JP6464227B2 - Optical lens comprising polycarbonate copolymer resin composition - Google Patents

Description

  The present invention relates to an optical lens made of a polycarbonate resin composition having high transparency, high refractive index, low birefringence, and high fluidity.

  In recent years, resins using bisphenols as raw materials (for example, epoxy resins, polyester resins, polycarbonate resins, polyester carbonate resins, etc.) are widely used as materials with heat resistance, transparency, impact resistance, and high refractive index. Has been. A resin comprising a fluorene derivative such as 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is promising as a highly transparent and high refractive index material, and is used as an automotive headlamp lens, CD, CD-ROM. It is expected as an optical material such as a pickup lens, a Fresnel lens, an fθ lens for a laser printer, a camera lens, and a projection lens for a rear projection television.

  In particular, for an optical lens made of an optical resin, polycarbonate resin or the like is used for a camera lens because it can be mass-produced by injection molding. However, in recent years, development of a resin having a high refractive index has been demanded due to the lighter, thinner and smaller products. In general, when the refractive index of an optical material is high, a lens element having the same refractive index can be realized on a surface with a smaller curvature. Therefore, the amount of aberration generated on this surface can be reduced, the number of lenses can be reduced, Decentration sensitivity can be reduced, or the lens thickness can be reduced to reduce the weight.

  When an optical resin is used as an optical lens, heat resistance, transparency, low water absorption, chemical resistance, light resistance, low birefringence, and wet heat resistance are required in addition to the refractive index and Abbe number. Therefore, there exists a weak point that a use location is limited by the characteristic balance of resin. In particular, in recent years, a camera lens having higher imaging performance and lower birefringence has been demanded as the resolution is increased by increasing the number of pixels. In general, as a method of reducing the birefringence, there is a method in which the compositions having positive and negative birefringences having different signs cancel each other's birefringence. For this reason, the composition ratio of materials having birefringence with different signs is very important. Moreover, in order to project a clear image, it is necessary to maintain high transmittance at all wavelengths in the visible light region.

  In recent years, the reduction in size and thickness of optical lenses has been accelerated with the downsizing of electronic devices. For example, camera lenses for mobile phones are extremely small and thin with a diameter of about 5 mm and a thickness of about 0.3 mm, and further miniaturization and thinning are expected to continue in the future. When injection molding such a small thin lens, if the resin has insufficient fluidity, a lens having a desired shape may not be obtained.

Accordingly, a balanced resin having high transparency, high refractive index, low birefringence and excellent molding fluidity has been developed. For example, a polycarbonate composed of a fluorene-containing dihydroxy compound and a bisphenol compound has been proposed (Patent Document 1). However, the polycarbonate has characteristics of low birefringence and high fluidity, but has a problem that its refractive index is still low for use in an optical lens. In addition, a polycarbonate having both excellent heat resistance, moldability and low birefringence has been proposed (Patent Document 2). However, the polycarbonate also has a low refractive index, and the fluidity and birefringence are not sufficient.
A polycarbonate copolymer for optical lenses that satisfies all the properties of high transparency, high refractive index, low birefringence and high molding fluidity in a balanced manner has not yet been achieved.

JP-A-10-101786 JP-A-11-269259

  Accordingly, an object of the present invention is to provide an optical lens comprising a polycarbonate copolymer resin composition for an optical lens that is highly transparent, has a high refractive index, low birefringence, and satisfies all properties of high molding fluidity in a well-balanced manner. There is to do.

  The present inventors have intensively studied to achieve this object. As a result, by copolymerizing a naphthol component and a diol component having a fluorene ring at a specific composition ratio, all properties of high transparency, high refraction, low birefringence and high molding fluidity are satisfied in a well-balanced manner. The inventors have found that the optical lens is composed of a polycarbonate copolymer resin composition for optical lenses, and have reached the present invention.

（式中のＲ_１〜Ｒ_８は、それぞれ水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、炭素数２〜６のアルケニル基、炭素数１〜６のアルコキシ基又は炭素数７〜１７のアラルキル基を示す。Ｘは炭素数２〜８のアルキレン基、炭素数５〜１２のシクロアルキレン基または炭素数６〜２０のアリーレン基である。ｎは１〜１０の整数である。）

（式中、Ｒ_９、Ｒ_１０は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数５〜２０のシクロアルキル基、炭素数５〜２０のシクロアルコキシル基、炭素数６〜２０のアリール基または炭素数６〜２０のアリールオキシ基である。Ｙは炭素数２〜８のアルキレン基、炭素数５〜１２のシクロアルキレン基または炭素数６〜２０のアリーレン基である。ｍは１〜１０の整数である。）
２．式（ＩＩ）中のＹは、エチレン基であり、Ｒ_９、Ｒ_１０が水素原子である前記１に記載のポリカーボネート共重合体樹脂組成物からなる光学レンズの製造方法。
３．式（Ｉ）中のＲ_１〜Ｒ_８が、水素原子である前記１に記載のポリカーボネート共重合体樹脂組成物からなる光学レンズの製造方法。
４．式（Ｉ）中のｎが１である前記１に記載のポリカーボネート共重合体樹脂組成物からなる光学レンズの製造方法。
５．式（Ｉ）に記載の構成単位が、１，１−ビ（２−（２−ヒドロキシエトキシ）ナフチル）構造である前記１に記載のポリカーボネート共重合体樹脂組成物からなる光学レンズの製造方法。
６．屈折率が１．６４０〜１．６６５である前記１〜５のいずれかに記載のポリカーボネート共重合体樹脂組成物からなる光学レンズの製造方法。
７．配向複屈折が０〜６×１０^−３である前記１〜６のいずれかに記載のポリカーボネート共重合体樹脂組成物からなる光学レンズの製造方法。
８．５０〜２０モル％の上記式（Ｉ）で表される構成単位及び５０〜８０モル％で表される上記式（ＩＩ）で表される構成単位を含有し、比粘度０．１２〜０．４０である前記１〜７のいずれかに記載のポリカーボネート共重合体樹脂組成物からなる光学レンズの製造方法。 That is, the present invention
It contains a structural unit represented by the following formula (I) of 1.50 to 2 mol% and a structural unit represented by the following formula (II) represented by 50 to 98 mol%, and has a specific viscosity of 0.12 to 0.12 A polycarbonate copolymer having a residual phenol content of 1 to 300 ppm relative to the polycarbonate copolymer and a 5% weight reduction temperature of 380 ° C. or higher measured at a temperature rising rate of 20 ° C./min is 0.40. The manufacturing method of the optical lens whose thickness of the center part which consists of a polycarbonate copolymer resin composition to be used is 0.05-2.0 mm, and whose lens diameter is 1.0-10.0 mm.
(As a structural unit represented by the following formula (I), those containing 30 to 40 mol % of 1,1-bi (2- (2-hydroxyethoxy) naphthalene ) are excluded.
The specific viscosity of the polycarbonate copolymer is a value measured by dissolving 0.7 g of the polycarbonate copolymer in 100 ml of methylene chloride at 20 ° C. )

(In the formula, R _{1 to} R ₈ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 2 to 6 carbon atoms. An alkenyl group, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 to 20 carbon atoms. N is an integer of 1 to 10.)

