JP5808960B2 - Polycarbonate copolymer and optical lens having high refractive index and excellent heat resistance - Google Patents

Description

  The present invention relates to a polycarbonate copolymer containing a specific dihydroxy compound in a specific ratio and having a high refractive index and excellent heat resistance.

  Optical glass or optical transparent resin is used as a material for optical lenses used in optical systems of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of materials with various refractive indexes and Abbe numbers, but the material cost is high and moldability is high. However, there is a problem that productivity is low.

  On the other hand, optical transparent resins, especially thermoplastic transparent resins, have the advantage that they can be mass-produced by injection molding, and polycarbonate resins and the like are currently used as materials for camera lenses. However, due to the recent reduction in lens thickness, a higher refractive index of the lens resin is required. Further, the product is lighter, thinner and shorter, and may be used closer to a heat source or may require post-processing by heat. Heat resistance is required. Therefore, it is desired to develop a new material having a higher refractive index and better heat resistance than before.

  For example, a polycarbonate copolymer having a fluorene structure is disclosed (Patent Document 1). However, according to the patent document, although it has excellent optical characteristics, it has not been investigated with respect to refractive index, heat resistance, and birefringence, which are important optical properties for a lens, and an optical material such as an optical disk as an effect of the invention. It is only intended for infrastructure use. Therefore, it is insufficient as a high refractive index and high heat resistance lens, and there is still room for improvement.

JP-A-10-101786

  The present invention is intended to solve the above problems, and relates to a polycarbonate copolymer containing a specific proportion of a specific dihydroxy compound and an optical lens formed from the polycarbonate copolymer. More specifically, the present invention relates to a polycarbonate copolymer for optical lenses having a high refractive index and excellent heat resistance, low birefringence and transparency.

  As a result of intensive research aimed at achieving this object, the present inventors have found that the above object can be achieved by copolymerizing a specific fluorene-containing dihydroxy compound and a dihydroxy compound at a specific ratio, and have reached the present invention. .

（式中、Ｒ１、Ｒ２、Ｒ３およびＲ４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６〜２
０のアリールオキシ基である。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およびｍは１〜１０の整
数である。）

（式中、Ｒ５およびＲ６は、それぞれ独立に水素原子である。）

（式中、Ｒ７およびＲ８は、それぞれ独立に水素原子である。）
２．全ヒドロキシ化合物中の一般式（１）で表されるジヒドロキシ化合物及び一般式（２）もしくは一般式（３）で表されるジヒドロキシ化合物の合計の割合が１００〜８０％であり、且つ一般式（１）：一般式（２）もしくは一般式（３）の割合がモル比で５％以上〜５０％未満：９５％以下〜５０％を超える範囲で構成された前記１記載のポリカーボネート共重合体。
３．一般式（２）で表される化合物が、ハイドロキノン、レゾルシノール、カテコールからなる群より選ばれる少なくとも１種である前記１または２記載のポリカーボネート共重合体。
４．一般式（３）で表される化合物が、２，６−ナフタレンジオールである前記１または２記載のポリカーボネート共重合体。
５．一般式（１）で表される化合物において、Ｒ１、Ｒ２、Ｒ３およびＲ４が水素原子、Ｘがエチレン基、ｎ＝１およびｍ＝１である前記１〜４のいずれか１項に記載のポリカーボネート共重合体。
６．屈折率が１．６４〜１．６７、かつガラス転移温度が１５５℃〜１８０℃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。
７．該ポリカーボネート樹脂はそのポリマー０．７ｇを１００ｍｌの塩化メチレンに溶解し、２０℃で測定した比粘度が０．１２〜０．５５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。
８．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より形成された光学レンズ。 1. Dihydroxy compound represented by general formula (1) in all hydroxy compounds and general formula (2)
Or the ratio of the sum total of the dihydroxy compound represented by General formula (3) is 100 to 70%, and the ratio of General formula (1): General formula (2) or General formula (3) is 5% by molar ratio. that's all~
Less than 50%: A polycarbonate copolymer constituted in a range of 95% or less to more than 50%.

