JP2003055543A - Aromatic-aliphatic copolymerized polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an aromatic-aliphatic polycarbonate resin exhibiting excellent impact resistance even at a low temperature and having high heat-resistance, high Abbe number and low photoelastic constant at a low production cost. SOLUTION: The polycarbonate resin composition is composed of (A) an aromatic-aliphatic copolymerized polycarbonate resin having the units of formula (1) and formula (2) as constituent units and (B) a copolymerized polycarbonate resin having the units of formula (1) and formula (3) as constituent units.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a high refractive index and an inverse dispersion value, a low photoelastic constant, and impact resistance, heat resistance,
The present invention relates to a transparent polycarbonate resin composition having an excellent hue. The polycarbonate resin composition can be suitably used for plastic optical materials such as various lenses, prisms and optical disk substrates.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as engineering plastics in many fields because they are excellent in mechanical properties such as impact resistance, heat resistance and transparency. In particular, it has many uses as an optical material due to its excellent transparency. For example, it is used as various optical materials such as various lenses, prisms, and optical disk substrates.

However, a polycarbonate resin composed of an aromatic dihydroxy compound has a large photoelastic constant and a relatively poor melt flowability, so that the birefringence of the molded product increases, and the refractive index is as high as 1.58. Number is 30
Since it is low, it has a drawback that it does not have sufficient performance to be widely used for applications such as optical recording materials and optical lenses.

As a method of improving these drawbacks, an aromatic-aliphatic copolymer polycarbonate resin (Japanese Patent Laid-Open No.
No. 66234 and Japanese Patent Laid-Open No. 11-165426) have been proposed. These aromatic-aliphatic copolymerized polycarbonate resins have excellent impact resistance and heat resistance, and also have a low photoelastic constant and a good balance of refractive index and dispersion characteristics, and thus are widely used as optical materials. It can be used. However, simple copolymerization lacks impact resistance at low temperatures, and may cause problems in use in a wide temperature environment.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, exhibits excellent impact resistance even at low temperatures, and has high heat resistance and a high Abbe number. And an inexpensive method for producing an aromatic-aliphatic polycarbonate resin having a low photoelastic constant.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, have aromatic units having units represented by the following formulas (1) and (2) as constitutional units. -A polycarbonate resin composition comprising an aliphatic copolycarbonate resin (A) and a copolycarbonate resin (B) having units represented by the following formulas (1) and (3) as constitutional units has excellent durability. They have found that they have impact resistance, heat resistance, high Abbe number and low photoelastic constant, and completed the present invention.

[0007]

[Chemical 7] (In the above formula (1), X is

[0008]

[Chemical 8] Where R ₃ and R ₄ are hydrogen atoms or 1 carbon atoms
It is an alkyl group or a phenyl group of 10 and R ₃ and R ₄ may combine to form a ring. R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or halogen. R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. Moreover, m and n represent the number of substituents and are integers of 0-4. )

[0009]

[Chemical 9]

[0010]

[Chemical 10] (In the formula, R _{5 to} R ₁₂ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, carbon It is an alkoxy group having 1 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms.
R ₁₃ represents an aliphatic group having 1 to 6 carbon atoms or a single bond. Y
Is a --SiO (R ₁₄ ) (R ₁₅ )-homopolymer or --SiO (R ₁₄ ) (R
₁₅ )-and -SiO (R ₁₆ ) (R ₁₇ )-represent a random copolymer.
The degree of polymerization is 0 to 200, and R _{14 to} R ₁₇ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 2 to 5 carbon atoms. Is an alkenyl group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. )

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic-aliphatic copolymer polycarbonate resin according to the present invention will be specifically described below.

The aromatic-aliphatic copolymer polycarbonate resin (A) used in the present invention contains a random, block or alternating copolymer and the like, and is composed of the aliphatic dihydroxy compound represented by the above formula (2). The mole fraction of the derived structural unit is preferably 30% or more, more preferably 40% or more. Below 30%,
The effect of improving optical properties such as photoelastic constant and Abbe number is reduced. The weight average molecular weight (Mw) of the aliphatic-aromatic copolymer polycarbonate resin (A) is 10,000 to.
It is preferably 100,000, more preferably 30,000 to 80,000.

