JP2001279079A - Polycarbonate resin composition and use therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in melt flowability, residence stability, etc., when being molded, and to provide optical components such as an optical disk substrate, a pick up lens, a plastic substrate for liquid crystal cells, a prism and an optical fiber which are obtained from the resin composition, are high in transparency and are excellent in a hue. SOLUTION: This resin composition comprises a polycarbonate copolymer having structural units represented by general formulas (1-a) and (2-a) (R1 and R3 are each an alkyl group, an alkoxy group, a nitro group or a halogen atom; R2 is H or methyl group; k and l are each an integer of 0 to 3; and m and n are each an integer of 0 to 20 with proviso that m+n is not equal to 0), and an epoxy compound alone or together with a phosphonic ester compound. The optical components are obtained by molding the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate copolymer containing a specific repeating structural unit and an epoxy compound or a polycarbonate resin composition containing an epoxy compound and a phosphite compound.
Further, the present invention relates to an optical component obtained by molding the resin composition. The resin composition of the present invention is excellent in transparency, mechanical properties, heat resistance, and the like, and has low birefringence, and further has excellent melt fluidity, excellent retention heat stability, and excellent moldability.
It is useful for optical components such as optical disk substrates, pickup lenses, plastic substrates for liquid crystal cells, prisms, and optical fibers.

[0002]

2. Description of the Related Art Polycarbonate is widely used as an engineering plastic in the fields of automobiles, electricity, and optics. At present, polycarbonates widely used are usually produced from 2,2-bis (4'-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) and carbonyl halide compounds such as phosgene. Polycarbonate produced from bisphenol A is a resin having well-balanced properties such as transparency, heat resistance, low moisture permeability, impact resistance, and dimensional stability, and is widely used. Particularly in recent years, it has been used in the field of optical components such as optical disk substrates. In an optical disk used as an information recording medium, since a laser beam passes through the disk main body, the disk substrate is of course transparent, and optical homogeneity is strongly required to reduce reading errors. .

[0003] However, for example, bisphenol A
When using polycarbonate manufactured from a resin substrate, the laser beam is generated by thermal stress, molecular orientation, residual stress due to volume change near the glass transition point, etc., generated during the cooling and flowing processes of the resin during molding of the disk substrate. When passing through, birefringence occurs. The large optical non-uniformity due to the birefringence is a fatal defect for an optical component such as an optical disk substrate, for example, causing an error in reading recorded information. Further, because the polycarbonate has a high viscosity at the time of melting, for example,
There is a problem in moldability such as it is very difficult to obtain a disk substrate having a smaller pit diameter by injection molding in order to increase the recording density.

[0004] As a method of solving such a problem,
Various new polymers have been proposed, for example, spirobiindanol alone in folicarbonate or a copolymerized polycarbonate of spirobiindanol and bisphenol A (Japanese Patent Application Laid-Open No. 63-314235). However, although the former polycarbonate has low birefringence, it has poor transparency and mechanical strength, for example, cracks are formed in a molded product during molding, and thus has a practical problem. Further, the latter polycarbonate, as the content of bisphenol A increases, transparency and mechanical properties are improved, but the birefringence increases,
There has been a problem in using it as an optical component such as an information recording medium as described above. Further, these polycarbonates have a somewhat lower viscosity at the time of melting than polycarbonates manufactured from existing bisphenol A, but have the above-mentioned discs for information recording media that require the precision workability described above. In practice, it is difficult to say that the substrate has sufficient melt fluidity to obtain by injection molding the substrate,
The solution of these problems has been strongly desired.

The present inventors have overcome the above problems and have good transparency, mechanical properties, heat resistance, etc. useful for optical parts, low birefringence, and As a resin having good fluidity and excellent moldability, a polycarbonate copolymer containing a repeating structural unit represented by the following general formulas (1-a) and (2-a) has been found, An application has already been filed (Japanese Patent Laid-Open No. 11-263833).
issue).

It is desired that a material for an optical component has a high light transmittance at a wavelength of a light source or light used for reading. That is, the degree of coloring of the resin as the material needs to be small. In addition, when molding an optical component, it is necessary to increase the melt flowability of the resin in order to transfer the precise shape of the component from a mold or to obtain an optical component with little residual distortion. Improving the melt fluidity is achieved, for example, by increasing the molding temperature in injection molding. However, when the molding is performed at a high temperature, the resin is likely to be decomposed or colored. For this reason, in order to use a resin for an optical component, stagnant heat stability is required.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems, to have excellent transparency, mechanical properties, heat resistance, etc., to have a low birefringence, and to obtain a melt fluidity during molding. Another object of the present invention is to provide a polycarbonate resin composition having excellent retention stability and good hue, and an optical component obtained by molding the polycarbonate resin composition.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to a polycarbonate copolymer containing a repeating structural unit represented by the following general formulas (1-a) and (2-a) (formula 2), and 100% by weight of the copolymer. The present invention relates to a polycarbonate resin composition containing 0.0005 to 5 parts by weight of an epoxy compound per part by weight.

