JPH10310692A - Aromatic polycarbonate resin composition, and optical article member produced therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an arom. polycarbonate resin compsn. excellent in optical properties, such as clarity and low birefringence, and used for optical information materials, by compounding an arom. polycarbonate resin having structural units derived from bishydroxyphenylfluorene, etc., and structural units derived from bishydroxyphenylphenylethane, etc., with an arom. polycarbonate resin having structural units derived from bishydroxyphenylpropane. etc. SOLUTION: This compsn. comprises 1-99 wt.% arom. copolycarbonate resin (A) comprising 10-60 mol.% structural units represented by formula I and 90-40 mol.% structural units represented by formula II (wherein R<1> is H, an alkyl, or phenyl) and an arom. polycarbonate resin (B) having higher than 50 mol.%, pref. 80 mol.% or higher, structural units represented by formula II (wherein R<2> and R<3> are each H or an alkyl) and/or formula IV (wherein X is an ether bond, etc.). provided each benzene ring in formulas I to IV may be substd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aromatic polycarbonate resin composition having excellent optical properties such as transparency, optical homogeneity, and low birefringence, and also having excellent moldability. The present invention relates to an optical product member comprising the same.

[0002]

2. Description of the Related Art Conventionally, aromatic polycarbonate resins, for example, bisphenol A as a diol component,
That is, an aromatic polycarbonate resin obtained using an aromatic diol represented by 2,2-bis (4-hydroquinphenyl) propane has excellent transparency, mechanical properties, heat resistance, dimensional stability, and the like. Because of its excellent properties, it is widely used as an engineering plastic in many fields. In particular, its excellent transparency has many uses as optical product members. However, the conventional polycarbonate resin has a drawback of having a large birefringence as an optical material, and in recent years, a demand for reduction thereof has been increasing. In particular, when used as an optical information material utilizing a digital signal, for example, a digital audio disc, a digital video disc, and a disc for information reading and writing, not only transparency, but also optical distortion and birefringence. The requirement for reduction is strict, and among them, in the magneto-optical recording system, it is required that the birefringence (perpendicular birefringence) in the cross-sectional direction of the substrate be 5 × 10 ⁻⁵ or less. On the other hand, in order to reduce optical distortion in injection molding which is usually performed, a method of increasing the molten resin temperature to improve the melt fluidity is adopted, but when the resin temperature is increased, the resin is increased. Various troubles have occurred due to the deterioration of, and it has not been a sufficient solution.

On the other hand, various polycarbonate resin materials have been developed for the purpose of reducing birefringence. For example, as a diol component, 9,9-
A polycarbonate resin using bis (4-hydroxyphenyl) fluorene is known, but this resin has a significant birefringence reduction effect, but has a problem that molding is difficult. For example, U.S. Pat. No. 5,486,577. In order to solve this point, the book states that 2,2-bis (4-
It has been proposed to mix a polycarbonate resin using (hydroxyphenyl) propane. However, as far as the inventor knows, this composition has low birefringence, but has problems in transparency and optical homogeneity, and has insufficient moldability. JP-A-2-304741 discloses the above-mentioned fluorene and aromatic diols such as 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) -1-phenylethane. Although a polycarbonate copolymer obtained by copolymerizing the component with the component is described, also in this case, as far as the present inventor knows, although the effect of reducing birefringence is recognized, transparency, optical homogeneity is insufficient, In addition, there is a problem in moldability.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems in using an aromatic polycarbonate resin for an optical material. It is an object of the present invention to provide an aromatic polycarbonate resin composition having excellent optical properties such as mechanical homogeneity and low birefringence, and also excellent in moldability, and an optical product member comprising the same.