The aromatic-aliphatic copolymer polycarbonate resin (A) can be produced by a known method as a general method for producing a polycarbonate resin. In particular, polymerization can be carried out by a known melt polycondensation method using a carbonic acid diester, and specifically, an aromatic dihydroxy compound represented by the following formula (6) and an aliphatic dihydroxy compound represented by the following formula (7). Using the compound, carbonic acid diester and catalyst,
Melt polycondensation is carried out while removing by-products under heating under normal pressure or reduced pressure. The reaction is generally carried out in two or more steps.

[0014]

[Chemical 11]

(In the above formula (6), X is

[0016]

[Chemical 12] Where R ₃ and R ₄ are hydrogen atoms or 1 carbon atoms
It is an alkyl group or a phenyl group of 10 and R ₃ and R ₄ may combine to form a ring. R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or halogen. R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. Moreover, m and n represent the number of substituents and are integers of 0-4. )

[0017]

[Chemical 13]

Specific examples of the aromatic dihydroxy compound represented by the above formula (6) include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane and 2,2-bis ( 4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1 , 1-bis (4-hydroxy-3-
t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane , 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide,
4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-
Examples thereof include dihydroxy-3,3'-dimethyldiphenyl sulfone. Of these, 1,1-bis (4-hydroxyphenyl) cyclohexane is particularly preferable.

In the method for producing a polycarbonate according to the present invention, the carbonic acid diester used in the transesterification reaction includes diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate and diethyl. Carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. may be mentioned. Among these, diphenyl carbonate is particularly preferable. The chlorine content in diphenyl carbonate, which also causes coloring, is preferably 20 ppm or less. More preferably, it is 10 ppm or less. The diphenyl carbonate is used in an amount of 0.97 to 1.% per 1 mol of the total amount of the aromatic dihydroxy compound and the aliphatic dihydroxy compound.
It is preferably used in an amount of 2 mol, particularly preferably an amount of 0.99 to 1.10 mol.

In the method for producing a polycarbonate according to the present invention, the catalyst used in the transesterification reaction is
Basic compounds are used. Examples of such basic compounds include alkali metal compounds and / or alkaline earth metal compounds, nitrogen-containing compounds and the like.

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

As such an alkali metal compound,
Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate,
Lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate , 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 sodium phenyl phosphate, 2 sodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium Salt or the like is used.

As the alkaline earth metal compound,
Specifically, magnesium hydroxide, calcium hydroxide,
Strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, phenyl phosphate Magnesium or the like is used.

Specific examples of the nitrogen-containing compound include alkyl, aryl such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide. Ammonium hydroxides having an aryl group, tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine,
Imidazoles such as 2-methylimidazole and 2-phenylimidazole, or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate are used.

These catalysts are used in an amount of 10 ^-9 to 10 ^-3 mol, preferably 10 ^-7 to 1 per 1 mol of the total amount of the aromatic dihydroxy compound and the aliphatic dihydroxy compound.
Used in an amount of 0 ^-5 mol.

The transesterification reaction relating to the present invention is specifically carried out in the first stage reaction at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0 to 5 hours, preferably 0.5 to 3 React for hours. Next, the reaction temperature is raised while raising the degree of vacuum of the reaction system to cause the reaction of the aromatic dihydroxy compound, the aliphatic dihydroxy compound and the carbonic acid diester, and finally under a reduced pressure of 133 Pa or less, 200 to 3
The polycondensation reaction is carried out at a temperature of 00 ° C. Such a reaction
It may be carried out continuously or batchwise. The reaction apparatus used in carrying out the above reaction is a tank type,
It may be an extruder type or a horizontal type device having a stirring blade having an excellent surface renewal property such as a paddle blade, a lattice blade, and a spectacle blade.