[0009]

Embedded image (Wherein R ₁ and R ₃ are each independently an alkyl group,
Represents an alkoxy group, a nitro group or a halogen atom;
₂ represents a hydrogen atom or a methyl group, k and l each independently represent an integer of 0 to 3, and m and n each independently represent an integer of 0 to 20. However, m + n is never 0)

Further, the present invention relates to the above general formula (1-a)
And a polycarbonate copolymer 100 containing a repeating structural unit represented by the general formula (2-a) (Formula 2)
The polycarbonate resin composition according to claim 1 or 2, further comprising 0.0005 to 5 parts by weight of an epoxy compound and 0.0005 to 5 parts by weight of a phosphite compound, based on parts by weight. An optical component obtained by molding the composition.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polycarbonate resin composition of the present invention comprises a polycarbonate copolymer containing a repeating structural unit represented by the general formula (1-a) and the general formula (2-a), an epoxy compound or an epoxy compound and It is characterized by containing a phosphate compound. The polycarbonate copolymer used in the resin composition of the present invention (hereinafter also referred to as the polycarbonate copolymer of the present invention) comprises a dihydroxy compound represented by the general formula (1) (formula 3) and a general formula (2) ) Which is obtained by reacting a dihydroxy compound represented by the formula (3) with a carbonate precursor to copolymerize the compound, and which is derived from a compound represented by the general formula (1) and a carbonate precursor. Both a repeating structural unit represented by the formula (1-a) and a repeating structural unit represented by the general formula (2-a) derived from the compound represented by the general formula (2) and a carbonate precursor It is a copolymer having a repeating structural unit as an essential repeating structural unit, and may be any of a random copolymer, an alternating copolymer, and a block copolymer.

[0012]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , k, l, m and n are the same as above)

Among these polycarbonate copolymers, considering the balance of various properties such as heat resistance and mechanical properties, all repeating structural units represented by the general formulas (1-a) and (2-a) The proportion of the repeating structural unit represented by the general formula (1-a) contained therein is preferably from 5 to 5.
90 mol%, more preferably 10 to 80 mol%
And more preferably 20 to 70 mol%.

Formulas (1-a) and (2-a)
In the formula, R ₁ and R ₃ each independently represent an alkyl group, an alkoxy group, a nitro group or a halogen atom, preferably a linear, branched or cyclic alkyl group which may have a substituent, Represents a straight-chain, branched or cyclic alkoxy group, nitro group or halogen atom which may have, more preferably a straight-chain, branched or cyclic having 1 to 20 carbon atoms which may have a substituent; It represents an alkyl group, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent, a nitro group or a halogen atom.

More preferably, R ₁ and R ₃ are an unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms,
An unsubstituted straight-chain or branched alkoxy group having 1 to 10 carbon atoms or a chlorine atom, still more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
n-butyl group, isobutyl group, tert-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-
Butoxy group or chlorine atom. As R ₁ and R ₃ , a methyl group or a chlorine atom is particularly preferred. In the general formula (1-a), R ₂ represents a hydrogen atom or a methyl group.

Formulas (1-a) and (2-a)
In the formulas, k and l each independently represent an integer of 0 to 3, preferably 0, 1 or 2, and more preferably 0 or 1. The integer 0 is particularly preferred as k and l. In the general formula (1-a), m and n each independently represent an integer of 0 to 20, preferably an integer of 0 to 10, more preferably 0 to 10.
It is an integer of 5 and more preferably an integer of 0 to 2. The integer 1 is particularly preferred as m and n. However,
In these cases, m + n is never zero.

Formulas (1-a) and (2-a)
In the repeating structural unit represented by, the substitution position of the carbonate bond is respectively 4, 5, 6 or 7 on the benzene ring in the spirobiindane structure, or 4 ',
It is the 5 ', 6' or 7 'position. Among the repeating structural units represented by the general formula (1-a), a repeating structural unit represented by the following formula (1-a-A) (formula 4) also has a general formula (2)
Among the repeating structural units represented by -a),
A repeating structural unit represented by the following formula (2-a-A) (Formula 4) is particularly preferred.

[0018]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ , k, l, m and n are the same as described above)

As described above, the polycarbonate copolymer according to the present invention is obtained by allowing the dihydroxy compound represented by the general formula (1) and the dihydroxy compound represented by the general formula (2) to act on a carbonate precursor. It is obtained by copolymerization (JP-A-11-263833).
The dihydroxy compound represented by the general formula (1) and the dihydroxy compound represented by the general formula (2) are known compounds, respectively, and are preferably produced by a known method. The dihydroxy compound represented by the general formula (1)
The reaction itself is suitably produced by a known method using the dihydroxy compound represented by the general formula (2) as a production raw material. That is, the dihydroxy compound represented by the general formula (1) is obtained by combining the dihydroxy compound represented by the general formula (2) with an alkylene oxide such as ethylene oxide and propylene oxide, and a cyclic alkylene carbonate such as ethylene carbonate and propylene carbonate. , 2-
It can be produced by reacting with β-halohydrins such as bromoethanol, 2-chloroethanol, 2-bromo-1-propanol and the like. The dihydroxy compound represented by the general formula (2) is suitably produced by a known method, for example, a method described in JP-A-62-10030 or the like. For example, bisphenol A can be obtained by heating in the presence of an acid catalyst.

Examples of the method for producing the polycarbonate copolymer according to the present invention include various known polycarbonate polymerization methods [for example, Experimental Chemistry Course, 4th Edition, (28) Polymer Synthesis, pp. 231-242, Maruzen Publishing (1988) ), For example, a solution polymerization method, a transesterification method, or an interfacial polymerization method] is used. Typically, a dihydroxy compound represented by the general formula (1) and a dihydroxy compound represented by the general formula (2) are added to a carbonate precursor (for example, a diester carbonate compound such as dimethyl carbonate, diethyl carbonate, or diphenyl carbonate, or phosgene). And the like) are used.