[0005]

The gist of the present invention is an aromatic polycarbonate resin composition comprising the following components (A) and (B), and an optical product member comprising the same. Component (A); the following general formula (I)

[0006]

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(Wherein each benzene ring may have a substituent) and 10 to 60 mol% of a structural unit represented by the following general formula (II):

[0008]

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(Wherein, R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent, and each benzene ring has a substituent. Structural units 90 to 40 represented by
-99% by weight of an aromatic polycarbonate copolymer resin consisting of

Component (B): The following general formula (III)

[0011]

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(Wherein, R ² and R ³ represent a hydrogen atom or an alkyl group which may have a substituent, and each benzene ring may have a substituent). And / or the following general formula (IV)

[0013]

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(Wherein, X represents an ether bond, a thioether bond, or a sulfone bond, and each benzene ring may have a substituent). Aromatic polycarbonate resin 99
~ 1% by weight

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The substituent of the benzene ring in the structural unit represented by the above general formula (I) of the component (A) in the present invention is an alkyl group having 1 to 4 carbon atoms, 4
Specific examples of the aromatic diol for obtaining the structural unit represented by the general formula (I) include 9, 9 and 14.
9-bis (4-hydroxyphenyl) fluorene, 9,
9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene , 9,9-bis (3-methoxy-4-hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-chloro-4-hydroxyphenyl) Fluorene, 9,9-bis (3-trichloromethyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) -3,6
-Dimethylfluorene, 9,9-bis (4-hydroxyphenyl) -4,5-dimethylfluorene, 9,9-bis (4-hydroxyphenyl) -3,6-dichlorofluorene, 9,9-bis (4- Hydroxyphenyl)-
3,6-diphenylfluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) -3,6-dimethylfluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) -3,6- Dichlorofluorene and the like can be mentioned. Among them, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene are preferable.

Examples of R ¹ in the structural unit represented by the general formula (II) include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group and an ethyl group, and a phenyl group. The substituents on the benzene ring are the same as those in the general formula (I), and specific examples of the aromatic diol for obtaining the structural unit represented by the general formula (II) include bis (4 -Hydroxyphenyl) phenylmethane, bis (3-methyl-4-hydroxyphenyl) phenylmethane, bis (3-t-butyl-4-hydroxyphenyl) phenylmethane, bis (2,6-dimethyl-4)
-Hydroxyphenyl) phenylmethane, bis (3,5
-Dimethyl-4-hydroxyphenyl) phenylmethane, bis (2,3,5-trimethyl-4-hydroxyphenyl) phenylmethane, bis (3-phenyl-4-hydroxyphenyl) phenylmethane, bis (3-fluoro-4) -Hydroxyphenyl) phenylmethane, bis (3-bromo-4-hydroxyphenyl) phenylmethane, bis (3-fluoro-4-hydroxyphenyl)-
4-fluorophenylmethane, bis (4-hydroxyphenyl) -4-fluorophenylmethane, bis (4-hydroxyphenyl) -4-chlorophenylmethane, bis (4-hydroxyphenyl) -4-bromophenylmethane, bis (3 , 5-Dimethyl-4-hydroxyphenyl) -4-fluorophenylmethane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylethane, 1,1
-Bis (3-methyl-4-hydroxyphenyl) -1-
Phenylethane, 1,1-bis (3-t-butyl-4-
(Hydroxyphenyl) -1-phenylethane, 1,1-
Bis (3-phenyl-4-hydroxyphenyl) -1-
Phenylethane, 1,1-bis (4-hydroxyphenyl) -1- (4-nitrophenyl) ethane, 1,1-bis (3-bromo-4-hydroxyphenyl) -1-phenylethane, 1,1- Bis (4-hydroxyphenyl)
Examples thereof include -1-phenylpropane and bis (4-hydroxyphenyl) diphenylmethane. Inside,
1,1-bis (4-hydroxyphenyl) -1-phenylethane and 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane are preferred.