(In formula, R <_9> , R < ₁₀ > is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, and C5-C20. A cycloalkoxyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, Y is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 carbon atoms. An arylene group of ˜20, m is an integer of 1-10.)
2. Y in Formula (II) is an ethylene group, The manufacturing method of the optical lens which consists of a polycarbonate copolymer resin composition of said 1 whose R <_9> , R < ₁₀ > is a hydrogen atom.
3. Method of manufacturing R ₁ to R ₈ in formula (I), an optical lens made of polycarbonate copolymer resin composition according to 1 above, wherein a hydrogen atom.
4). 2. A method for producing an optical lens comprising the polycarbonate copolymer resin composition according to 1 above, wherein n in the formula (I) is 1.
5. The manufacturing method of the optical lens which consists of a polycarbonate copolymer resin composition of said 1 whose structural unit as described in Formula (I) is a 1, 1-bi (2- (2-hydroxyethoxy) naphthyl) structure.
6). The manufacturing method of the optical lens which consists of a polycarbonate copolymer resin composition in any one of said 1-5 whose refractive index is 1.640-1.665.
7). The manufacturing method of the optical lens which consists of a polycarbonate copolymer resin composition in any one of said 1-6 whose orientation birefringence is 0-6 * 10 < ^-3 >.
8. Containing the structural unit represented by the said Formula (I) of 50-20 mol% and the structural unit represented by the said Formula (II) represented by 50-80 mol%, specific viscosity 0.12- The manufacturing method of the optical lens which consists of a polycarbonate copolymer resin composition in any one of said 1-7 which is 0.40.

  An optical lens comprising the polycarbonate resin composition for an optical lens of the present invention has a high transparency, a high refraction, a low birefringence by copolymerizing a binaphthol component and a diol component having a fluorene ring at a specific composition ratio. Since all the properties of high molding fluidity are balanced, the industrial effect exerted by them is exceptional.

2 is a proton NMR of the polycarbonate copolymer obtained in Example 6.

<Polycarbonate copolymer>
Hereafter, each component which comprises the polycarbonate copolymer for optical lenses used for the optical lens of this invention, those compounding ratios, the adjustment method, etc. are demonstrated concretely one by one.

  The polycarbonate copolymer used for the optical lens of the present invention (hereinafter sometimes abbreviated as copolymer) contains a carbonate unit represented by the following formula (I). Content of the unit of a formula (I) is 2-50 mol%, Preferably it is 20-50 mol%. If it is less than 2 mol%, the refractive index is undesirably lowered. On the other hand, when it is larger than 50 mol%, the glass transition temperature becomes high and handling becomes difficult.

(In the formula, R _{1 to} R ₈ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 2 to 6 carbon atoms. An alkenyl group, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 to 20 carbon atoms. N is an integer of 1 to 10.)
In the structure represented by the general formula (I) in the polycarbonate copolymer, R _{1 to} R ₈ are preferably hydrogen.
In the structure represented by the general formula (I) in the polycarbonate copolymer, it is preferably 1.

  In the structure represented by the general formula (I) in the polycarbonate copolymer, the bonding position of the oxygen atom is not particularly limited, and may be symmetric or asymmetrical. In terms of surface. Particularly preferred is a 1,1-bi (2- (2-hydroxyethoxy) naphthyl structure, in which the ring structures on both sides of one bond are mutually sterically hindered and do not exist in the same plane. , Birefringence is low.

  The polycarbonate copolymer contains a carbonate unit represented by the following formula (II). Content of the unit of a formula (II) is 50-98 mol%, Preferably it is 50-80 mol%. When it is less than 50 mol% or more than 98 mol%, birefringence occurs, which is not preferable.

(In formula, R <_9> , R < ₁₀ > is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, and C5-C20. A cycloalkoxyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, Y is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 carbon atoms. An arylene group of ˜20. N and m are integers of 0-10.)

In the structure represented by the general formula (II) in the polycarbonate copolymer, it is preferable that Y is an ethylene group having 2 carbon atoms and m is 0 or 1.
R ₉ and R ₁₀ are preferably a hydrogen atom or a methyl group.

  The specific viscosity of the polycarbonate copolymer is in the range of 0.12 to 0.40, preferably 0.15 to 0.35, and more preferably 0.18 to 0.35. The specific viscosity is measured at 20 ° C. by dissolving 0.7 g of the polycarbonate copolymer in 100 ml of methylene chloride. When the specific viscosity is less than 0.12, the molded product becomes brittle, and when it is higher than 0.40, the melt viscosity and the solution viscosity are increased, the fluidity is lowered, and injection molding such as insufficient filling is caused. In addition, the solubility and stability in a solvent during wet molding are reduced, and precipitation from the solvent makes it impossible to perform wet molding.

  The refractive index of the polycarbonate copolymer is preferably 1.640 to 1.665, more preferably 1.645 to 1.665, and still more preferably 1.650 to 1.665. The refractive index is measured at 25 ° C. and wavelength 589 nm. A refractive index of 1.635 or more is preferable because spherical aberration of the lens can be reduced and the focal length of the lens can be shortened.

The Abbe number (ν) of the polycarbonate copolymer is preferably 19 to 25, more preferably 19 to 24, and still more preferably 21 to 23. The Abbe number is calculated from the refractive index at 25 ° C., wavelengths 486 nm, 589 nm, and 656 nm using the following formula.
v = (nD-1) / (nF-nC)
nD: Refractive index at a wavelength of 589 nm nF: Refractive index at a wavelength of 656 nm nC: Refractive index at a wavelength of 486 nm

The orientation birefringence (Δn) of the polycarbonate copolymer is preferably 0 to 6 × 10 ⁻³ , more preferably 0 to 4 × 10 ⁻³ , and still more preferably 0 to 1 × 10 ⁻³ . The orientation birefringence (Δn) is measured at a wavelength of 589 nm when a cast film having a thickness of 100 μm obtained from the polycarbonate copolymer is stretched twice at Tg + 10 ° C.

  The spectral transmittance of the polycarbonate copolymer is preferably 80% or more, more preferably 81% or more, and further preferably 82% or more. The transmittance is measured at a wavelength of 395 nm on a molded plate having a thickness of 0.1 mm. Unless the spectral transmittance is 80% or more, it is not preferable as an optical member.