Although the molecular weight of the polycarbonate copolymer according to the present invention is not particularly limited, the weight average molecular weight is usually a molecular weight in terms of standard polystyrene measured by GPC (gel permeation chromatography). 5,000 to 200,000, preferably 10,000 to 150,000, and more preferably 15,000 to 120,000. The polydispersity index expressed as a ratio between the weight average molecular weight and the number average molecular weight is not particularly limited, but is preferably 1.5 to 20.0, more preferably 2. 0 to 15.0, and more preferably,
2.0 to 10.0.

The polycarbonate copolymer according to the present invention is a repeating unit represented by the general formula (1-a) or (2-a), and comprises a plurality of different repeating structural units. It may be a polymer. Also, a polycarbonate containing another repeating structural unit other than the repeating structural unit represented by the general formula (1-a) or the general formula (2-a) as long as the desired effects of the present invention are not impaired. It may be a copolymer.

Formula (1-a) or Formula (2-a)
The other repeating structural unit other than the repeating structural unit represented by is a repeating structural unit derived from another dihydroxy compound other than the dihydroxy compound represented by the general formula (1) or (2), Examples of the dihydroxy compound include various known aromatic dihydroxy compounds or aliphatic dihydroxy compounds.

Specific examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane,
1,1-bis (4′-hydroxyphenyl) ethane, 1,2-bis (4′-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4 -Hydroxyphenyl) -1-naphthylmethane, 1,1-bis (4′-hydroxyphenyl) -1-phenylethane, 2,2-bis (4′-hydroxyphenyl) propane [“bisphenol A”], 2- (4'-
Hydroxyphenyl) -2- (3′-hydroxyphenyl) propane, 2,2-bis (4′-hydroxyphenyl) butane,
1,1-bis (4'-hydroxyphenyl) butane, 2,2-bis (4'-hydroxyphenyl) -3-methylbutane, 2,2-bis (4'-hydroxyphenyl) pentane, 3,3-bis (4'-hydroxyphenyl) pentane, 2,2-bis (4'-hydroxyphenyl) hexane, 2,2-bis (4'-hydroxyphenyl) octane, 2,2-bis (4'-hydroxyphenyl)- 4-methylpentane, 2,2-bis (4'-hydroxyphenyl) heptane, 4,4-bis (4'-hydroxyphenyl) heptane, 2,
2-bis (4'-hydroxyphenyl) tridecane, 2,2-bis (4'-hydroxyphenyl) octane, 2,2-bis (3'-
Methyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-ethyl-4'-hydroxyphenyl) propane,
2-bis (3'-n-propyl-4'-hydroxyphenyl)
Propane, 2,2-bis (3'-isopropyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-sec-butyl-4 '
-Hydroxyphenyl) propane, 2,2-bis (3'-tert-
Butyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-cyclohexyl-4'-hydroxyphenyl) propane, 2,2-bis (3'-allyl-4'-hydroxyphenyl) propane, 2-bis (3'-methoxy-4'-hydroxyphenyl) propane, 2,2-bis (3 ', 5'-dimethyl-4'
-Hydroxyphenyl) propane, 2,2-bis (2 ', 3',
5 ', 6'-tetramethyl-4'-hydroxyphenyl) propane, bis (4-hydroxyphenyl) cyanomethane, 1-
Cyano-3,3-bis (4′-hydroxyphenyl) butane,
Bis (hydroxyaryl) alkanes such as 2,2-bis (4′-hydroxyphenyl) hexafluoropropane,

1,1-bis (4'-hydroxyphenyl) cyclopentane, 1,1-bis (4'-hydroxyphenyl) cyclohexane, 1,1-bis (4'-hydroxyphenyl) cycloheptane, 1,1 -Bis (3'-methyl-4'-hydroxyphenyl) cyclohexane, 1,1-bis (3 ', 5'-dimethyl-
4'-hydroxyphenyl) cyclohexane, 1,1-bis (3 ', 5'-dichloro-4'-hydroxyphenyl) cyclohexane, 1,1-bis (3'-methyl-4'-hydroxyphenyl) -4- Methylcyclohexane, 1,1-bis (4'-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,
2-bis (4'-hydroxyphenyl) norbornane, 2,2-
Bis (hydroxyaryl) cycloalkanes such as bis (4'-hydroxyphenyl) adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,
Bis (hydroxyaryl) ethers such as 3'-dimethyldiphenylether and ethylene glycol bis (4-hydroxyphenyl) ether, 4,4'-dihydroxydiphenylsulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenylsulfide , 3,3'-Dicyclohexyl-
Bis (hydroxyaryl) sulfides such as 4,4'-dihydroxydiphenyl sulfide and 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfide;

Bis (hydroxyaryl) sulfoxides such as 4,4'-dihydroxydiphenylsulfoxide and 3,3'-dimethyl-4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4 ' -
Bis (hydroxyaryl) sulfones such as dihydroxy-3,3'-dimethyldiphenylsulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3-
Bis (hydroxyaryl) ketones such as methylphenyl) ketone, and 7,7′-dihydroxy-3,3 ′,
4,4'-tetrahydro-4,4,4 ', 4'-tetramethyl-2,2'-spirobi (2H-1-benzopyran), trans-2,3-bis (4'-hydroxyphenyl) -2 -Butene, 9,9-bis (4'-hydroxyphenyl) fluorene, 3,3-bis (4 '
-Hydroxyphenyl) -2-butanone, 1,6-bis (4'-
Hydroxyphenyl) -1,6-hexanedione, α, α,
α ', α'-tetramethyl-α, α'-bis (4-hydroxyphenyl) -p-xylene, α, α, α', α'-
Tetramethyl-α, α′-bis (4-hydroxyphenyl) -m-xylene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin and the like. Further, an aromatic dihydroxy compound containing an ester bond which can be produced, for example, by reacting 2 mol of bisphenol A with 1 mol of isophthaloyl chloride or terephthaloyl chloride is also useful.