(In the formula, R1, R2, R3 and R4 each independently represent 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 carbon atoms. -20 cycloalkoxyl group, aryl group having 6-20 carbon atoms, or 6-2 carbon atoms
0 aryloxy group. X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms. n and m are integers of 1-10. )

(Wherein, R5 and R6, are each independently hydrogen atom.)

(Wherein, R7 and R8, are each independently hydrogen atom.)
2. The total proportion of the dihydroxy compound represented by the general formula (1) and the dihydroxy compound represented by the general formula (2) or the general formula (3) in all the hydroxy compounds is 100 to 80%, and the general formula ( 1): The polycarbonate copolymer according to 1 above, wherein the ratio of the general formula (2) or the general formula (3) is in a range of 5% to less than 50%: 95% or less to more than 50% in molar ratio.
3. 3. The polycarbonate copolymer according to 1 or 2, wherein the compound represented by the general formula (2) is at least one selected from the group consisting of hydroquinone, resorcinol, and catechol.
4). 3. The polycarbonate copolymer according to 1 or 2, wherein the compound represented by the general formula (3) is 2,6-naphthalenediol.
5. 5. The polycarbonate according to any one of 1 to 4 above, wherein in the compound represented by the general formula (1), R1, R2, R3 and R4 are hydrogen atoms, X is an ethylene group, n = 1 and m = 1. Copolymer.
6). The polycarbonate copolymer according to any one of 1 to 5 above, which has a refractive index of 1.64 to 1.67 and a glass transition temperature of 155 to 180 ° C.
7). 7. The polycarbonate copolymer according to any one of 1 to 6 above, wherein 0.7 g of the polymer is dissolved in 100 ml of methylene chloride and the specific viscosity measured at 20 ° C. is 0.12 to 0.55.
8). 8. An optical lens formed from the polycarbonate copolymer according to any one of 1 to 7 above.

  According to the present invention, a polycarbonate copolymer having a high refractive index and excellent heat resistance, low birefringence, and transparency can be obtained, and an optical lens formed from the polycarbonate copolymer can be injection molded. Since it is highly productive and inexpensive, it can be used in fields where expensive glass lenses have been used, such as cameras, telescopes, binoculars, and television projectors. Further, according to the present invention, a high refractive index and high heat-resistant aspherical lens, which is technically difficult to process with a glass lens, can be easily obtained by injection molding, which is extremely useful.

  When the proportion of the dihydroxy compound represented by the general formula (1) in the polycarbonate copolymer of the present invention exceeds 50 mol%, the optical member obtained from the polycarbonate copolymer is not preferable because the heat resistance is poor.

  When the ratio of the dihydroxy compound represented by the chemical formula (2) or the chemical formula (3) in the polycarbonate copolymer of the present invention is more than 95 mol%, the fluidity at the time of melting is poor and the moldability is lowered, which is not preferable. Moreover, the use which can use a large optical distortion is limited and is not preferable.

  As the dihydroxy compound represented by the general formula (1) in the polycarbonate copolymer of the present invention, specifically, as the dihydroxy compound, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9- Bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3- Enirufeniru) fluorene, and the like, among which 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene is preferable. You may use these individually or in combination of 2 or more types.

The dihydroxy compound represented by the general formula (2) in the polycarbonate copolymer of the present invention may be an aromatic dihydroxy component, and among them, hydroquinone, resorcinol and catechol are preferable. You may use these individually or in combination of 2 or more types.
The dihydroxy compound represented by the general formula (3) in the polycarbonate copolymer of the present invention may be a naphthalenediol component, and 2,6-naphthalenediol is particularly preferable. You may use these individually or in combination of 2 or more types.

  General formula (1): Ratio of general formula (2) or general formula (3) is 5% to less than 50% in molar ratio: 95% or less to more than 50%, and more than 10% to less than 50% : 90% or less to a range exceeding 50% is preferable, and 20% or more to less than 50%: a range of 80% or less to more than 50% is even more preferable.