The structural unit derived from the aromatic diol represented by the general formula (I) in the aromatic polycarbonate copolymer resin of the component (A) (hereinafter may be abbreviated as "FL unit"). And a structural unit derived from the aromatic diol represented by the general formula (II) (hereinafter referred to as “T
It may be abbreviated as "P unit". ), The FL unit is 1 with respect to the total amount of the FL unit and the TP unit.
It is essential that the TP unit is 0 to 60 mol% and the TP unit is 90 to 40 mol%, the FL unit is 10 to 45 mol%, and the TP unit is 90 to 55 mol%. It is particularly preferred that 30 mol% and the TP unit are 90 to 70 mol%. When the FL unit is less than 10 mol%, the effect of reducing the birefringence of the composition is not recognized, and 6
If it exceeds 0 mol%, the transparency and optical homogeneity of the composition will be reduced, and further, there will be problems in the moldability. In addition, as the component (A) in the present invention, a structural unit derived from an aromatic diol or an aliphatic diol other than the FL unit and the TP unit may be copolymerized, as long as the properties are not impaired. The aromatic polycarbonate copolymer resin as the component (A) in the present invention has a limiting viscosity [η] at 20 ° C. of a methylene chloride solution.
It is preferably in the range of 0.20 to 0.46 dl / g.

In the component (B) of the present invention, R ² and R ³ in the structural unit represented by the above general formula (III) include a hydrogen atom, a methyl group, an ethyl group, a propyl group and a butyl group. Examples thereof include an alkyl group having 1 to 4 carbon atoms and the like. Further, R ² and R ³ may form a cycloalkylene ring, and are represented by the general formulas (III) and (IV). The substituent of the benzene ring in the structural unit is the same as that in the general formula (I), and specific examples of the aromatic diol for obtaining the structural unit represented by the general formula (III) include bis (4-hydroxyphenyl)
Methane, bis (3-methyl-4-hydroxyphenyl)
Methane, 1,1-bis (3-methyl-4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-ethyl-
4-hydroxyphenyl) propane, 2,2-bis (3
-Isopropyl-4-hydroxyphenyl) propane,
2,2-bis (3-s-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-
(Hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) hexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, , 1-
Bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) dibenzylmethane and the like can be mentioned. Specific examples of the aromatic diol for obtaining the structural unit represented by the general formula (IV) include:
4,4′-dihydroxydiphenyl ether, 4,4 ′
-Dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide and the like. Among them, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, and 2,2- Bis (4-hydroxyphenyl) hexafluoropropane is preferred, and 2,2
-Bis (4-hydroxyphenyl) propane is particularly preferred.

The component (B) in the present invention is a majority of the structural units represented by the general formulas (III) and / or (IV) (hereinafter sometimes abbreviated as "BP units"). And the BP unit is preferably at least 80 mol%. In this case, the other structural unit may be the FL in the component (A).
A unit, a TP unit, a constituent unit derived from an aliphatic diol, or the like is used, but a unit composed of only a BP unit is preferably used. The aromatic polycarbonate resin as the component (B) in the present invention has a limiting viscosity [η] at 20 ° C. of 0.26 to 0.64 in a methylene chloride solution.
It is preferably in the range of dl / g.

The aromatic polycarbonate resin of each of the component (A) and the component (B) in the aromatic polycarbonate resin composition of the present invention can be produced by a known industrially used method. For example, using a known catalyst, the aromatic diol and phosgene are subjected to interfacial polymerization (phosgene method or interfacial polymerization method), or transesterification between the aromatic diol and a carbonate such as diphenyl carbonate (ester exchange method). , Or a melt polymerization method).

The aromatic polycarbonate resin composition of the present invention is specifically composed of the following combination of an aromatic polycarbonate copolymer resin as the component (A) and an aromatic polycarbonate resin as the component (B). Can be exemplified.・ FL unit / TP unit copolymer + BP unit polymer ・ FL unit / TP unit copolymer + BP unit / FL unit copolymer ・ FL unit / TP unit copolymer + BP unit / TP unit copolymer FL unit / TP unit / BP unit copolymer + BP unit polymer FL unit / TP unit / BP unit copolymer + BP unit / FL unit copolymer FL unit / TP unit / BP unit copolymer + BP unit / TP unit copolymer

The composition ratio of component (A) to component (B) in the aromatic polycarbonate resin composition of the present invention is such that component (A) is 1 to 99% by weight and component (B) is 99 to 1% by weight. Preferably, component (A) is 5 to 60% by weight and component (B) is 95 to 40% by weight. Component (A) is 1
When the amount is less than 100% by weight, the effect of reducing the birefringence of the composition is not recognized.