Specific examples of the aliphatic dihydroxy compound include 1,2-dihydroxyethane, 1,3-dihydroxypropane, 1,4-dihydroxybutane, and 1,5-dihydroxybutane.
Dihydroxypentane, 3-methyl-1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1,7
-Dihydroxyheptane, 1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,
12-dihydroxydodecane, dihydroxyneopentyl, 2-ethyl-1,2-dihydroxyhexane, 2-
Dihydroxyalkanes such as methyl-1,3-dihydroxypropane, 1,3-dihydroxycyclohexane,
Examples include dihydroxycycloalkanes such as 1,4-dihydroxycyclohexane and 2,2-bis (4′-hydroxycyclohexyl) propane. Furthermore, o-dihydroxyxylylene, m-dihydroxyxylylene, p-dihydroxyxylylene, 1,4-bis (2′-hydroxyethyl) benzene, 1,4-bis (3′-hydroxypropyl) benzene, 4-bis (4'-hydroxybutyl) benzene, 1,4-bis (5'-hydroxypentyl) benzene, 1,4-bis (6'-hydroxyhexyl) benzene, 2,2-bis [4 '-( 2 "-hydroxyethyloxy) phenyl]
Examples include dihydroxy compounds such as propane.

Further, as another repeating structural unit other than the repeating structural unit represented by the general formula (1-a) or (2-a), two repeating units other than the above-mentioned dihydroxy compound are used.
It may contain a repeating structural unit derived from a functional compound. That is, examples of the bifunctional compound other than the dihydroxy compound include compounds such as aromatic dicarboxylic acids, aliphatic dicarboxylic acids, aromatic diamines, aliphatic diamines, aromatic diisocyanates, and aliphatic diisocyanates. By using these bifunctional compounds, in addition to the carbonate group, an imino group, an ester group, an ether group, an imide group, an amide group, a urethane group, a polycarbonate copolymer containing a group such as a urea group is obtained, The present invention also includes such a polycarbonate copolymer.

Formula (1-a) or Formula (2-a)
When other repeating structural units other than the repeating structural unit represented by are contained, the general formula (1)
The proportion occupied by the repeating structural units represented by -a) and the general formula (2-a) is not particularly limited as long as the desired effect of the present invention is not impaired.
Mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more. In order to obtain the maximum effect of the present invention, only the repeating structural units represented by the general formulas (1-a) and (2-a) are contained without containing other repeating structural units. Copolymers are particularly preferred.

In the polycarbonate copolymer according to the present invention, the terminal group is a hydroxy group, a haloformate group,
It may be a reactive terminal group such as a carbonate group, or may be an inert terminal group sealed with a molecular weight regulator. The amount of the terminal group in the polycarbonate copolymer according to the present invention is not particularly limited, but is usually 0.001 to 10 mol%, preferably 0.01 to 10 mol%, based on the total number of moles of the structural units. 5 mol%, more preferably 0.1 mol%.
1 to 3 mol%.

When the polycarbonate copolymer according to the present invention is produced by polymerization according to the above-mentioned method, it is preferable to carry out the polymerization in the presence of a molecular weight regulator for the purpose of controlling the molecular weight. Such a molecular weight regulator is not particularly limited, and may be any of various known molecular weight regulators used in a known polycarbonate polymerization.
For example, monovalent hydroxyaliphatic compounds or hydroxyaromatic compounds or derivatives thereof (eg, monovalent hydroxyaliphatic compounds or alkali metal or alkaline earth metal salts of hydroxyaromatic compounds, monovalent hydroxyaliphatic compounds or A haloformate compound of a hydroxyaromatic compound, a monovalent hydroxyaliphatic compound or a carbonate of a hydroxyaromatic compound, a monovalent carboxylic acid or a derivative thereof (eg, an alkali metal or alkaline earth metal of a monovalent carboxylic acid) Salts, acid halides of monovalent carboxylic acids, esters of monovalent carboxylic acids, and the like). The amount of the molecular weight modifier used is not particularly limited, and may be used as desired to adjust the molecular weight to a target. Usually, the amount is 0.001 to 10 based on the total number of moles of the dihydroxy compound to be polymerized. Mol%
And preferably 0.01 to 5 mol%.

The resin composition of the present invention comprises the above-mentioned polycarbonate copolymer of the present invention and an epoxy compound or an epoxy compound and a phosphite compound. The epoxy compound contained in the resin composition of the present invention is based on 100 parts by weight of the polycarbonate copolymer containing the repeating structural units represented by the general formulas (1-a) and (2-a). 0.0005 to 5 parts by weight, and preferably 0.1 to 5 parts by weight.
001 to 3 parts by weight, more preferably 0.01 to 2 parts by weight.