  The polycarbonate copolymer of the present invention may be added with other dihydroxy compounds copolymerizable with the general formulas (1), (2) and (3) depending on the purpose, and 4,4′-biphenol, 1,1 -Bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C) ), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1 , 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pe Tan, 4,4 '-(p-phenylenediisopropylidene) diphenol, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) ) -4-isopropylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxy) Aromatic diols such as phenyl) fluorene, aliphatic diols such as ethylene glycol, tricyclo [5.2.1.02,6] decanedimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol , Norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1, And cycloaliphatic diols such as 3-dimethanol and spiroglycol, particularly 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 9,9-bis (3-methyl-4-hydroxyphenyl). Fluorene is preferred. These other dihydroxy compounds are 30 mol% or less, preferably 20 mol% or less of the total dihydroxy compound components.

The polycarbonate copolymer of the present invention is produced by a reaction means known per se for producing an ordinary polycarbonate copolymer, for example, a method of reacting a dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester.
In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours.

  The transesterification reaction using a carbonic acid diester as a carbonate precursor is a known melt polycondensation method in which two or more dihydroxy compounds are reacted in the presence of a carbonic acid diester and a basic compound catalyst, a transesterification catalyst or a mixed catalyst composed of both. Can be manufactured. Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Of these, diphenyl carbonate is particularly preferred. The carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to 1 mol of the diol component.

Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
Examples of such compounds include organic acid salts such as alkali metal and alkaline earth metal compounds, inorganic salts, oxides, hydroxides, hydrides or alkoxides, quaternary ammonium hydroxides and salts thereof, amines, and the like. Are preferably used, and these compounds can be used alone or in combination.

  Examples of the alkali metal compound used in the present invention include alkali metal organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, stearin Sodium phosphate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, hydrogen phosphate 2 potassium, 2 lithium hydrogen phosphate, 2 sodium phenyl phosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt, etc. It is needed.

  Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, acetic acid Magnesium, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate and the like are used.

  Examples of the nitrogen-containing compound include quaternary ammonium hydroxide and salts thereof, amines and the like. Specifically, quaternary ammonium hydroxides having alkyl, aryl, groups, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, Tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2-phenylimidazole and benzimidazole Imidazoles such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetra Bases or basic salts such as traphenylborate and tetraphenylammonium tetraphenylborate are used.

As the transesterification catalyst, zinc, tin, zirconium and lead salts are preferably used, and these can be used alone or in combination.
Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, and dibutyltin. Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate and the like are used.
These catalysts are used in a ratio of 10 ⁻⁹ to 10 ⁻³ mol, preferably 10 ⁻⁷ to 10 ⁻⁴ mol, per 1 mol of the total of dihydroxy compounds.

The melt polycondensation method according to the present invention is a method in which melt polycondensation is carried out using the above-mentioned raw materials and catalyst while removing by-products by a transesterification reaction under normal pressure or reduced pressure. The reaction is generally carried out in a multistage process of two or more stages.
Specifically, the reaction at the first stage is allowed to react at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is raised while raising the degree of vacuum of the reaction system to react the dihydroxy compound and the carbonic acid diester, and finally polycondensation is carried out at a temperature of 200 to 350 ° C. under a reduced pressure of 1 mmHg or less for 0.05 to 2 hours. Perform the reaction. Such a reaction may be carried out continuously or batchwise. The reaction apparatus used for carrying out the above reaction is equipped with paddle blades, lattice blades, glasses blades, etc. even with vertical types equipped with vertical stirring blades, Max blend stirring blades, helical ribbon stirring blades, etc. It may be a horizontal type or an extruder type equipped with a screw, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer.

