of deposits on the mold at the time of injection molding increases or the amount of deposits on the roll increases when the film is formed by extrusion molding. The surface appearance may be impaired.

  In this Embodiment, the addition time of the said antioxidant mix | blended with polycarbonate resin (a) and the addition method are not specifically limited. As the addition time, for example, when the polycarbonate resin (a) is produced by the transesterification method, at the end of the polymerization reaction; further, regardless of the polymerization method, such as during the kneading of the polycarbonate resin (a) and other compounding agents A state in which the polycarbonate resin (a) is melted; for example, when it is blended and kneaded with a solid polycarbonate resin (a) such as pellets or powder using an extruder or the like. As an addition method, a method of directly mixing or kneading the acid value inhibitor to the polycarbonate resin (a); a high concentration master prepared by using a small amount of the polycarbonate resin (a) or other resin and the antioxidant. It can also be added as a batch.

<Release agent (e)>
The polycarbonate resin composition of the present invention preferably further contains a release agent (e) in order to further improve the releasability from the mold during melt molding. As the release agent (e), higher fatty acids, higher fatty acid esters of monohydric or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, natural petroleum waxes such as paraffin wax, montan Examples thereof include natural coal waxes such as waxes, olefin waxes, silicone oils, organopolysiloxanes, and the like, and higher fatty acid and higher fatty acid esters of mono- or polyhydric alcohols are particularly preferable.

  The higher fatty acid ester is preferably a partial ester or a total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms. . Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbite, stearyl stearate, behenic acid monoglyceride, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate 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 substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable. Examples of such saturated fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like. One of these release agents (e) may be used alone, or two or more thereof may be mixed and used. The content of the release agent (e) is 0.0001 to 2 parts by weight, preferably 0.01 to 1 part by weight, more preferably 100 parts by weight of the polycarbonate resin (a). Is 0.1 to 0.5 parts by weight.

  In this Embodiment, the addition time of the said mold release agent (e) mix | blended with polycarbonate resin (a) and the addition method are not specifically limited. As the addition time, for example, when the polycarbonate resin (a) is produced by the transesterification method, at the end of the polymerization reaction; further, regardless of the polymerization method, such as during the kneading of the polycarbonate resin (a) and other compounding agents A state in which the polycarbonate resin (a) is melted; for example, when it is blended and kneaded with a solid polycarbonate resin (a) such as pellets or powder using an extruder or the like. As an addition method, the release agent (e) is directly mixed or kneaded with the polycarbonate resin (a); prepared by using a small amount of the polycarbonate resin (a) or other resin and the release agent (e). It can also be added as a high concentration master batch.

The polycarbonate resin composition of the present invention preferably has a glass transition temperature of 90 ° C. or higher, more preferably 120 ° C. or higher.
If the glass transition temperature is too low, the heat resistance is insufficient, and deformation may occur under high heat. When the glass transition temperature is within the above range, it is suitable for use as a lens as an optical component. That is, by using a polycarbonate resin composition having such a glass transition temperature, a lens that is less likely to be deformed and has less variation in surface accuracy even under high temperature and high humidity conditions such as a temperature of 85 ° C. and a relative humidity of 85%. Etc. can be obtained.

(Other additives)
The polycarbonate resin composition of the present invention may contain an acidic compound as long as the object of the present invention is not impaired.
The compounding amount of the acidic compound is 0.00001 part by weight or more and 0.1 part by weight or less, preferably 0.0001 part by weight or more and 0.01 part by weight or more based on 100 parts by weight of the polycarbonate resin (a). Part or less, more preferably 0.0002 part by weight or more and 0.001 part by weight or less.
If the blending amount of the acidic compound is excessively small, it may not be possible to sufficiently suppress coloring when the residence time of the polycarbonate resin composition in the injection molding machine becomes long during injection molding. Moreover, when there are too many compounding quantities of an acidic compound, the hydrolysis resistance of resin may fall remarkably.

Examples of acidic compounds include hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, adenosine phosphoric acid, benzoic acid Acid, formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, nicotinic acid , Bronsted acids such as picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof. Among these acidic compounds or derivatives thereof, sulfonic acids or esters thereof are preferable, and p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferable.
These acidic compounds can be added in the production process of the polycarbonate resin composition as a compound that neutralizes the basic transesterification catalyst used in the polycondensation reaction of the polycarbonate resin (a) described above.