The epoxy compound used in the present invention is:
A compound having an epoxy group (oxirane ring),
It may be aromatic or aliphatic, and the aliphatic may be linear, branched or cyclic. The epoxy compound may be a halogen atom, a carboxyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, an alkylaminocarbonyl group, a hydroxyl group, an alkoxy group, a cyano group, a nitro group, an amino group, an aminoalkyl group, or a sulfo group. And so on. Further, among these substituents, two or more same or different substituents may be contained in the molecule.

Examples of the epoxy compound include cyclohexene oxide compounds, cyclic epoxy compounds other than cyclohexene oxide, glycidyl ether compounds, carboxylic acid glycidyl ester compounds, epoxy resin compounds, epoxidized natural oils, and the like.

Specific examples of the cyclohexene oxide compound include cyclohexene oxide, 3,4-dimethyl-1,
2-epoxycyclohexane, 3,5-dimethyl-1,2-
Epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, 4-vinyl-1-cyclohexene oxide, 4-vinyl-1-cyclohexene diepoxide, 2,6,6-trichloro-1,2- Epoxycyclohexane, dipentene dioxide, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5-epoxytetrahydrophthalic anhydride, diglycidyl 4,5-epoxytetrahydrophthalate, 4,5-epoxytetrahydrophthalic Diethyl acid
Di-n-butyl 4,5-epoxytetrahydrophthalate, 4,5-
Di-2-ethylhexyl epoxy tetrahydrophthalate,
Isodecyl 4,5-epoxytetrahydrophthalate, bis (3,4-epoxy-6-methylcyclohexylmethyl) succinate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-adipate) 6-methylcyclohexylmethyl), 3- (3,4-epoxycyclohexyl) -2 ', 3'-epoxy-2,4-dioxaspiro (5
. 5) Undecane, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-
3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3',
4'-epoxycyclohexylcarboxylate, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, octadecyl-3,4-
Epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'-epoxycyclohexylcarboxylate, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, 4- (3,4-epoxycyclohexyl) butyl-3 ', 4'-Epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3', 4'-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-6-methylcyclohexyl ) Butyl-3 ', 4'-epoxy-6'-methylcyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylcyclohexylcarboxylate and the like.

Specific examples of the cyclic epoxy other than cyclohexene oxide include cyclopentene oxide, cyclooctene oxide, cyclododecane epoxide, α-pinene oxide, exo-2,3-epoxynorbornane, 1,2,5,
6-diepoxycyclooctane, limonene oxide, 3,4-
Epoxytricyclo [5.2.1.0 ^2,6 ] -decane, allyloxy 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] -decane,
1,2-epoxy-5-trans-9-cis-cyclododecadiene, cedrene epoxide, 5,6-epoxy-4,7-methano-1
-Oxaspiro- [2,5] -octane, 1,4,4A, 8A-tetrahydro-1,4-methanonaphthalene-5,8-dione-6,7-
Epoxide, cycloheptene oxide, 9-oxabicyclo [6.1.0] non-4-ene, cis-1,2-epoxycyclodecane, dicyclopentadiene dioxide and the like can be mentioned.

Specific examples of the glycidyl ether compound include phenyl glycidyl ether, glycidyl benzyl ether, glycidyl 2-methylphenyl ether, glycidyl 4-ethylphenyl ether, t-butylphenyl glycidyl ether, glycidyl mesityl ether, and glycidyl-4- Methoxyphenyl ether, 2-
Biphenyl glycidyl ether, glycidyl 1-naphthyl ether, allyl glycidyl ether, glycidyl isopropyl ether, butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl lauryl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, tri Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether,
1,3-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol A diglycidyl ether, tetramethylbisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol F di Glycidyl ether, bisphenol S diglycidyl ether, resorcinol diglycidyl ether, 4,4'-bis (2,3-epoxypropoxy) biphenyl, 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl, neopentyl alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether,
Examples include trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycidyl lauryl ether, and the like.

Specific examples of the carboxylic acid glycidyl ester compound include diglycidyl adipate, diglycidyl o-phthalate, diglycidyl terephthalate, glycidyl phthalimide, glycidyl oleate, diglycidyl hexahydrophthalate,
4,5-cyclohexene-1,2-dicarboxylic acid diglycidyl ester and the like. Specific examples of the epoxy resin compound include a bisphenol A type epoxy resin, a novolak type epoxy resin, an o-cresol novolak type epoxy resin, a Xyloc type epoxy resin, and the like. Specific examples of epoxidized natural oils include epoxidized soybean oil,
Epoxidized linseed oil, epoxidized tall oil fatty acid 2-ethylhexyl, epoxidized (ethylene glycol di-
Tall oil fatty acid ester) and the like.

Other epoxy compounds include:
Butyl epoxy stearate, octyl epoxy stearate, 2-ethylhexyl epoxy stearate, benzyl epoxy stearate, allyl epoxy stearate, bisepoxydicyclopentadienyl ether,
1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1 1,2-epoxyoctadecane, butadiene monoxide, butadiene diepoxide, 2-methyl-2-vinyloxirane, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2,7,8 -Diepoxy octane,
Tetraphenylethylene epoxide, epoxidized polybutadiene, glycidol, 2-methylglycidol,
-Propyloxirane methanol, styrene oxide,
2,3-epoxypropylbenzene, 1-phenylpropylene oxide, stilbene oxide, 4,5,9,10
-Diepoxy-1-decene, 1,2,4,5,9,10-triepoxydecane, 9,10-epoxyoctadecane, 2
-Epoxyethylbicyclo [2. 2. 1] heptane, 2-
(Benzyloxymethyl) -2-methyloxirane and the like.