  The glass transition temperature (Tg) of the polycarbonate copolymer is preferably 130 to 160 ° C, more preferably 135 to 155 ° C, and still more preferably 140 to 155 ° C. The glass transition temperature (Tg) is measured at a heating rate of 20 ° C./min. If the Tg is less than 130 ° C, the heat resistance is not sufficient depending on the use of the optical component formed using the polycarbonate copolymer. On the other hand, if the Tg is higher than 160 ° C, the melt viscosity becomes high, Handling in forming becomes difficult.

  The polycarbonate copolymer preferably has a 5% weight loss temperature of 350 ° C. or higher, more preferably 380 ° C. or higher, as a thermal stability index measured at a temperature rising rate of 20 ° C./min. When the 5% weight reduction temperature is lower than 350 ° C., the thermal decomposition during the molding is severe and it becomes difficult to obtain a good molded product, which is not preferable.

  The melt viscosity of the polycarbonate copolymer at 280 ° C. and a shear rate of 1000 / sec is preferably 30 to 300 Pa · s, more preferably 30 to 250 Pa · s, and still more preferably 50 to 200 Pa · s.

  The residual phenol content of the polycarbonate copolymer is 1 to 500 ppm, preferably 1 to 400 ppm, more preferably 1 to 300 ppm.

  The phenol content can be adjusted by increasing the vacuum, that is, the reaction time at 1.3 kPa or less. When the reaction is not performed at a vacuum degree of 1.3 kPa or less, the phenol content increases. Moreover, when reaction time is too long, it will distill off too much from resin.

  Further, the phenol content may be adjusted after obtaining the polycarbonate copolymer. For example, using a kneading apparatus such as a method in which a polycarbonate copolymer is dissolved in an organic solvent and the organic solvent layer is washed with water, or a commonly used single- or twin-screw extruder or various kneaders. A method of devolatilizing and removing at a pressure of 3 Pa and a temperature of 200 to 320 ° C. may be used.

  The residual phenol content in the polycarbonate copolymer can improve the molding fluidity without impairing the heat resistance. However, if it exceeds 500 ppm, the thermal stability when melted by heating is poor, and further, mold contamination during resin injection molding becomes severe, which is undesirable because it causes a decrease in wet heat resistance. Furthermore, phenol has a property of coloring when oxidized, and the hue in the polycarbonate copolymer is deteriorated. If it is less than 1 ppm, the molding fluidity is inferior.

  The content of the diol component represented by the following formula (III) in the polycarbonate copolymer is preferably 5 to 500 ppm, more preferably 5 to 400 ppm, and still more preferably 5 to 300 ppm.

(In formula, R <_11> , R < ₁₂ > is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, and C5-C20. A cycloalkoxyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, z is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 carbon atoms. An arylene group of ˜20, o is an integer of 0-10.)

  Content of the diol represented by general formula (III) in a polycarbonate copolymer can be adjusted with the preparation amount of the carbonate precursor at the time of superposition | polymerization. When the preparation amount of the carbonate precursor is small relative to the diol, the content of the diol represented by the formula (III) increases. Moreover, when there are too many preparation amounts of a carbonate precursor, content of the diol represented by Formula (III) will increase.

  The content of the compound represented by the general formula (III) in the polycarbonate copolymer can improve the molding fluidity without impairing the heat resistance. However, if it is 500 ppm or more, mold contamination during injection molding becomes severe, and it is preferable because hydrolysis is accelerated in a moist heat environment, causing a decrease in strength and a decrease in hue due to a decrease in specific viscosity. Furthermore, the heat and humidity resistance is lowered, which is not preferable. If it is less than 5 ppm, the molding fluidity is inferior, which is not preferable.

  The specific viscosity retention is preferably 80% or more, more preferably 85% or more, after leaving for 2000 hours under conditions of 85 ° C. and 85% RH, which is an indicator of heat and humidity resistance in polycarbonate copolymerization. Preferably, it is 90% or more. When the specific viscosity retention is 80% or more, there is no deterioration in hue or strength price of the molded product even when used in a humid heat environment, and there are no restrictions on the use environment of copolymerization. If it is 80% or less, the strength accompanying a decrease in specific viscosity is decreased, cracking and deformation are preferably caused, and the hue is deteriorated.

  The specific viscosity retention after the heat retention test, which is an index of heat resistance in polycarbonate copolymerization, is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. A specific viscosity retention of 70% or more is preferred because there is no limitation on the molding of copolymerization, and it is possible to mold a thin molded article having a high molding temperature. Further, the hue of the molded product is preferable without deteriorating. When it is 70% or less, the strength of the molded product is lowered with a decrease in specific viscosity, and cracking and deformation are preferably caused, and the hue of the molded product is also deteriorated. Moreover, the molding conditions at the time of injection molding are limited, which is not preferable.

<Production method of polycarbonate copolymer>
The polycarbonate copolymer can be produced by reacting a diol component and a carbonate precursor.

(Diol component)
One of the diol components in the copolymerization is a diol represented by the following formula (IV).

(R _{13 to} R ₂₀ in the formula are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 2 to 6 carbon atoms. An alkenyl group, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms.)
Content of this diol becomes like this. Preferably it is 50-2 mol%, More preferably, it is 50-10 mol%, More preferably, it is 45-15 mol%.

In the diol represented by the general formula (IV) in the polycarbonate copolymer, R _{13 to} R ₂₀ are preferably hydrogen atoms.
In the diol represented by the general formula (IV) in the polycarbonate copolymerization, p is preferably 1.

  In the diol represented by the general formula (IV) in the polycarbonate copolymer, the bonding position of the oxygen atom is not particularly limited, and may be symmetric or asymmetrical. In terms of surface. Particularly preferred is 1,1-bi (2- (2-hydroxyethoxy) naphthyl. In the naphthyl structure, the ring structures on both sides of one bond are sterically hindered from each other, and do not exist in the same plane. Birefringence is lowered.

One of the diol components in the copolymerization is a diol represented by the following formula (III).

Wherein R _{11 to} R ₁₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or 5 to 20 carbon atoms. A cycloalkoxyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, z is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 carbon atoms. An arylene group of ˜20. O and p are integers of 0-10.)
In the diol represented by the general formula (III) in the polycarbonate copolymer, R _{11 to} R ₁₂ are preferably hydrogen atoms, Z is an ethylene group having 2 carbon atoms, and O is preferably 1.

The diol represented by the general formula (III) in the polycarbonate copolymer is preferably 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene.
Content of this diol becomes like this. Preferably it is 98-50 mol% or more, More preferably, it is 90-50 mol%, More preferably, it is 85-55 mol% or more.