  The polycarbonate resin composition of the present invention can contain an antistatic agent as long as the object of the present invention is not impaired. Examples of the antistatic agent include polyether ester amide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, maleic anhydride monoglyceride, maleic anhydride diglyceride and the like.

The polycarbonate resin composition of the present invention can contain an ultraviolet absorber and a light stabilizer as long as the object of the present invention is not impaired. Specifically, for example, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole 2- (2′-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′- p-phenylenebis (1,3-benzoxazin-4-one) and the like. As for content of this stabilizer, 0.01-2 mass parts is preferable with respect to 100 mass parts of polycarbonate resin (a).

  The polycarbonate resin composition used in the present invention can contain a bluing agent in order to counteract the yellowishness of the lens based on the polymer or the UV absorber. As the bluing agent, any conventional bluing agent can be used as long as it is used for polycarbonate resin. 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 131 [CA. No 68210], common name Solvent Violet 133 [CA. No. 60725], generic name Solvent Blue 94 [CA. No 61500], generic name Solvent Violet 36 [CA. No. 68210], general name Solvent Blue 97 [manufactured by Bayer "Macrolex Violet RR"], general name Solvent Blue 45 [CA. No. 61110] and the like are given as representative examples. 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 parts by weight to 2 × 10 ⁻⁴ parts by weight when the polycarbonate resin (a) is 100 parts by weight.

  The polycarbonate resin composition used in the present invention may contain an inorganic filler. The compounding amount of the inorganic filler is 1 part by weight or more and 100 parts by weight or less, preferably 3 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin (a). When the blending amount of the inorganic filler is excessively small, the reinforcing effect is small, and when it is excessively large, the appearance tends to deteriorate.

  Examples of the inorganic filler include glass fiber, glass milled fiber, glass flake, glass bead, carbon fiber, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc, mica, and wallast. Calcium silicate such as knight; carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber, whisker, etc. It is done. Among these, glass fiber filler, glass powder filler, glass flake filler; carbon fiber filler, carbon powder filler, carbon flake filler; various whiskers, mica Talc is preferred. More preferably, glass fiber, glass flake, glass milled fiber, carbon fiber, wollastonite, mica and talc are mentioned.

Among inorganic fillers, any glass fiber or glass milled fiber may be used as long as it is used in thermoplastic resins. In particular, alkali-free glass (E glass) is preferable. The diameter of glass fiber becomes like this. Preferably they are 6 micrometers-20 micrometers, More preferably, they are 9 micrometers-14 micrometers. If the diameter of the glass fiber is too small, the reinforcing effect tends to be insufficient. On the other hand, if it is excessively large, the product appearance is liable to be adversely affected.
The glass fiber is preferably chopped strands cut to a length of 1 mm to 6 mm; preferably glass milled fibers that are commercially available after being pulverized to a length of 0.01 mm to 0.5 mm. You may use these individually or in mixture of both.
In order to improve the adhesion with the polycarbonate resin (a), the glass fiber used in the present invention is a surface treatment with a silane coupling agent such as aminosilane, epoxysilane, or the like, or an acrylic resin. You may use it, performing the bundling process by resin, urethane type resin, etc.

  Any glass beads can be used as long as they are used in thermoplastic resins. Among these, alkali-free glass (E glass) is preferable. The shape of the glass beads is preferably spherical with a particle size of 10 μm to 50 μm.

  As glass flakes, scaly glass flakes can be mentioned. The maximum diameter of the glass flake after blending the polycarbonate resin is generally 1000 μm or less, preferably 1 μm to 500 μm, and the aspect ratio (the ratio of the maximum diameter to the thickness) is 5 or more, preferably 10 or more, Preferably it is 30 or more.

  The carbon fiber is not particularly limited, and is produced by firing using, for example, acrylic fiber, petroleum or carbon-based special pitch, cellulose fiber, lignin or the like as a raw material, such as flame resistance, carbonaceous, and graphite. There are various types. The average of the aspect ratio (fiber length / fiber diameter) of the carbon fibers is preferably 10 or more, more preferably 50 or more. If the average aspect ratio is too small, the conductivity, strength, and rigidity of the polycarbonate resin composition tend to be reduced. The diameter of the carbon fiber is 3 μm to 15 μm, and any shape such as chopped strand, roving strand, milled fiber, etc. can be used to adjust the aspect ratio. Carbon fiber can be used 1 type or in mixture of 2 or more types.