The epoxy compound used in the present invention is preferably a cyclohexene oxide compound, a cyclic epoxy compound other than cyclohexene oxide, a glycidyl ether compound, a glycidyl carboxylate compound, or an epoxy resin compound, and more preferably a cyclohexene oxide compound. Compounds, cyclic epoxy compounds other than cyclohexene oxide, glycidyl ether compounds and glycidyl carboxylate compounds, more preferably cyclohexene oxide compounds and glycidyl carboxylate compounds, particularly preferably cyclohexene oxide compounds. Among the cyclohexene oxide compounds, compounds containing no unsaturated bond are particularly preferred.

The resin composition of the present invention comprises the above-mentioned polycarbonate copolymer of the present invention and an epoxy compound or an epoxy compound and a phosphite compound. It is a resin composition containing an epoxy compound and a phosphite compound. The phosphite compound contained in the resin composition of the present invention has the general formula (1-a) and the general formula (2-
0.000 parts by weight based on 100 parts by weight of the polycarbonate copolymer containing the repeating structural unit represented by a)
It is 5 to 5 parts by weight, preferably 0.001 to 3 parts by weight, more preferably 0.01 to 2 parts by weight.

As the phosphite compound used in the present invention, various known derivatives can be used. As specific examples of the phosphite compound, for example,
Trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, tris (2-ethylhexyl phosphite), trinonyl phosphite, tridecyl phosphite, tris (tridecyl) phosphite, trioctadecyl phosphite, tristearyl Trialkyl phosphites such as phosphite, tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl phosphite), triscycloalkyl phosphites such as tricyclohexyl phosphite, triphenyl phosphite, triphenyl Trisure such as cresyl phosphite, tris (ethylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite Lumpur phosphites, phenyl - didecyl phosphite, diphenyl - isooctyl phosphite, diphenyl 2-ethylhexyl phosphite, diphenyl - decyl phosphite, diphenyl - arylalkyl phosphites such as tridecyl phosphite,

Bis (tridecyl) -pentaerythryl-diphosphite, distearyl-pentaerythryl-diphosphite, diphenyl-pentaerythryl-
Diphosphite, bis (nonylphenyl) -pentaerythryl-diphosphite, bis (2,4-di-ter
t-butylphenyl) -pentaerythryl-diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) -pentaerythryl-diphosphite, tetraphenyl-dipropylene glycol-diphosphite, tetra (tridecyl)- Diphosphites such as 4,4'-isopropylidenediphenyl-diphosphite; tetra (2,4-di-tert-butylphenyl) -4,4'-diphenylphosphite; tetraphenyltetra (tridecyl) pentaerythryltetraphosphite , Trilauryl trithiophosphite and the like, but are not limited thereto. These phosphite compounds can be used alone or in combination of two or more.

The method for producing the polycarbonate resin composition of the present invention is not particularly limited, and can be usually carried out by various known methods for producing a resin composition.
That is, (1) after isolating polycarbonate as a solid from the polycarbonate solution, adding the epoxy compound or the epoxy compound and the phosphite compound to the solid, and further mixing various known mixing devices (Eg, a turn bull mixer, Henschel mixer, ribbon blender, super mixer, etc.), or (2) as described above, disperse and mix with various mixers, then melt with an extruder, Banbury mixer, roll, etc. A method of kneading may be used. Also, these methods may be used in combination.

The polycarbonate resin composition of the present invention comprises
To the extent that the desired effects of the present invention are not impaired, at the time of manufacture or molding, further known various additives, such as ultraviolet absorbers, lubricants, mold release agents, organic halogen compound flame retardants, pigments, dyes, A fluidity improver, an antistatic agent, a filler (calcium carbonate, clay, silica, glass fiber, glass beads, carbon fiber, etc.) can be added together. Further, an antioxidant other than the phosphite compound described in the present invention (for example, phenol-based, hindered phenol-based, sulfur-based, metal phosphate, metal phosphite, etc.) may be added.

The polycarbonate resin composition of the present invention comprises:
As long as the desired effect is not impaired, it can be used as a molding material by blending it with an aromatic polycarbonate derived from 2,2-bis (4'-hydroxyphenyl) propane during production or molding. is there.
Further, it can be used as a molding material in combination with another polymer. Other polymers include polyethylene, polypropylene, polystyrene, ABS resin, polymethyl methacrylate, polytrifluoroethylene, polytetrafluoroethylene, polyacetal, polyphenylene oxide, polybutylene terephthalate,
Examples include polyethylene terephthalate, polyamide, polyimide, polyamideimide, polyetherimide, polysulfone, polyethersulfone, paraoxybenzoyl-based polyester, polyarylate, and polysulfide.

The polycarbonate resin composition of the present invention is thermoplastic and can be injection-molded, extruded, blow-molded, impregnated in a filler or the like in a molten state.
It can be easily molded by various known molding methods such as compression molding and solution casting. The polycarbonate copolymer according to the present invention has a characteristic that it has lower birefringence and better fluidity at the time of melting as compared with general-purpose bisphenol A polycarbonate. The polycarbonate resin composition of the present invention can be used as a molding material for chassis and housing materials for electric equipment, etc., electronic components, automobile parts, substrates for information recording media such as optical disks, optical materials such as lenses for cameras and glasses, and building materials in place of glass. Etc. can be formed. In particular, the polycarbonate resin composition of the present invention has excellent transparency, mechanical properties, heat resistance, low birefringence, excellent melt fluidity, and excellent thermal stability. It is very useful as a molding material for parts.