Other diols include aliphatic diols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol, cyclohexane-1,4-dimethanol , Decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1,4: 3,6-dianhydro-D-sorbitol, 1,4 : 3,6-dianhydro-D-mannitol, alicyclic diol such as 1,4: 3,6-dianhydro-L-iditol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ) Ethane, bis (4-hydroxyphenyl) ether, bis (4 Hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 9 , 9-bis (4-hydroxyphenyl) fluorene, 9,9-bi (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) anthrone, α, ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, α, ω-bis [3- (O-hydroxyphenyl) propyl] polydimethylsiloxane, aromatic diols such as 4,4 ′-[1,3-phenylenebis (1-methylethylidene) droxyphenyl] -1-phenylethane, bisphenol A and the like. It is done.

  The birefringence of the optical lens made of a polycarbonate copolymer is such that the molar ratio of the diol component made of the general formula (IV) and the diol component made of the general formula (III) is in the range of 50:50 to 2:98. Is particularly preferable because it is small. More preferably, it is 50: 50-10: 90, More preferably, it is 45: 55-15: 85.

(Carbonate precursor)
As carbonate precursors, phosgene, bischloroformate of 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di- -Carbonic acid diesters such as -p-chlorophenyl carbonate and dinaphthyl carbonate. Of these, diphenyl carbonate is preferred.

(Production method)
In the reaction of diol and phosgene, the reaction is performed in a non-aqueous system in the presence of an acid binder and a solvent. Examples of the acid binder include pyridine, dimethylaminopyridine, tertiary amine and the like. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is desirable to use a terminal terminator such as phenol or p-tert-butylphenol as the molecular weight regulator. The reaction temperature is usually 0 to 40 ° C., and the reaction time is preferably several minutes to 5 hours.

In the transesterification reaction, a diol and bisaryl carbonate are mixed in the presence of an inert gas, and usually 120 to 350 ° C. under reduced pressure in the presence of a mixed catalyst composed of an alkali metal compound catalyst or an alkaline earth metal compound or both. The reaction is preferably performed at 150 to 300 ° C. The degree of vacuum is changed stepwise, and finally the alcohol produced at 133 Pa or less is distilled out of the system. The reaction time is usually about 1 to 4 hours.
As a polymerization catalyst, an alkali metal compound or an alkaline earth metal compound may be used as a main component, and a nitrogen-containing basic compound may be used as a subsidiary component if necessary.

  The alkali metal compound used as the catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate. Sodium stearate, potassium stearate, lithium stearate, sodium salt, potassium salt, lithium salt of bisphenol A, sodium benzoate, potassium benzoate, lithium benzoate and the like. Alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate , Calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like.

  Nitrogen-containing basic compounds used as promoters include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine Etc.

These catalysts may be used alone or in combination of two or more, and the amount of these polymerization catalysts used is in a ratio of 10 ⁻⁹ to 10 ⁻³ mol with respect to 1 mol of the total diol component. . Moreover, you may add antioxidant, a heat stabilizer, etc. for a hue improvement.

In the polycarbonate copolymer of the present embodiment, the catalyst may be removed or deactivated after the polymerization reaction to maintain thermal stability and hydrolysis stability. As for the alkali metal compound or the alkaline earth metal compound, generally, a method of deactivating the catalyst by adding a known acidic substance is preferably carried out. Specific examples of the deactivation include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, butyl p-toluenesulfonate, hexyl p-toluenesulfonate, and the like. Sulfonic acid esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, Phosphorous esters such as di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, phosphoric acid Phosphate esters such as dibutyl, dioctyl phosphate, monooctyl phosphate, diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, etc. Phosphonic acid esters such as phonic acids, diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, tetrabutylphosphonium dodecylbenzenesulfonate, etc. Aromatic sulfonates, stearic acid chloride, benzoyl chloride, organic halides such as p-toluenesulfonic acid chloride, alkylsulfuric acid such as dimethylsulfuric acid, and organic halides such as benzyl chloride are preferably used. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient, which is not preferable. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, since heat resistance falls and it becomes easy to color a molded object, it is unpreferable.
After catalyst deactivation, a step of devolatilizing and removing low-boiling compounds in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C may be provided.

<Optical lens>
The optical lens of the present invention can be molded by, for example, injection molding, compression molding, injection compression molding, or casting of the polycarbonate resin composition of the present invention.
The optical lens of the present invention may contain various additives in order to impart various characteristics within a range that does not impair the object of the present invention. Additives include mold release agents, heat stabilizers, UV absorbers, bluing agents, antistatic agents, flame retardants, heat ray shielding agents, fluorescent dyes (including fluorescent whitening agents), pigments, light diffusing agents, reinforcing fillers Other resins and elastomers can be blended.

  As a mold release agent, that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable. Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester, partial ester or total ester of polyhydric alcohol and fatty acid. The ester of the monohydric alcohol and the fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial ester or total ester of a polyhydric alcohol and a fatty acid is preferably a partial ester or a total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

  Specific examples of the monohydric alcohol, saturated fatty acid and ester include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like. Stearyl stearate is preferred.

  As partial ester or total ester of polyhydric alcohol and saturated fatty acid, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, All or partial esters of dipentaerythritol such as pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, etc. Can be mentioned. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.

The amount of the ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more when the release agent is 100% by weight.
The content of the release agent in the optical lens of the present invention is preferably in the range of 0.005 to 2.0 parts by weight, and in the range of 0.01 to 0.6 parts by weight with respect to 100 parts by weight of the polycarbonate copolymer. More preferably, the range of 0.02-0.5 weight part is further more preferable.
Examples of the heat stabilizer include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer.

  Examples of phosphorus heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, Tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite Phyto, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bi (Nonylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite Phosphite, Tributyl phosphate, Triethyl phosphate, Trimethyl phosphate, Triphenyl phosphate, Diphenyl monoorthoxenyl phosphate, Dibutyl phosphate, Dioctyl phosphate, Diisopropyl phosphate, Dimethyl benzenephosphonate, Diethylbenzenephosphonate, Dipropylbenzenephosphonate, Tetrakis (2 , 4-Di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl) Ruphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) Examples include -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite.

  Among them, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4 , 4′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -3,3 '-Biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite Is used. Particularly preferred is tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite.

  The content of the phosphorus-based heat stabilizer in the polycarbonate copolymer is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the polycarbonate copolymer.

  As the sulfur-based heat stabilizer, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthiopropionate), Examples include dilauryl-3, 3′-thiodipropionate, dimyristyl-3, 3′-thiodipropionate, distearyl-3, 3′-thiodipropionate. Among them, pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), dilauryl-3, 3′-thiodipropionate, dimyristyl-3, 3′-thio Dipropionate is preferred. Particularly preferred is pentaerythritol-tetrakis (3-laurylthiopropionate). The thioether compounds are commercially available from Sumitomo Chemical Co., Ltd. as Sumilizer TP-D (trade name), Sumilizer TPM (trade name), and the like, and can be easily used.

  As for content of the sulfur type heat stabilizer in a polycarbonate copolymer, 0.001-0.2 weight part is preferable with respect to 100 weight part of polycarbonate copolymers.