  In order to increase the affinity with the polycarbonate resin (a), the carbon fiber is subjected to surface treatment such as epoxy treatment, urethane treatment, oxidation treatment, etc., as long as the properties of the polycarbonate resin composition of the present invention are not impaired. Also good.

  The polycarbonate resin composition of the present invention can be produced by mixing the above components simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. . Furthermore, a nucleating agent, a flame retardant, an inorganic filler, an impact modifier, a foaming agent, a dye / pigment and the like that are usually used in the resin composition may be contained within a range not impairing the object of the present invention.

  In the present embodiment, a polycarbonate resin molded product obtained by molding the above-described polycarbonate resin composition is obtained. The method for molding the polycarbonate resin molded product is not particularly limited, but the injection molding method is preferable.

  The polycarbonate resin composition used in the present embodiment can be formed into an optical film. Moreover, a retardation film can be manufactured by extending | stretching this optical film formed into a film. Examples of the film forming method include conventionally known melt extrusion methods and solution casting methods.

  In addition to the polycarbonate resin composition used in the present embodiment as a raw material for the optical film described above, other polycarbonate resins obtained from bisphenol A, bisphenol Z, etc., 9,9-bis (4-hydroxyphenyl) fluorene , 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, polycarbonate resins and polyester resins modified with 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, polyethylene terephthalate, polybutylene Even if it is a composition with 1 type, or 2 or more types of other resins, such as polyester resins, such as terephthalate, polynaphthalene dicarboxylate, polycyclohexane dimethylene cyclohexane dicarboxylate, polycyclohexane dimethylene terephthalate There.

The retardation film is a retardation film composed of a single polymer orientation film, which satisfies the following conditions (i) to (iv), and has a characteristic that the retardation at wavelengths from 450 nm to 630 nm is larger toward the longer wavelength side. It is.
(I) a polymer monomer unit having positive refractive index anisotropy (hereinafter referred to as "first monomer unit") and a polymer monomer unit having negative refractive index anisotropy (hereinafter referred to as "first monomer unit"). 2 monomer units)), and a polymer comprising
(Ii) Re450 / Re550 of the polymer based on the first monomer unit is smaller than Re450 / Re550 of the polymer based on the second monomer unit (where “Re450” means “the polymer at a wavelength of 450 nm” "Re550" indicates "the phase difference of the polymer at a wavelength of 550".)
(Iii) has a positive refractive index anisotropy;
(Iv) It is comprised from the polymer whose absolute value of a photoelastic coefficient is 20 * 10 <^-12> Pa <^-1> or less.
The above conditions can be easily realized by using the polycarbonate resin composition of the present invention.

  The thickness of the optical film is usually 30 μm to 200 μm, preferably 50 μm to 150 μm. Further, the retardation value of the film formed is preferably 20 nm or less, more preferably 10 nm or less. When the retardation value of the film is excessively large, the in-plane variation of the retardation value tends to increase when the film is stretched to obtain a retardation film.

As the stretching method of the optical film, a known stretching method such as uniaxial stretching in either the longitudinal direction or the lateral direction or biaxial stretching in which the stretching is performed in the longitudinal and lateral directions can be used. It is also possible to control the three-dimensional refractive index of the film by performing special biaxial stretching.
The stretching conditions for producing the retardation film are preferably performed in the range of −20 ° C. to + 40 ° C. of the glass transition temperature of the film raw material. More preferably, it is the range of -10 degreeC to +20 degreeC of the glass transition temperature of a film raw material. If the stretching temperature is excessively lower than the glass transition temperature of the polycarbonate resin composition, the retardation of the stretched film becomes large, and in order to obtain the desired retardation, the stretching ratio must be lowered, and the film in-plane position is reduced. There is a tendency for variation in phase difference to increase. On the other hand, if the stretching temperature is excessively higher than the glass transition temperature, the phase difference of the resulting film becomes small, and the stretching ratio for obtaining a desired retardation has to be increased, and the appropriate stretching condition width tends to be narrowed. There is.

  The retardation film can be used as a retardation plate for various liquid crystal display devices. When the retardation film is used for color compensation of the STN liquid crystal display device, the retardation value is generally selected in the range from 400 nm to 2000 nm. When the retardation film is used as a half-wave plate, the retardation value is selected in the range of 200 nm to 400 nm. When the retardation film is used as a quarter wavelength plate, the retardation value is selected in the range from 90 nm to 200 nm. A more preferable retardation value as a quarter wavelength plate is from 100 nm to 180 nm. A phase difference film can also be used independently, can also be used in combination of 2 or more sheets, and can also be used in combination with another film etc.