Examples of the optical components of the present invention include various optical components such as optical recording medium substrates such as optical disk substrates and magneto-optical disk substrates, optical lenses such as pickup lenses, plastic substrates for liquid crystal cells, and prisms. Preferred molding conditions for the optical component of the present invention are a resin temperature of 200 to 380 ° C and a mold temperature of 40 to 160 ° C. The optical component of the present invention obtained in this manner has low birefringence, good color tone, and excellent performances (for example, optical recording characteristics and durability as an optical disk). Useful.

[0049]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. The physical properties of the polycarbonate copolymers produced in the following Production Examples and Comparative Production Examples were measured by the following methods. [Measurement of molecular weight] A 0.2% by weight chloroform solution of a polycarbonate copolymer was subjected to GPC (gel permeation chromatography) [Sys, manufactured by Showa Denko KK]
tem-11], weight average molecular weight (Mw)
I asked. The measured value is a value in standard polystyrene conversion. [Melt viscosity] Shimadzu Koka type flow tester (CFT500
A) was measured using an orifice with a load of 100 kg and a diameter of 0.1 cm and a length of 1 cm using A).

Production Example 1 A 5-liter content flask was equipped with a stirrer, a reflux condenser,
A dip tube for blowing phosgene (carbonyl chloride) was provided. In this flask, 277.5 g (0.70 mol) of a dihydroxy compound represented by the following formula (1-1) (Chem. 5) and a dihydroxy compound represented by the following formula (2-1) (Chem. 5): 51 g (0.30 mol) were charged, and 0.846 g (0.04 g) of phenol was added as a terminal stopper.
090 mol; 0.9 mol% to diol), pyridine 3
95.5 (5.0 mol) and dichloromethane 1400
g was charged.

[0051]

Embedded image

To this mixture, phosgene 128,
7 g (1.30 mol) were fed in over 3 hours, after which the reaction mixture was stirred and mixed for an additional hour. After completion of the reaction, the resultant was washed with a 5% aqueous hydrochloric acid solution to remove excess pyridine as a hydrochloride, and then repeatedly washed with water until the aqueous layer became neutral. The organic layer was separated and the organic layer was taken out. Dichloromethane was distilled off under reduced pressure, followed by crushing and drying at 100 ° C. for 1 hour to obtain the following formulas (1-a-1) and (2-a- 1) A polycarbonate copolymer (random copolymer) containing a repeating structural unit represented by Chemical Formula 6 was obtained as a white powdery solid. Weight average molecular weight is 960
00. Differential thermal analysis was performed with a scanning calorimeter (DSC-3100, manufactured by Mac Science) in a temperature range of 0 ° C to 300 ° C. As a result, the glass transition temperature (Tg) was 14 ° C.
4 ° C. The melt viscosity at 220 ° C. is 540.
It was 0 poise.

[0053]

Embedded image

The result of ¹ H-NMR measurement of a ¹ % by weight solution of the obtained polycarbonate copolymer in deuterated chloroform was shown below. ¹ H-NMR δ (CDCl ₃ ): 1.3 (s, 12
H), 1.4 (s, 12H), 2.3 (m, 8H),
3.9-4.5 (m, 8H), 6.3-7.2 (m, 1
2H) IR (KBr method): 1750 cm ^-1 , 1780 cm ^-1
[-OC (= O) -O-] By calculating the integral ratio between the protons of the ethylene chain and the protons on the aromatic ring by the above ¹ H-NMR measurement, the formula (I) in the obtained polycarbonate copolymer is obtained. It was confirmed that the molar ratio of the repeating structural unit represented by 1-a-1) to the repeating structural unit represented by formula (2-a-1) was 70:30.

Comparative Production Example 1 A known polycarbonate was produced from bisphenol A and phosgene according to a conventional method (interfacial polymerization method). That is,
A 2-liter baffled flask was equipped with a stirrer equipped with a lattice blade, a reflux condenser, and a dip tube for blowing phosgene. In this flask, 114 g (0.50 mol)
Of bisphenol A, 56 g (1.40 mol) of sodium hydroxide, 2.58 g of 4-tert-butylphenol and 600 ml of deionized water were prepared to prepare an aqueous solution. Thereafter, 600 ml of dichloromethane was added to the aqueous solution to form a two-phase mixture. While stirring the two-phase mixture, 59.4 g (0.6%) was added to the mixture.
0 mol) of phosgene at a feed rate of 9.9 g / min. After the supply of phosgene was completed, 0.08 g of triethylamine was added to the reaction mixture, and the mixture was further stirred and mixed for 90 minutes. Stirring was then stopped, the reaction mixture was separated, the dichloromethane phase was neutralized with aqueous hydrochloric acid and washed with deionized water until substantially no electrolyte was detected in the aqueous washing solution. Thereafter, dichloromethane was evaporated from the dichloromethane phase by distillation to obtain a solid aromatic polycarbonate. Weight average molecular weight is 5100
The melt viscosity at 300 ° C. was 5,400 poise.