  Examples of the hindered phenol heat stabilizer include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide) 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1,1- And dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane. . Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is particularly preferably used.

The content of the hindered phenol heat stabilizer in the polycarbonate copolymer is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the copolymer.
About a heat stabilizer, a phosphorus stabilizer or a hindered phenol heat stabilizer is preferable. Addition of 0.001 to 0.3 parts by weight of a phosphorus stabilizer or a hindered phenol heat stabilizer to 100 parts by weight of the polycarbonate copolymer improves the heat and moisture resistance.
The phosphorus stabilizer and the hindered phenol heat stabilizer can be used in combination.

  Examples of the ultraviolet absorber include at least one ultraviolet absorber selected from the group consisting of benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic imino ester ultraviolet absorbers, and cyanoacrylates. preferable.

  Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy- 3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1 , 3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- ( 2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy 3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3- Benzoxazin-4-one), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole. These can be used alone or in a mixture of two or more.

  Preferably, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dicumyl) Phenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetra Methylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole And more preferably 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2,2 ′ Methylenebis [4- (1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl) phenol].

  Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4- Methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2- Methoxyphenyl) meta , 2-hydroxy -4-n-dodecyloxy benzoin phenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone.

  Examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6-bis ( And 2.4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-[(octyl) oxy] -phenol.

  Examples of cyclic imino ester UV absorbers include 2,2′-bis (3,1-benzoxazin-4-one) and 2,2′-p-phenylenebis (3,1-benzoxazin-4-one). 2,2′-m-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 ′-(1,5-naphthalene) bis (3,1-benzoxazin-4-one) ), 2,2 ′-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2 ′-(2-nitro-p-phenylene) bis (3,1- Benzoxazin-4-one) and 2,2 ′-(2-chloro-p-ph) Ylene) bis (3,1-benzoxazin-4-one) is illustrated.

  Among them, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazin-4-one) And 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) are preferred. In particular, 2,2'-p-phenylenebis (3,1-benzoxazin-4-one) is preferred. Such a compound is commercially available from Takemoto Yushi Co., Ltd. as CEi-P (trade name) and can be easily used.

  As the cyanoacrylate ultraviolet absorber, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenyl) Examples include acryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  The content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, further preferably 100 parts by weight of the polycarbonate copolymer. Is 0.05 to 0.8 part by weight. If it is the range of this compounding quantity, it is possible to provide sufficient weather resistance to a polycarbonate copolymer molded object according to a use.

  Examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer and polysynthremble-RLS manufactured by Clariant. The bluing agent is effective for eliminating the yellow color of the polycarbonate copolymer. In particular, in the case of a polycarbonate copolymer imparted with weather resistance, since a certain amount of UV absorber is blended, there is a reality that the molded body tends to be yellowish depending on the action and color of the UV absorber, especially sheets and lenses. In order to impart a natural transparency to the skin, the blending of the bluing agent is very effective.

  The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm with respect to the polycarbonate copolymer.

  In order to add various additives to the polycarbonate copolymer in the present invention, a known method can be used. For example, a method of mixing each component in a solution state and evaporating the solvent or precipitating in the solvent can be mentioned. From an industrial point of view, a method of kneading each component in a molten state is preferable. For melt kneading, generally used kneading apparatuses such as a single or twin screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable. In melt kneading, the cylinder set temperature of the kneading device is preferably in the range of 200 to 340 ° C, more preferably 250 to 320 ° C. When it is higher than 320 ° C., the polycarbonate copolymer is decomposed, and coloring and defective molding due to the decomposition product increase, which is not preferable. Furthermore, if it is less than 200 degreeC, the viscosity of a polycarbonate copolymer is high and cannot disperse | distribute various additives uniformly. The melt kneading may be performed in a vacuum state. Melting and kneading in a vacuum state is preferable because low molecular weight materials such as residual PhOH of the polycarbonate copolymer can be reduced and molding defects can be reduced. The degree of vacuum is preferably a pressure of 13.3 kPa or less, and more preferably 1.3 kPa or less.

  At the time of kneading, each component may be mixed uniformly in advance with a device such as a tumbler or a Henschel mixer, or if necessary, a method of omitting the mixing and separately supplying each of the components separately to the kneading device is also used. be able to.

  In addition, the optical lens of the present invention is characterized by a small optical distortion. An optical lens made of a general bisphenol A type polycarbonate resin has a large optical distortion. Although it is not impossible to reduce the value depending on molding conditions, the condition width is very small and molding becomes very difficult. Since the polycarbonate copolymer of the present invention has a very small optical strain caused by the orientation of the resin and a small molding strain, a good optical element can be obtained even if the molding conditions are not strictly set.

  When the optical lens of the present invention is manufactured by injection molding, it is preferable to mold it under conditions of a cylinder temperature of 260 to 320 ° C and a mold temperature of 100 to 140 ° C.

  The optical lens of the present invention is preferably used in the form of an aspheric lens as necessary. Since an aspheric lens can substantially eliminate spherical aberration with a single lens, there is no need to remove spherical aberration with a combination of a plurality of spherical lenses, thus reducing weight and reducing production costs. It becomes possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.

  Further, since the polycarbonate copolymer of the present invention has high fluidity, it is particularly useful as a material for an optical lens having a thin and small size and a complicated shape. As a specific lens size, the thickness of the central portion is 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and still more preferably 0.1 to 2.0 mm. Moreover, a diameter is 1.0 mm-20.0 mm, More preferably, it is 1.0-10.0 mm, More preferably, it is 3.0-10.0 mm. In addition, it is preferably a meniscus lens having a convex surface on one side and a concave surface on the other side.

On the surface of the optical lens of the present invention, a coating layer such as an antireflection layer or a hard coating layer may be provided as necessary. The antireflection layer may be a single layer or a multilayer, and may be organic or inorganic, but is preferably inorganic. Specific examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.
Moreover, the optical lens of the present invention may be molded by any method such as mold molding, cutting, polishing, laser processing, electric discharge machining, and edging. Furthermore, mold molding is more preferable.

The following examples further illustrate the present invention.
Reference Examples 1-4, Examples 5-7, Comparative Examples 1-6
An evaluation sample was prepared by the following method.
(A) Cast film:
5 g of the obtained polycarbonate copolymer is dissolved in 50 ml of methylene chloride and cast on a glass petri dish. After sufficiently drying at room temperature, the polycarbonate copolymer was dried for 8 hours at a temperature of 20 ° C. or less from the Tg of the polycarbonate copolymer. A cast film was created.
(B) Aspheric lens:
The obtained polycarbonate copolymer was vacuum-dried at 120 ° C. for 8 hours, and then a thickness of 0 using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a molding temperature Tg + 110 ° C. and a mold temperature Tg−10 ° C. A lens having a radius of curvature of 3 mm, a convex radius of curvature of 5 mm, a concave radius of curvature of 4 mm, and Φ5 mm was injection molded.
(C) Molded piece In the same manner as (b) above, molded pieces having a width of 2.5 cm, a length of 5 cm, and a thickness of 1, 2, and 3 mm were injection molded.