  The retardation film can be laminated and bonded via a known iodine-based or dye-based polarizing plate and an adhesive. When laminating, it is necessary to laminate the polarizing axis of the polarizing plate and the slow axis of the retardation film at a specific angle depending on the application. Moreover, a retardation film can be used as a quarter wave plate, and this can be laminated and bonded with a polarizing plate and used as a circular polarizing plate. In that case, in general, the polarizing axis of the polarizing plate and the slow axis of the retardation film are laminated while maintaining a relative angle of substantially 45 °. Furthermore, you may laminate | stack using a retardation film as a polarizing protective film which comprises a polarizing plate. Furthermore, the retardation film can be used as a color compensation plate of an STN liquid crystal display device, and can be used as an elliptically polarizing plate by laminating and laminating this with a polarizing plate.

  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. Below, the characteristic evaluation of the resin composition was performed by the following method.

(1) Injection molding The pellets of the polycarbonate resin composition were pre-dried at 80 ° C for 4 hours. Next, the pellets of the dried polycarbonate resin composition were measured using a J75EII type injection molding machine manufactured by Nippon Steel Works under the molding conditions of a cylinder temperature of 230 ° C., a molding cycle of 45 seconds, and a mold temperature of 60 ° C. of 60 mm × 60 mm × 3 mmt. A flat plate was formed. In addition, a Charpy impact test piece was also molded under the above molding conditions.

(2) Measurement of yellow index (YI value) and calculation of color difference (ΔYI value) Using a spectral color difference meter (SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.), the flat plate molded in the above (1) was subjected to the C light source transmission method. The yellow index (YI value) was measured. The color difference (ΔYI value) was calculated by the following formula using the YI value of the flat plate of Comparative Example 1 containing no antioxidant as a reference. Here, the lower the ΔYI value, the better the color tone.
ΔYI value = YI value−YI value (flat plate of Comparative Example 1)

(3) Haze and total light transmittance measurement Using Nippon Denshoku Industries Co., Ltd. haze meter NDH2000, the total light transmittance and haze of the flat plate shape | molded by said (1) were measured with D65 light source.

(4) Glass transition temperature (Tg)
Based on JIS K7121 (1987), the glass transition temperature (Tg) was measured from the differential scanning calorimeter ("DSC822" manufactured by METTLER). About 10 mg of polycarbonate resin composition pellets are set in the differential scanning calorimeter, heated at a rate of temperature increase of 10 ° C./min, and the base line on the low temperature side is extended to the high temperature side, and the step change of the glass transition The extrapolated glass transition start temperature Tg, which is the temperature of the intersection with the broken line drawn at the point where the slope of the curve of the portion is maximized, was determined and was used as the glass transition temperature (Tg).

(5) Charpy impact strength According to ISO179, the Charpy impact strength with a notch was measured using the Charpy impact test piece formed in (1) above.

[Example 1]
13.4-cyclohexanedimethanol (Eastman, hereinafter abbreviated as “1,4-CHDM”) with respect to 27.7 parts by weight (0.516 mol) of isosorbide (Rocket Fleure) 0 parts by weight (0.221 mol), diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “DPC”) 59.2 parts by weight (0.752 mol), and cesium carbonate (Wako Pure Chemical Industries, Ltd.) as a catalyst Product) 2.21 × 10 ⁻⁴ parts by weight (1.84 × 10 ⁻⁶ mol) was charged into a reaction vessel, and the reaction medium was heated in the first stage of the reaction under a nitrogen atmosphere. Was heated to 150 ° C., and the raw materials were dissolved in about 15 minutes while stirring as necessary.
Subsequently, the pressure was reduced from normal pressure to 13.3 kPa, and the generated phenol was extracted out of the reaction vessel while raising the temperature of the heat medium in the reaction vessel to 190 ° C. over 1 hour.
After holding the entire reaction vessel at 190 ° C. for 15 minutes, as a second step, the pressure in the reaction vessel is reduced to 6.67 kPa, and the temperature of the heat medium in the reaction vessel is increased to 230 ° C. in 15 minutes. The generated phenol was extracted out of the reaction vessel. Since the stirring torque of the stirrer increased, the temperature was further 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 stopped, and a molten polycarbonate resin was obtained from the outlet of the polymerization machine. Further, the molten polycarbonate resin was continuously supplied to a twin screw extruder provided with 3 vents and water injection equipment.
In a twin-screw extruder, the antioxidants ADK STAB 2112 and ADK STAB AO-412S are continuously added to have the composition shown in Table 1, and the release agent NAA-180 is continuously added. After pouring water with a low molecular weight substance such as phenol at each vent portion, pelletization was performed with a pelletizer to obtain a heterocyclic ring-containing polycarbonate resin (a).
About the obtained polycarbonate, various physical properties etc. were evaluated by the evaluation method of the said description. The obtained results are shown in Table 1.