  In the polycarbonate resin according to the present invention, the catalyst is removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolysis stability. In general, a method of deactivating a catalyst by adding a known acidic substance is preferably performed. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate. Esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, phosphorous acid Phosphorous esters such as di-n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphorus Phosphate esters such as dioctyl acid and monooctyl phosphate, phosphones such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid , Phosphonic acid esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, and aromatics such as tetrabutylphosphonium dodecylbenzenesulfonate Organic halides such as aromatic sulfonates, stearic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, 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 not preferable.

  After deactivation of the catalyst, a step of devolatilizing and removing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350 ° C. may be provided. For this purpose, paddle blades, lattice blades, glasses A horizontal apparatus provided with a stirring blade having excellent surface renewability such as a blade or a thin film evaporator is preferably used.

  The polycarbonate copolymer in the present invention is preferably one having 0.7 g of the polymer dissolved in 100 ml of methylene chloride and having a specific viscosity in the range of 0.12 to 0.55 measured at 20 ° C. The thing of the range of 45 is more preferable. If the specific viscosity is less than 0.12, the molded product becomes brittle, and if it is higher than 0.55, the melt viscosity and the solution viscosity become high and handling becomes difficult.

  The polycarbonate copolymer in the present invention preferably has a glass transition temperature (Tg) measured at a heating rate of 20 ° C./min of 155 to 180 ° C., more preferably 155 to 175 ° C. When the Tg is less than 155 ° C., the heat resistance is not sufficient, the use is limited, and it is not preferable as a heat resistant lens. On the other hand, when Tg is higher than 180 ° C., the melt viscosity becomes high, and it becomes difficult to handle when forming a molded body, which is not preferable.

  The polycarbonate copolymer according to the present invention preferably has a 5% weight loss temperature of 350 ° C. or higher as a thermal stability index measured at a temperature rising rate of 20 ° C./min. Furthermore, it is preferable that it is 400 degreeC or more. 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 polycarbonate resin in the present invention preferably has a refractive index of 1.64 to 1.67 at 25 ° C. and a wavelength of 587 nm.
The optical lens made of the polycarbonate copolymer in the present invention is molded by an arbitrary method such as an injection molding method, a compression molding method, or an injection compression molding method.

  Various additives can be used for the optical lens formed from the polycarbonate copolymer of the present invention 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, and 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 and / or 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, and stearyl stearate is preferable.

  Specific examples of partial esters or total esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetra All esters or parts of dipentaerythritol, such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate Examples include esters. 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.
As content of the mold release agent in a polycarbonate copolymer granular material, the range of 0.005-2.0 weight part is preferable with respect to 100 weight part of polycarbonate copolymer granular material, 0.01-0 The range of 0.6 parts by weight is more preferable, and the range of 0.02 to 0.5 parts by weight is more preferable.

Examples of the heat stabilizer include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer.
Examples of the phosphorous heat stabilizer 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 Phyto, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erisrito Diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol di Phosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, Dipropyl benzenephosphonate, tetrakis (2,4-di-t-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. 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 And particularly preferably tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite is used. The

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

  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, and pentaerythritol-tetrakis (3- Lauryl thiopropionate), pentaerythritol-tetrakis (3-myristyl thiopropionate), dilauryl-3, 3'-thiodipropionate, dimyristyl-3, 3'-thiodipropionate. 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 content of the sulfur type thermal stabilizer in a polycarbonate copolymer granular material, 0.001-0.2 weight part is preferable with respect to 100 weight part of polycarbonate copolymer granular material.

  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.

  As content of the hindered phenol type heat stabilizer in a polycarbonate copolymer granular material, 0.001-0.3 weight part is preferable with respect to 100 weight part of polycarbonate copolymer granular material.

  As the UV absorber, at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic imino ester UV absorbers, and cyanoacrylates Is preferred.