The copolymerized polycarbonate resin (B) used in the present invention is produced by a known polymerization method such as a transesterification method and an interfacial polymerization method. The production method is not particularly limited, but it is generally commercially available. Na, K, C as well as existing polycarbonate (bisphenol A type, etc.)
Impurity metal components such as a and Fe and Cl and the like are preferably 10 ppm or less, more preferably 1 ppm or less from the viewpoint of hue and the like. Also, a copolymerized polycarbonate resin (B)
The structure of the structural unit and the structural unit derived from the aromatic compound in the aromatic-aliphatic copolymer polycarbonate resin (A) may be the same or different.

The copolymerized polycarbonate resin (B) used in the present invention is produced from the compounds represented by the following formulas (6) and (8).

[0029]

[Chemical 14] (In the above formula (6), X is

[0030]

[Chemical 15] Where R ₃ and R ₄ are hydrogen atoms or 1 carbon atoms
It is an alkyl group or a phenyl group of 10 and R ₃ and R ₄ may combine to form a ring. R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or halogen. R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. Moreover, m and n represent the number of substituents and are integers of 0-4. )

[0031]

[Chemical 16] (In the formula, R _{5 to} R ₁₂ are each independently hydrogen, a substituted or unsubstituted C 1-5 alkyl group, a C 6-12 aryl group, a C 2-5 alkenyl group, or a carbon atom. It is an alkoxy group having 1 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms.As a substituent, an alkyl group having 1 to 5 carbon atoms and 2 carbon atoms
To alkenyl groups having 1 to 5 carbon atoms and alkoxy groups having 1 to 5 carbon atoms. R ₁₃ represents an aliphatic group having 1 to 6 carbon atoms or a single bond. Y _{is, -SiO (R 14) (R} 15) - homopolymers or -SiO of _{(R 14) (R 15)} - and _{-SiO (R 16) (R 17} ) - represents a random copolymer. The degree of polymerization is 0 to 200, and R _{14 to} R ₁₇ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 2 to 5 carbon atoms. Alkenyl group, C1-5 alkoxy group, or C7
~ 17 aralkyl groups. 1 to 5 carbon atoms as a substituent
And an alkyl group having 2 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms).

Specific examples of the aromatic dihydroxy compound represented by the above formula (6) include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane and 2,2-bis ( 4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl)
Phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3) -
Bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '-Dimethylphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,
4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4 '
-Dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone and the like can be mentioned. Of these, 1,1-bis (4-hydroxyphenyl) cyclohexane and 2,2-bis (4-hydroxyphenyl) propane are particularly preferable.

As the compound represented by the above formula (8),
Specifically, the following are exemplified.

[0034]

[Chemical 17]

[0035]

[Chemical 18] (In the above formula, Z is

[0036]

[Chemical 19] Alternatively, a plurality of blocks are randomly combined, and a ≧ 0, b ≧ 0, c ≧ 0, and 200 ≧
(A + b + c) ≧ 0. )

It is also possible to use two or more of these in combination. Z preferably contains 1 to 100 dimethylsiloxane or 1 to 100 diphenylsiloxane and a random copolymer thereof. Above all,
α, ω-bis [3- (o-hydroxyphenyl) propyl]
Polydimethylsiloxane is preferred.

The polycarbonate resin of the present invention preferably has a catalyst removed or deactivated in order to maintain thermal stability and hydrolysis stability. Generally, a method of deactivating a transesterification catalyst such as an alkali metal or an alkaline earth metal by adding a known acidic substance is preferably carried out. Specific examples of these substances include p
-Aromatic sulfonic acids such as toluene sulfonic acid, p-
Aromatic sulfonates such as butyl toluene sulfonate, aromatic sulfonates such as dodecylbenzene sulfonic acid tetrabutylphosphonium salt, stearic acid chloride, butyric acid chloride, benzoyl chloride, organic halides such as toluene sulfonic acid chloride, Alkyl sulfates such as dimethylsulfate, organic halides such as benzyl chloride, inorganic acids such as boric acid and phosphoric acid, and phosphite esters such as diphenylphosphite are preferably used. There is no limitation on the timing of adding the catalyst deactivator, and it may be added at the same time as the melt mixing with the copolycarbonate resin (B), before the melt mixing, or after the melt mixing.