Comparative Production Example 2 According to the method described in Example 7 of JP-A-63-314235, a polycarbonate copolymer of bisphenol A and spirobiindanol (molar ratio: 50:50) was produced. The weight average molecular weight is 44,800 and 280 ° C.
Was 4,800 poise.

Example 1 (Production of resin composition and pellets) 100 parts by weight of the polycarbonate copolymer produced in Production Example 1, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate 0.1 After mixing parts by weight with a Henschel mixer, using a single screw extruder (65 mm),
Pellets of the resin composition were obtained. The pelletizing temperature is shown in (Table 1). (Preparation of a disk-shaped substrate) The above-mentioned pellets were injection-molded with a 50-t molding machine to obtain a thickness of 1.2 mm and a diameter of 120 m.
m was obtained. Molding conditions are: mold temperature 95
° C and the molding temperature is shown in (Table 1). (Evaluation of Disc-Type Substrate) 1) Birefringence: Measured by a Babinet corrector method using a precision strain meter [SVP-30-II manufactured by Toshiba Glass Co., Ltd.]. The results are shown in (Table 1). 2) Hue The yellowness index (YI) was measured according to the ASTM D-1925 method. (Table 1)
It was shown to. (Measurement of melt index)
The melt index (MI) was measured at 280 ° C according to the ASTM D-1283 method. After 6 minutes and 30 minutes residence time, respectively. I. Was measured. The results are shown in (Table 1).

Example 2 100 parts by weight of the polycarbonate copolymer produced in Production Example 1, 0.1 part by weight of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate,
After 0.1 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite was mixed with a Henschel mixer, pellets of the resin composition were obtained using a single screw extruder (65 mm). Evaluation was performed in the same manner as in Example 1 using the pellets. The results are shown in (Table 1).

Example 3 Example 2 was repeated, except that tetraphenyl-tetra (tridecyl) -pentaerythrityl-tetraphosphite was used instead of tris (2,4-di-tert-butylphenyl) phosphite. In the same manner as described in Example 2, a pellet was obtained and evaluated in the same manner. The results are shown in (Table 1).

Example 4 In Example 3, 3,4-epoxycyclohexylmethyl
Pellets were prepared in the same manner as in Example 3, except that bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate was used instead of -3 ', 4'-epoxycyclohexylcarboxylate. And evaluated similarly. The results are shown in (Table 1).

Comparative Example 1 In Example 1, 3,4-epoxycyclohexylmethyl
Except not using -3 ', 4'-epoxycyclohexyl carboxylate, in the same manner as described in Example 1,
Pellets were obtained and evaluated similarly. The results are shown in (Table 1).

Comparative Example 2 In Example 3, 3,4-epoxycyclohexylmethyl
Pellets were obtained and evaluated in the same manner as in Example 3, except that -3 ', 4'-epoxycyclohexylcarboxylate was not used. The results are shown in (Table 1).

Comparative Example 3 100 parts by weight of the polycarbonate produced in Comparative Production Example 1, 0.1 part by weight of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, tris (2,4-di- After mixing 0.1 part by weight of tert-butylphenyl) phosphite with a Henschel mixer,
Pellets were obtained with a single screw extruder (65 mm) and evaluated in the same manner. The results are shown in (Table 1).

Comparative Example 4 The polycarbonate copolymer 10 produced in Comparative Production Example 2
0 parts by weight, 3,4-epoxycyclohexylmethyl-3 ', 4'-
0.1 parts by weight of epoxycyclohexylcarboxylate and 0.1 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite are mixed by a Henschel mixer, and then pelletized by a single screw extruder (65 mm). And evaluated similarly. The results are shown in (Table 1).

[0065]

[Table 1]

[0066]

The resin composition of the present invention is excellent in melt fluidity, retention stability, etc. at the time of molding, and the molded article obtained is excellent in transparency, mechanical properties, heat resistance, etc., and has a good hue. And has low birefringence, so that it is useful for optical components such as optical disk substrates, pickup lenses, plastic substrates for liquid crystal cells, prisms, and optical fibers.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // (C08L 69/00 C08L 63:00) 63:00) C08K 5/15 (72) Inventor Hiromasa Marubayashi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals Co., Ltd. FD206 GP00 GS00 4J029 AA09 AB07 AC02 AC03 AE04 AE05 BD08 BE01 BF04 BF19 BF23 BF24 BG06X BG17X BG21 BG24X BG25X BH01 DA03 HA01 HC01 HC02 HC03 JB243 JC583 JE153

Claims (3)

[Claims] 1. The following general formula (1-a) and general formula (2)
-A) a polycarbonate copolymer containing a repeating structural unit represented by (Chemical Formula 1), and 0.0005 to 5 parts by weight of an epoxy compound based on 100 parts by weight of the copolymer. Characteristic polycarbonate resin composition. Embedded image (Wherein R ₁ and R ₃ are each independently an alkyl group,
Represents an alkoxy group, a nitro group or a halogen atom;
₂ represents a hydrogen atom or a methyl group, k and l each independently represent an integer of 0 to 3, and m and n each independently represent an integer of 0 to 20. However, m + n is never 0) 2. The polycarbonate copolymer 10
The polycarbonate resin composition according to claim 1, wherein the composition contains 0.0005 to 5 parts by weight of a phosphite compound per 0 parts by weight. 3. An optical component obtained by molding the polycarbonate resin composition according to claim 1 or 2.