The aromatic polycarbonate resin composition of the present invention is obtained by mixing the component (A) and the component (B), for example, by mixing the respective powders or granules with a mixer such as a super mixer, a Henschel mixer or a tumbler. It can be manufactured by a known method such as a method of melt-kneading with a twin-screw extruder, a kneader, a roll, or the like, or a method of mixing in a solution state. Incidentally, the aromatic polycarbonate resin composition of the present invention, in order to impart the required thermal stability, release properties, antistatic properties and the like when used as a molding material,
For example, phosphite-based, hindered phenol-based antioxidants, benzotriazole-based, benzophenone-based, dibenzoylmethane-based, salicylate-based light stabilizers, silicon-based, fatty acid-based, fatty acid ester-based, fatty acid glyceride-based, A lubricant such as a beeswax or a release agent, an antistatic agent such as a polyalkylene glycol or a fatty acid glyceride can be added.

In order to mold optical product members and the like using the aromatic polycarbonate resin composition of the present invention, extrusion molding,
Known molding methods such as injection molding, blow molding, compression molding, and injection compression molding can be used, but injection compression molding is suitable for molding the optical product member according to the present invention. Specific examples of the optical product member molded using the aromatic polycarbonate resin composition of the present invention include a high-density optical disk substrate, an optical disk pickup lens,
Examples include an optical lens, an LCD substrate, a PDP substrate, a television screen for projection, and a retardation film.

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. Production of Aromatic Polycarbonate Resin Production Example 1 17 parts by weight of 9,9-bis (4-hydroxyphenyl) fluorene for FL unit, 1,1 for TP unit
83 parts by weight of 1-bis (4-hydroxyphenyl) -1-phenylethane, 41 parts by weight of sodium hydroxide, water 62
A mixture of 0 parts by weight and 290 parts by weight of methylene chloride was charged into a reactor equipped with a stirrer, stirred at 800 rpm, and 63 parts by weight of phosgene was blown into the mixture for 1 hour to perform interfacial polymerization. Only the methylene chloride solution containing the polycarbonate oligomer was collected. The obtained methylene chloride solution of the oligomer was analyzed by the following method, and the following results were obtained. -Oligomer concentration (measured by evaporating to dryness); 20.3% by weight-Terminal chloroformate group concentration (Neutralization titration of aniline hydrochloride obtained by reacting with aniline with 0.2N sodium hydroxide aqueous solution) 0.27 regulation-Terminal phenolic hydroxyl group concentration (colorimetric determination at 546 nm when dissolved in titanium tetrachloride, acetic acid solution);
0.025 N Subsequently, a mixture of 100 parts by weight of the oligomer solution, 1.8 parts by weight of 3-pentadecylphenol, and 140 parts by weight of methylene chloride was charged into a reactor equipped with a stirrer.
The mixture was stirred at 550 rpm, and 48 parts by weight of a 4% by weight aqueous solution of sodium hydroxide and 0.27 parts by weight of a 2% by weight aqueous solution of triethylamine were added. After interfacial polymerization was performed for 7 hours, the reaction product was separated, and the polycarbonate resin was separated. Was washed with an aqueous sodium hydroxide solution, an aqueous hydrochloric acid solution, and water in this order, and finally, the methylene chloride was evaporated to collect a resin. The intrinsic viscosity [η] of this resin was 0.29 dl / g. Table 1 shows the above results.

Production Examples 2 to 8 Except that the various conditions were changed as shown in Table 1 (however, in Production Examples 2 to 6, the stirring speed at the time of producing the polymer was 200 rpm). Similarly, an oligomer was produced, the solution was analyzed, and a polycarbonate resin was produced, and its intrinsic viscosity was measured. They are shown in Table 1.