[Example 2]
The same procedure as in Example 1 was conducted except that the antioxidant was changed to ADK STAB 2112, ADK STAB AO-412S and ADK STAB AO-60.

[Comparative Example 1]
The same procedure as in Example 1 was performed except that the antioxidant of Example 1 was not added.

[Comparative Example 2]
The same procedure as in Example 1 was performed except that the antioxidant of Example 1 was changed to ADK STAB 2112.

[Comparative Example 3]
The same procedure as in Example 1 was performed except that the antioxidant of Example 1 was changed to ADK STAB AO-412S.

[Comparative Example 4]
The same procedure as in Example 1 was performed except that the antioxidant of Example 1 was changed to ADK STAB AO-60.

[Comparative Example 5]
The procedure of Example 1 was repeated except that the antioxidant of Example 1 was changed to ADK STAB 2112 and ADK STAB AO-60.

[Comparative Example 6]
The procedure of Example 1 was repeated except that the antioxidant of Example 1 was changed to Adeka Stub AO-412S and Adeka Stub AO-60.

In addition, the additives described in Table 1 are as follows.
(Antioxidant)
ADK STAB 2112: Tris (2,4-di-tertbutylphenyl) phosphite (manufactured by ADEKA)
ADK STAB AO-412S: Tetrakis [methylene-3- (dodecylthio) propionate] methane (manufactured by ADEKA)
ADK STAB AO-60: Pentaerythrityl-tetrakis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by ADEKA)
(Release agent)
NAA-180: Stearic acid (manufactured by NOF Corporation)

  From the results shown in Table 1, a polycarbonate resin composition comprising a polycarbonate resin obtained by melt polycondensation of isosorbide, 1,4-cyclohexanedimethanol and diphenyl carbonate, and a phosphite antioxidant and a sulfur antioxidant. It can be seen that the product is excellent in transparency, retains strength, has a good appearance of the molded product, and has a very excellent color tone after molding.

  The polycarbonate resin composition of the present invention and the molded product thereof are excellent in transparency, retain strength, have a good appearance of the molded product, have excellent color tone after molding, electrical / electronic parts, automotive parts, etc. Injection molding field, film, sheet field, bottle, container field, camera lens, finder lens, lens application such as CCD and CMOS lens, retardation film used for liquid crystal and plasma display, diffusion sheet, The present invention can be applied to a wide range of fields such as a binder application for fixing a film such as a polarizing film, a sheet, an optical disk, an optical material, an optical component, a dye, and a charge transfer agent.

Claims (5)

100 parts by weight of a polycarbonate resin (a) containing at least a structural unit derived from a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure;
The polycarbonate resin (a) contains a phosphite antioxidant (b) 0.0001 part by weight to 1 part by weight and a sulfur antioxidant (c) 0.0001 part by weight to 1 part by weight. A structural unit derived from at least one compound selected from the group consisting of a group dihydroxy compound, an alicyclic dihydroxy compound, and an oxyalkylene glycol;
The polycarbonate resin composition characterized by the dihydroxy compound which has a site | part represented by the said General formula (1) in a part of structure being a compound represented by following General formula (2) .

(However, the site represented by the above general formula (1) unless it is part of _-CH 2 -O-H.)

  2. The polycarbonate resin composition according to claim 1, further comprising 0.0001 parts by weight to 1 part by weight of the phenolic antioxidant (d) with respect to 100 parts by weight of the polycarbonate resin (a). 3. The polycarbonate resin composition according to claim 1, wherein the release agent (e) is contained in an amount of 0.0001 part by weight to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin (a). The polycarbonate resin composition according to any one of claims 1 to 3 , wherein the polycarbonate resin composition has a glass transition temperature of 90 ° C or higher. A molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 4 .