After deactivating the catalyst, a step of devolatilizing low-boiling compounds in the polymer at a pressure of 13 to 133 Pa and a temperature of 200 to 300 ° C. may be provided. For this purpose, paddle blades, lattice blades, Horizontal type, thin film evaporator equipped with spectacle blades, etc.
Alternatively, a multi-vent type extruder is preferably used.

In the present invention, in addition to the catalyst deactivator, known antioxidants, pigments, dyes, reinforcing agents and fillers, ultraviolet absorbers, which are commonly used in polycarbonate,
A lubricant, a release agent, a crystal nucleating agent, a plasticizer, a fluidity improver, an antistatic agent and the like can be added. Further, other polycarbonate resin or thermoplastic resin may be blended and used for the purpose of further improving the characteristics of the resin.

In the polycarbonate resin composition of the present invention, the aromatic-aliphatic copolymer polycarbonate resin (A) is used.
It is preferable that the mixing ratio of the copolycarbonate resin (B) and the copolycarbonate resin (B) is 5:95 to 95: 5 by weight. When the mixing ratio of the copolymerized polycarbonate resin (B) in the polycarbonate resin composition is 5% by weight or less, the characteristics such as impact resistance and heat resistance of the aromatic polycarbonate resin are not sufficiently reflected in the composition, and the effect of addition is obtained. Can't get On the other hand, the mixing ratio of the copolymerized polycarbonate resin (B) is 95% by weight.
If it is above, the original effect of improving the photoelastic constant, Abbe number, etc. cannot be sufficiently obtained. Within this range, the addition amount of the copolymerized polycarbonate resin (B) is appropriately determined in consideration of the physical properties of the aromatic-aliphatic copolymerized polycarbonate resin (A) to obtain a polycarbonate resin composition having desired physical properties. be able to. Further, the aromatic of the present invention-
The molar ratio of the structural unit (1) derived from the aromatic compound and the structural unit (2) derived from the aliphatic compound in the aliphatic polycarbonate resin composition (A) (aromatic structural unit (1) / aliphatic Structural unit (2)) is 10/90 to 90
/ 10 is preferable, and more preferably 20/80 to 80
/ 20. The molar ratio of the structural unit (1) derived from an aromatic compound and the structural unit (2) derived from an aliphatic compound (aromatic structural unit (1) / aliphatic structural unit (2)) is from 10/90. If it is low, the heat resistance will be poor. On the other hand, if it is higher than 90/10, the photoelastic constant, the water absorption rate, etc. will be high, and the balance between the refractive index and the dispersion value will be poor.

The aromatic-aliphatic copolymerized polycarbonate resin (A) and the copolymerized polycarbonate resin (B) can be mixed by mechanical mixing or common solvent known as a method for producing a polymer alloy or a polymer blend. It is possible to use freeze-drying or spray-drying after dissolution, mixing of fine particles and the like. From an economical point of view, the mechanical mixing method is the most excellent, and representative mechanical mixing methods include a melt mixing method using a twin screw extruder, a single screw extruder, roll kneading, an internal mixer, or the like. Can be mentioned.

[0043]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

In the examples, the physical properties were measured by the following methods. MI: 240 ° C using a melt indexer, 5.00k
It was measured with a load of g. Tg: Measured with a differential scanning calorimeter. Refractive index: Measured with an Abbe refractometer according to JIS K 7105. Abbe number: Measured with an Abbe refractometer and calculated. Drop weight impact strength: 100 mmφ × 3 mm disc is molded by injection molding machine, and instrumented drop weight impact tester (CHAST, FRACTVIS) equipped with constant temperature bath, tip 20R
The instrumented falling weight of was collided at 7 m / sec and the breaking energy was measured. Weight average molecular weight Mw: GPC (Shodex GPC
It was measured as a polystyrene reduced molecular weight (weight average molecular weight: Mw) using a system 11). Chloroform was used as the developing solvent.