Evaluation was based on the following method.
(1) Specific viscosity: The polycarbonate copolymer pellet obtained after completion of the polymerization was sufficiently dried, and the specific viscosity (η _sp ) of the solution at 20 ° C. was obtained from a solution obtained by dissolving 0.7 g of the pellet in 100 ml of methylene chloride. Was measured.
(2) Copolymerization ratio: The polycarbonate copolymer pellet obtained after the completion of the polymerization was measured using proton NMR of JNM-AL400 manufactured by JEOL Ltd. As shown in FIG. 1, a peak due to ethylene of 3.2 to 4.8 ppm of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 1,1′- It calculated | required from the integral ratio of the peak resulting from the aromatic ring of bi-2-naphthol and 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. Alternatively, as shown in FIG. 2, 6.5-6.8 ppm of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene aromatic peak and 7.6-8.0 ppm of 9 , 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 1,1-bi (2- (2-hydroxyethoxy) naphthalene aromatic peaks.
(3) Glass transition point (Tg): The polycarbonate copolymer pellets were measured with a DuPont 910 type DSC at a heating rate of 20 ° C./min.
(4) Melt viscosity: Polycarbonate copolymer pellets obtained after completion of polymerization were dried at 120 ° C. for 4 hours, and then melt viscosity at 280 ° C. and shear rate of 1,000 / sec by Capillograph 1D manufactured by Toyo Seiki Co., Ltd. Was measured.
(5) Spectral transmittance: A 0.1 mm-thick disk obtained by injection molding was measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. Evaluation was performed as follows.
The transmittance at 395 nm is 80% or more:
Transmittance at 395 nm is below 80%: x
(6) Refractive index (nd), Abbe number (ν): A 0.3 mm-thick disk obtained by injection molding according to the method of (c) was used, using an Abbe DR-M2 Abbe refractometer, 25 The refractive index (wavelength: 589 nm) and Abbe number at 0 ° C. were measured.
(7) Oriented birefringence (Δn): A cast film having a thickness of 100 μm prepared by the method of (a) was stretched twice at Tg + 10 ° C., and the position at 589 nm was measured using an ellipsometer M-220 manufactured by JASCO Corporation. The phase difference (Re) was measured, and the orientation birefringence (Δn) was determined from the following formula.
Δn = Re / d
Δn: orientation birefringence
Re: Phase difference
d: Thickness (8) Optical distortion: The optical distortion was evaluated by sandwiching an aspheric lens molded by the method of (b) between two polarizing plates and visually observing light leakage from behind by the orthogonal Nicol method. Evaluation was performed according to the following criteria.
A: There is almost no light leakage.
○: Slight light leakage is observed.
X: Light leakage is remarkable.
(9) Moldability: The filling failure of each aspherical lens molded by the method of (b), each molding defect, the brittleness of the lens, the presence or absence of mold deposits, etc. were confirmed visually. Evaluation was classified according to the probability of being defective when 500 sheets were formed, with less than 1% (）), 1 to 5% (◯) 5 to 20% (Δ), and 20% or less (x).
(10) Content of unreacted diol and residual phenol The content of diol in the polycarbonate copolymer obtained after polymerization was eluted with acetonitrile / 0.2% acetic acid in a column of Develosil ODS-7 manufactured by Nomura Chemical. Using a mixed solution with acetonitrile, HPLC analysis was performed with a gradient program at a column temperature of 30 ° C. and a detector of 277 nm. Diols and phenols were quantified by using calibration standards and preparing calibration curves. Measurement is made by dissolving 1.5 g of polycarbonate copolymer in 15 ml of methylene chloride, adding 135 ml of acetonitrile, stirring, concentrating with an evaporator, filtering through a 0.2 μm filter, and injecting 10 μl of this measurement solution. went.
(11) Moisture and heat resistance: A molded piece having a thickness of 1 mm is allowed to stand for 2000 hours under the conditions of 85 ° C. and 85% RH, and then a solution of 0.7 g of the molded piece dissolved in 100 ml of methylene chloride is used. The specific viscosity (ηsp) was measured, and the specific viscosity retention rate (molecular weight retention rate) after the wet heat test was determined. The specific viscosity retention rate (molecular weight retention rate) was used as an index of moisture and heat resistance.
Δηsp = (ηsp1 / ηsp0) × 100
* Δηsp: Specific viscosity retention ratio, ηsp0: Specific viscosity before test, ηsp1: Specific viscosity after test (12) Thermal stability (heat retention test): Molded on an SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. After the copolymer was heated and melted at a temperature of Tg + 110 ° C. for 10 minutes, a molded product having a width of 2.5 cm, a length of 5 cm, and a thickness of 2 mm was molded at a mold temperature of Tg−10 ° C. From a solution obtained by dissolving 0.7 g of the molded piece in 100 ml of methylene chloride, the specific viscosity (ηsp) of the solution at 20 ° C. was measured to determine the specific viscosity retention rate (molecular weight retention rate). The specific viscosity retention rate (molecular weight retention rate) was used as an index of heat resistance.
Δηsp = (ηsp1 / ηsp0) × 100
* Δηsp: specific viscosity retention, ηsp0: specific viscosity before test, ηsp1: specific viscosity after test

Reference example 1
9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter “BPE”)
F ") 157.86 parts by weight, 1,1'-bi-2-naphthol (hereinafter sometimes abbreviated as" BN ") 11.45 parts by weight, DPC 89.97 parts by weight, and tetramethylammonium 1.82 × 10-2 parts by weight of hydroxide was placed in a reaction kettle equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under a nitrogen atmosphere and normal pressure, and stirred for 20 minutes. The temperature was adjusted to ˜30 kPa, the temperature was increased to 260 ° C. at a rate of 60 ° C./hr, and the transesterification reaction was performed, and then 0.13 k over 120 minutes while maintaining the temperature at 260 ° C.
The pressure was reduced to Pa or lower, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 260 ° C. and 0.13 kPa or lower. The polycarbonate copolymer has a BPEF to BN molar ratio of 90:10, a specific viscosity of 0.224, Tg of 149 ° C., unreacted BPEF of 300 ppm, and residual PhOH 2.
It was 50 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.0 based on the weight of the resulting resin composition.
50%, 0.10% pentaerythritol tetrastearate, φ3 with vent
Pelletized using a 0 mm single screw extruder. The heat and humidity resistance was good, and the specific viscosity retention after the wet heat test was 90%. Moreover, heat resistance was also favorable, and the specific viscosity retention after the heat resistance test was 80%.