Examples 1 to 6, Comparative Examples 1 to 10 Polycarbonate resins obtained in Production Examples 1 to 8 and polycarbonate resins comprising only structural units derived from 2,2-bis (4-hydroxyphenyl) propane (Mitsubishi Gas Chemical Co., Ltd., Iupilon H4000, intrinsic viscosity [η] 0.36 dl / g), and mixed in a mixing ratio shown in Table 2 with a super mixer, and then a resin temperature of 300 using a twin screw extruder. The resin composition was produced by melt-kneading under a temperature condition of ~ 320 ° C. Further, an injection compression molding machine (Disc 5AM3) manufactured by Sumitomo Heavy Industries, Ltd. was used for the obtained resin composition.
Injection compression molding with a diameter of 130 mm and a thickness of 1.2
mm optical disc substrate was molded. For each optical disk substrate obtained, total light transmittance, optical homogeneity,
The birefringence and mold transferability were evaluated by the following methods, and the results are shown in Tables 2 and 3.

The total light transmittance was measured according to ASTM D1003 using # 80 manufactured by Nippon Denshoku Co., Ltd. -Optical homogeneity Tester manufactured by PULSTEC (optical system: laser wavelength 6)
(80 nm, NA = 0.6), the focus error signal (FES) was measured in the tracking ON state, and the ratio was shown as a ratio to the amplitude value of the “Iupilon H4000”. The format was a 4.6 GB magneto-optical disk. -Birefringence Use ADR-130N manufactured by Oak Works, radius 27-6
The range of 2 mm is obliquely 30
The average value of the perpendicular birefringence measured at the incident angle is shown. Molding transferability The number of shots was set to 1500, and the number of double stamping (D / S) out of 10 sheets was evaluated. Judgment was made based on the depth ratio and the shape between the substrate replica and the glass master in the pit, and evaluated based on the following criteria. ◎; very good ○; good △; insufficient ×; very bad

Comparative Example 11 As the component (A), 28% by weight of the resin obtained in Production Example 7
A resin composition was prepared in the same manner as in Examples 1 to 6, etc., except that a mixed composition (intrinsic viscosity [η] of 0.30 dl / g) of the resin obtained in Production Example 8 and 72% by weight was used. Manufactured.
The results are shown in Table 3.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

The present invention provides an aromatic polycarbonate resin composition having excellent optical properties such as transparency, optical homogeneity, and low birefringence, and also having excellent moldability. An optical product member can be provided.

Claims (5)

[Claims] An aromatic polycarbonate resin composition comprising the following component (A) and component (B). Component (A); the following general formula (I): (In the formula, each benzene ring may have a substituent.) 10 to 60 mol% of a structural unit represented by the following general formula (II): (Wherein, R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent, and each benzene ring has a substituent. 1 to 99% by weight of an aromatic polycarbonate copolymer resin comprising 90 to 40% by mole of a structural unit represented by the following formula (III): (Wherein, R ² and R ³ represent a hydrogen atom or an alkyl group which may have a substituent, and each benzene ring may have a substituent.) And / or the following general formula (IV): (Wherein, X represents an ether bond, a thioether bond, or a sulfone bond, and each benzene ring may have a substituent). Resin 99-1% by weight 2. The composition according to claim 1, wherein the component (A) comprises 10 to 30 mol% of the structural unit represented by the general formula (I).
The aromatic polycarbonate resin composition according to claim 1, wherein the constituent unit represented by I) is 90 to 70 mol%. 3. The aromatic polycarbonate resin composition according to claim 1, wherein the component (A) is 5 to 60% by weight and the component (B) is 95 to 40% by weight. 4. An optical product member comprising the aromatic polycarbonate resin composition according to claim 1. 5. The optical product member according to claim 4, wherein the optical product member is a substrate for an optical disk.