Example 1 130 ° C. in a nitrogen gas atmosphere substantially free of oxygen
Diphenyl carbonate and 2,2 in a mixing tank kept warm
-Bis (4-hydroxyphenyl) propane (hereinafter BP
Z is abbreviated as a fixed ratio (diphenyl carbonate / B
The liquid of diphenyl carbonate kept at 130 ° C. was fed to the mixing tank so that PZ (molar ratio) = 2.02), and after the stirring was started, BPZ (powder) was charged into the mixing tank.
Sodium bicarbonate (catalyst, BPZ10
0.000054 parts by weight) was added while mixing with BPZ. Heating was started so that the internal temperature of the mixing tank was maintained at 155 ° C, and 1 hour after the internal temperature reached 155 ° C, the internal temperature was lowered to 130 ° C in 15 minutes and kept at 130 ° C. The solution was transferred to the buffer tank.
First vertical stirring polymerization tank (reaction conditions: 13.3 kPa, 20
The raw material molar ratio (diphenyl carbonate / (BPZ + TCDDM)) at 5 ° C. and a stirring speed of 160 rpm is 1.01.
So that the molten mixture of diphenyl carbonate and BPZ in the buffer tank is continuously supplied to the first polymerization tank at a flow rate of 47.5 kg / h, and at the same time, TCDDM is
It was continuously supplied at a flow rate of 3.2 kg / h. Further, when the two liquids were supplied, each liquid was passed through a metal filter of 0.6 μm and then supplied to the first tank. The liquid level was kept constant while controlling the valve opening degree provided in the polymer discharge line at the bottom of the tank so that the average residence time in the first polymerization tank was 60 minutes. The polymerization liquid (prepolymer) discharged from the bottom of the tank is successively successively passed through the second, third, and fourth vertical polymerization tanks and the fifth horizontal polymerization tank (Hitachi glass wing polymerization machine (trade name)). Supplied continuously. The liquid level was controlled so that the average residence time was 60 minutes for each of the second to fourth vertical polymerization tanks and 90 minutes for the fifth horizontal polymerization tank, and at the same time, by-produced phenol was distilled off. . The polymerization conditions of each of the second to fifth polymerization tanks are as follows: second polymerization tank (220 ° C., 2000 Pa, stirring speed 160 rpm), third polymerization tank (230 ° C., 40 Pa, stirring speed 60 rpm), fourth polymerization tank ( 240 ° C, 40Pa,
Stirring speed 20 rpm), 5th horizontal polymerization tank (245 ° C, 40
Pa, stirring speed 5 rpm). The polymer discharged from the fifth horizontal polymerization tank (Mw = 58700) is continuously in a molten state in a 3-vent type twin-screw extruder (46 mm twin-screw extruder).
(Made by Kobe Steel Co., Ltd.), the additives described below are supplied in the form of a masterbatch to the resin at a supply rate of 0.7 kg / h by a side-feed compactor before the vent port closest to the resin supply port. 66 in kneading and venting
After devolatilization at a reduced pressure of 6 Pa, the below-described copolymerized polycarbonate which was heated and melted by a 40 mmφ single screw extruder (L / D = 28) was supplied to the twin screw extruder at 4.0 kg / h, and kneaded and deaerated. Then, the mixture was passed through a 10 μm resin filter and then water-cooled pelletized. The composition of the masterbatch is based on the aromatic-aliphatic copolycarbonate produced by the method described above without adding the copolycarbonate,
The amount of butyl p-toluenesulfonate (manufactured by Tokyo Kasei Kogyo; pTSB hereinafter) is 9 times the neutralization equivalent of sodium hydrogen carbonate [27 μmol / mol (based on the total moles of BPZ and TCDDM)], and Based on 100 parts by weight of the total amount, 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one (HP-1
36; Ciba Specialty Chemicals) 300pp
m, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (HP-1 manufactured by Asahi Denka Co., Ltd.
0) was adjusted to 500 ppm. The evaluation results are shown in Table 1. The copolymerized polycarbonate is produced by copolymerizing the compounds represented by the following structural formulas (a) and (b) by an interfacial method at a weight ratio (a) / (b) = 95/5. .