Reference example 2
Polymerization was conducted in the same manner as in Reference Example 1 except that 140.32 parts by weight of BPEF and 22.91 parts by weight of BN were used.
The polycarbonate copolymer has a BPEF to BN molar ratio of 80:20, a specific viscosity of 0.220, Tg of 152 ° C., unreacted BPEF of 200 ppm, and residual PhOH of 200 pp.
m.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.0 based on the weight of the resulting resin composition.
50%, 0.10% pentaerythritol tetrastearate, φ3 with vent
Pelletized using a 0 mm single screw extruder. The heat and humidity resistance was good, and the specific viscosity retention after the wet heat test was 90%. Moreover, heat resistance was also favorable, and the specific viscosity retention after the heat resistance test was 85%.

Reference example 3
Polymerization was conducted in the same manner as in Reference Example 1 except that 122.78 parts by weight of BPEF and 34.36 parts by weight of BN were used.
The polycarbonate copolymer has a BPEF to BN molar ratio of 70:30, a specific viscosity of 0.215, a Tg of 154 ° C., unreacted BPEF of 150 ppm, and a residual PhOH of 100 pp.
m.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.0 based on the weight of the resulting resin composition.
50%, 0.10% pentaerythritol tetrastearate, φ3 with vent
Pelletized using a 0 mm single screw extruder. The wet heat resistance was good, and the specific viscosity retention after the wet heat test was 93%. Moreover, heat resistance was also favorable, and the specific viscosity retention after the heat resistance test was 85%.

Reference example 4
Polymerization was conducted in the same manner as in Reference Example 1 except that 87.70 parts by weight of BPEF and 57.26 parts by weight of BN were used.
The polycarbonate copolymer had a molar ratio of BPEF to BN of 50:50, a specific viscosity of 0.198, Tg of 159 ° C., unreacted BPEF of 90 ppm, and residual PhOH of 50 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.0 based on the weight of the resulting resin composition.
50%, 0.10% pentaerythritol tetrastearate, φ3 with vent
Pelletized using a 0 mm single screw extruder. The wet heat resistance was good, and the specific viscosity retention after the wet heat test was 94%. Moreover, heat resistance was also favorable, and the specific viscosity retention after the heat resistance test was 90%.

Example 5
BPEF 140.32 parts by weight, 1,1-bi (2- (2-hydroxyethoxy) naphthalene (hereinafter sometimes abbreviated as “BL-2EO”) 29.96 parts by weight, DPC 89.97 parts by weight, and tetramethyl Ammonium hydroxide (1.82 × 10 ⁻² parts by weight) was put in a reaction kettle equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under a normal pressure of nitrogen atmosphere, and stirred for 20 minutes. The temperature was adjusted to 20 to 30 kPa, the temperature was increased to 260 ° C. at a rate of 60 ° C./hr, and transesterification was performed, and then the pressure was reduced to 0.13 kPa or less over 120 minutes while maintaining 260 ° C. The polymerization reaction was carried out with stirring for 1 hour under the conditions of 0 ° C. and 0.13 kPa or less The polycarbonate copolymer had a molar ratio of BPEF to BL-2EO of 80:20. The specific viscosity was 0.218, Tg was 140 ° C., unreacted BPEF was 150 ppm, and residual PhOH was 300 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.050% and pentaerythritol tetrastearate based on the weight of the resulting resin composition. 0.10% was added and pelletized using a vented φ30 mm single screw extruder. The wet heat resistance was good, and the specific viscosity retention after the wet heat test was 95%. Moreover, heat resistance was also favorable, and the specific viscosity retention after the heat resistance test was 85%.

Example 6
Polymerization was conducted in the same manner as in Example 5 except that 87.70 parts by weight of BPEF and 74.89 parts by weight of BL-2EO were used.
The polycarbonate copolymer had a molar ratio of BPEF to BL-2EO of 50:50, specific viscosity of 0.202, Tg of 134 ° C., unreacted BPEF of 100 ppm, and residual PhOH of 60 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.050% and pentaerythritol tetrastearate based on the weight of the resulting resin composition. 0.10% was added and pelletized using a vented φ30 mm single screw extruder. The wet heat resistance was good, and the specific viscosity retention after the wet heat test was 95%. Moreover, heat resistance was also favorable, and the specific viscosity retention after the heat resistance test was 90%.

Example 7
Polymerization was conducted in the same manner as in Example 5 except that 70.08 parts by weight of bisphenol fluorene (hereinafter sometimes abbreviated as “BPFL”) and 74.89 parts by weight of BL-2EO were used.
The polycarbonate copolymer had a molar ratio of BPFL to BL-2EO of 50:50, a specific viscosity of 0.230, Tg of 159 ° C., unreacted BPFL of 200 ppm, and residual PhOH of 250 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.050% and pentaerythritol tetrastearate based on the weight of the resulting resin composition. 0.10% was added and pelletized using a vented φ30 mm single screw extruder. The heat and humidity resistance was good, and the specific viscosity retention after the wet heat test was 90%. Moreover, heat resistance was also favorable, and the specific viscosity retention after the heat resistance test was 80%.

Comparative Example 1
Polymerization was conducted in the same manner as in Reference Example 1 except that the reaction time under the conditions of BPEF 175.40 parts by weight, BN 00.0 parts by weight, DPC 94.26 g, 260 ° C., 0.13 kPa or less was 0.5 hour.
The polycarbonate copolymer had a BPEF to BN molar ratio of 100: 0, a specific viscosity of 0.223, Tg of 147 ° C., unreacted BPEF of 550 ppm, and residual PhOH of 600 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.050% and pentaerythritol tetrastearate based on the weight of the resulting resin composition. 0.10% was added and pelletized using a vented φ30 mm single screw extruder. As for the heat and moisture resistance, the specific viscosity retention after the wet heat test was 65%. The specific viscosity retention after the heat resistance test was 60%.

Comparative Example 2
Polymerization was carried out in the same manner as in Reference Example 1 except that the reaction time under the conditions of 70.16 parts by weight of BPEF, 68.72 parts by weight of BN, 260 ° C. and 0.13 kPa or less was 3 hours.
The polycarbonate copolymer had a BPEF to BN molar ratio of 40:60, a specific viscosity of 0.250, a Tg of 163 ° C., an unreacted BPEF of 900 ppm, and a residual PhOH of 800 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.050% and pentaerythritol tetrastearate based on the weight of the resulting resin composition. 0.10% was added and pelletized using a vented φ30 mm single screw extruder.

Comparative Example 3
Polymerization was carried out in the same manner as in Reference Example 1 except that the reaction time under the conditions of 87.70 parts by weight of BPEF, 57.16 parts by weight of BN, 260 ° C. and 0.13 kPa or less was 3 hours.
The polycarbonate copolymer had a BPEF to BN molar ratio of 40:60, a specific viscosity of 0.450, Tg of 170 ° C., unreacted BPEF of 50 ppm, and residual PhOH of 30 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.050% and pentaerythritol tetrastearate based on the weight of the resulting resin composition. 0.10% was added and pelletized using a vented φ30 mm single screw extruder.

Comparative Example 4
114 parts by weight of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) (corresponding to 50 mol%), 219 parts by weight of BPEF (corresponding to 50 mol%), 218 parts by weight of diphenyl carbonate and tetramethylammonium 9.1 × 10 ⁻³ parts by weight of hydroxide and 4.0 × 10 ⁻⁴ parts by weight of sodium hydroxide were charged into a reaction layer equipped with a stirrer, a distiller, and a decompressor, and after substituting with nitrogen, 140 ° C. Melted. After stirring for 30 minutes, the pressure was gradually reduced while raising the internal temperature to 180 ° C., and the reaction was carried out at 100 mmHg for 30 minutes to distill off the produced phenol.

  Next, the pressure was gradually reduced while raising the temperature to 200 ° C., and phenol was distilled off at 50 mmHg for 30 minutes for reaction. Furthermore, the temperature was gradually raised and reduced to 220 ° C / 30 mmHg, and the reaction was continued by repeating the same procedure as above to increase and decrease the pressure to the same temperature and pressure for 30 minutes, and further to 240 ° C / 10 mmHg and 260 ° C / 1 mmHg. Finally, the reaction was conducted at 260 ° C./1 mmHg or less for 1 hour.

Thereafter, the inside of the apparatus was purged with nitrogen, and 10.3 parts by weight of bis (2-methoxycarbonylphenyl) carbonate was added as an end-capping agent, stirred for 5 minutes and then gradually depressurized, and finally 30 ° C. at 260 ° C./1 mmHg. Stir for minutes. Thereafter, the inside of the apparatus was purged with nitrogen, and 1.2 × 10 ⁻² parts by weight of tetrabutylphosphonium salt of dodecylbenzenesulfonate was added as a neutralizing agent and stirred. When the polymerization was performed as described above, the melt viscosity of the reaction product was low, and the polymerization proceeded smoothly.

The polycarbonate copolymer had a molar ratio of BPEF to BPA of 50:50, a specific viscosity of 0.47, Tg of 147 ° C., unreacted BPEF of 500 ppm, and residual PhOH of 300 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.050% and pentaerythritol tetrastearate based on the weight of the resulting resin composition. 0.10% was added and pelletized using a vented φ30 mm single screw extruder.

Comparative Example 5
Polymerization was carried out in the same manner as in Comparative Example 4 except that 57 parts by weight of BPA (corresponding to 25 mol%) and 329 parts by weight of BPEF (corresponding to 75 mol%) were used.
The polycarbonate copolymer had a BPEF to BPA molar ratio of 75:25, a specific viscosity of 0.500, Tg of 146 ° C., unreacted BPEF of 450 ppm, and residual PhOH of 350 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.050% and pentaerythritol tetrastearate based on the weight of the resulting resin composition. 0.10% was added and pelletized using a vented φ30 mm single screw extruder.

  Since the polycarbonate copolymers obtained in Examples 5 to 7 in Table 1 have extremely low birefringence and good molding fluidity, the optical distortion of the optical lens obtained by injection molding is small. Furthermore, it has a high refractive index, has sufficient heat resistance, and is excellent as an optical lens. In contrast, the polymers obtained in Comparative Examples 1, 3, 4, and 6 do not sufficiently cancel the positive and negative intrinsic birefringence, so that the optical distortion of the optical lens obtained from the polymer is large. Further, Comparative Examples 1 and 3 to 6 have a low refractive index and are inferior in performance as an optical lens. Furthermore, since the polymers obtained in Comparative Examples 3 to 5 have a large specific viscosity of 0.40 or more, the melt viscosity is high, the optical distortion of the optical lens obtained from the polymer is large, and the moldability is poor.

  The polycarbonate copolymer resin composition of the present invention has high transparency, high refractive index, low birefringence and high fluidity, and the optical lens includes various cameras such as digital video cameras, telescopes, binoculars, TV projectors, It can be used in fields where expensive high refractive index glass lenses have been used, such as prisms, and is extremely useful.

Claims (8)

It contains 50 to 2 mol% of a structural unit represented by the following formula (I) and 50 to 98 mol% of a structural unit represented by the following formula (II), and has a specific viscosity of 0.12 to 0. Polycarbonate using a polycarbonate copolymer having a residual phenol content of 1 to 300 ppm relative to the polycarbonate copolymer and a 5% weight loss temperature of 380 ° C. or higher measured at a temperature rising rate of 20 ° C./min. The manufacturing method of the optical lens whose thickness of the center part which consists of a copolymer resin composition is 0.05-2.0 mm, and the diameter of a lens is 1.0-10.0 mm.
(As a structural unit represented by the following formula (I), those containing 30 to 40 mol % of 1,1-bi (2- (2-hydroxyethoxy) naphthalene ) are excluded.
The specific viscosity of the polycarbonate copolymer is a value measured by dissolving 0.7 g of the polycarbonate copolymer in 100 ml of methylene chloride at 20 ° C. )

(In the formula, R _{1 to} R ₈ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 2 to 6 carbon atoms. An alkenyl group, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 to 20 carbon atoms. N is an integer of 1 to 10.)

(In formula, R <_9> , R < ₁₀ > is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, and C5-C20. A cycloalkoxyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, Y is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 carbon atoms. An arylene group of ˜20, m is an integer of 1-10.) The method for producing an optical lens comprising the polycarbonate copolymer resin composition according to claim 1, wherein Y in the formula (II) is an ethylene group, and R ₉ and R ₁₀ are hydrogen atoms. R < ₁ > -R < ₈ > in formula (I) is a hydrogen atom, The manufacturing method of the optical lens which consists of a polycarbonate copolymer resin composition of Claim 1.   The method for producing an optical lens comprising the polycarbonate copolymer resin composition according to claim 1, wherein n in the formula (I) is 1.   The method for producing an optical lens comprising the polycarbonate copolymer resin composition according to claim 1, wherein the structural unit represented by the formula (I) has a 1,1-bi (2- (2-hydroxyethoxy) naphthyl) structure. .   A method for producing an optical lens comprising the polycarbonate copolymer resin composition according to any one of claims 1 to 5, wherein the refractive index is 1.640 to 1.665. The method for producing an optical lens comprising the polycarbonate copolymer resin composition according to claim 1, wherein the orientation birefringence is 0 to 6 × 10 ⁻³ .   It contains 50 to 20 mol% of the structural unit represented by the above formula (I) and 50 to 80 mol% of the structural unit represented by the above formula (II), and has a specific viscosity of 0.12 to 0. 40. A method for producing an optical lens comprising the polycarbonate copolymer resin composition according to any one of claims 1 to 7.

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