[0046]

[Chemical 20]

[0047]

[Chemical 21]

Example 2 The same operation as in Example 1 was carried out except that the composition of the copolycarbonate was changed to that described below.
The results obtained are shown in Table 1. The copolymerized polycarbonate is produced by copolymerizing the compounds represented by the following structural formulas (c) and (d) at a weight ratio (c) / (d) = 90/10 by an interfacial method. .

[0049]

[Chemical formula 22]

Comparative Example 1 Resin pellets were obtained in the same manner as in Example 1, except that the copolymerized polycarbonate resin was not added to the twin-screw extruder. The pellets were evaluated and the results obtained are shown in Table 1.

[0051]

INDUSTRIAL APPLICABILITY The polycarbonate resin of the present invention has improved properties such as refractive index, dispersion balance and photoelastic constant while maintaining the excellent properties such as impact resistance and heat resistance of polycarbonate. It can be suitably used for plastic optical materials such as, prisms and optical disk substrates.

[0052]

[Table 1]

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazumasa Kazumasa             Mie Prefecture Yokkaichi City Hinohito 2-4-16               Mitsubishi Gas Chemical Co., Ltd. Yokkaichi Plant (72) Inventor Fujio Sakuma             Mie Prefecture Yokkaichi City Hinohito 2-4-16               Mitsubishi Gas Chemical Co., Ltd. Yokkaichi Plant (72) Inventor Susumu Watanabe             Mie Prefecture Yokkaichi City Hinohito 2-4-16               Mitsubishi Gas Chemical Co., Ltd. Yokkaichi Plant F-term (reference) 4J002 CG01W CG02W CG02X GP00                       GP01 GS02                 5D029 KA07 KC09

Claims (5)

[Claims] 1. An aromatic-aliphatic copolymerized polycarbonate resin (A) having a unit represented by the following formula (1) and a unit represented by the formula (2) as a constitutional unit, and the following formula (A) as a constitutional unit: A polycarbonate resin composition comprising a unit represented by 1) and a copolymerized polycarbonate resin (B) having a unit represented by the formula (3). [Chemical 1] (In the above formula (1), X is Where R ₃ and R ₄ are a hydrogen atom and have 1 to 10 carbon atoms.
Which is an alkyl group or a phenyl group, and R ₃ and R ₄ may combine to form a ring. R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or halogen. R ₁ , R ₂ , R
₃ and R ₄ may be the same or different. Moreover, m and n represent the number of substituents and are integers of 0-4. ) [Chemical 3] [Chemical 4] (In the formula, R _{5 to} R ₁₂ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, carbon It is an alkoxy group having 1 to 5 carbon atoms or an aralkyl group having 7 to 17 carbon atoms.
R ₁₃ represents an aliphatic group having 1 to 6 carbon atoms or a single bond. Y
Is a --SiO (R ₁₄ ) (R ₁₅ )-homopolymer or --SiO (R ₁₄ ) (R
₁₅ )-and -SiO (R ₁₆ ) (R ₁₇ )-represent a random copolymer.
The degree of polymerization is 0 to 200, and R _{14 to} R ₁₇ are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 2 to 5 carbon atoms. Is an alkenyl group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. ) 2. An aromatic compound in a polycarbonate resin composition
2. The polycarbonate resin composition according to claim 1, wherein the proportion of the structural unit represented by the formula (1) in the aliphatic copolymer polycarbonate resin (A) is 10 to 90 mol%. 3. The constitutional unit represented by the formula (1) in the copolycarbonate resin (B), wherein the proportion of the copolycarbonate resin (B) in the polycarbonate resin composition is 5 to 95% by weight. Is 5% by weight or more, and the polycarbonate resin composition according to claim 1 or 2. 4. The constitutional unit represented by formula (1) is a unit represented by the following formula (4) or formula (5), wherein: Polycarbonate resin composition. [Chemical 5] [Chemical 6] 5. (1) Refractive index 1.54 to 1.60, (2)
An optical material comprising the polycarbonate resin composition according to claim 1, having an Abbe number of 33 to 50.