  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, and these may be used alone or in combination of two or more. Can be used in a mixture. 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, especially 2,2′-p-phenylenebis (3,1-benzoxazine-4 -On) 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 blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight with respect to 100 parts by weight of the polycarbonate copolymer powder. More preferably, it is 0.05-0.8 weight part. If it is the range of this compounding quantity, it is possible to provide sufficient weather resistance to a polycarbonate copolymer molded article 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 powder. In particular, in the case of polycarbonate copolymer granules with weather resistance, a certain amount of UV absorber is blended, so the reality is that the polycarbonate resin molded product tends to be yellowish due to the "action and color of the UV absorber". In particular, the blending of a bluing agent is very effective for imparting a natural transparency to a sheet or lens.
The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm based on the polycarbonate copolymer powder.

  In the optical lens formed from the polycarbonate copolymer in the present invention, the transmittance of the molded piece at 550 nm is preferably 80% or more. Further, it is preferably 85% or more. If the transmittance is lower than 80%, it is difficult to use as an optical lens.

  The optical lens of the present invention preferably has a small optical distortion. An optical lens made of a general bisphenol A type polycarbonate resin has a large optical distortion, and it may be possible to reduce the value depending on molding conditions, but the condition width is usually very small, and therefore molding is very difficult. It is difficult to. Since the polycarbonate copolymer of the present invention has a 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.

  A coating layer such as an antireflection layer or a hard coating layer may be provided on the surface of the optical lens formed from the polycarbonate copolymer in the present invention, if 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.

The following examples further illustrate the present invention. The evaluation was performed according to the following method.
(1) Specific viscosity: The polycarbonate copolymer pellet obtained after completion of the polymerization was dried at 120 ° C. for 4 hours, and a solution in which 0.35 g of the pellet was dissolved in 50 cc of methylene chloride was used as a measurement sample. In the measurement, the passage time between the marked lines of the Oswald viscosity tube was measured in a constant temperature bath of 20 ± 0.01 ° C., and the specific viscosity (η _sp ) of the solution at 20 ° C. was obtained from the following formula.
η _sp = (t ₁ −t ₀ ) / t ₀
Here, the specific viscosity t _{1 is the} passage time between the marked lines of the polymer solution, and t ₀ is the passage time between the marked lines of methylene chloride.
(2) Copolymerization ratio: The polycarbonate resin cut out from the molded piece of the aspherical lens was measured using proton NMR of JNM-AL400 manufactured by JEOL Ltd.
(3) Glass transition point (Tg): Measured by DuPont 910 DSC.
(4) refractive index _(n d): measured with an Abbe refractometer ATAGO Ltd. DR-M2.
(5) Optical distortion: The molded lens was sandwiched between two polarizing plates and evaluated by visually observing light leakage from behind by a direct Nicol method.
(6) Total light transmittance: A 1 mm-thick molded piece was measured using MDH-300A manufactured by Nippon Denshoku Co., Ltd.

Example 1 Synthesis of Polycarbonate Copolymer
9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter sometimes abbreviated as “BPEF”) 21.47 parts by weight, hydroquinone 5.61 parts by weight, diphenyl carbonate 22.06 parts by weight, 4.00 × 10 ⁻⁵ parts by weight of sodium hydroxide and 4.56 × 10 ⁻³ parts by weight of tetramethylammonium hydroxide were placed in a 10-liter reactor equipped with a stirrer and a distiller, and were taken for 30 minutes under a nitrogen atmosphere of 101 kPa. The mixture was heated to 180 ° C. and stirred.
Thereafter, the degree of vacuum was adjusted to 20 kPa over 20 minutes, the temperature was raised to 240 ° C. at a rate of 15.0 ° C./hr, and the temperature was maintained at 240 ° C. and 20 kPa for 10 minutes. Thereafter, the pressure was reduced from 20 kPa to 0.13 kPa or less over 80 minutes. Further, the polymerization reaction was carried out with stirring for 20 minutes under the conditions of 240 ° C. and 0.13 kPa or less. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and then 2.92 × 10 ⁻³ parts by weight of tetrabutylphosphonium dodecylbenzenesulfonate was added to deactivate the catalyst. Thereafter, the produced polycarbonate copolymer was extracted while pelletizing. The polycarbonate copolymer had a molar ratio of BPEF to hydroquinone of 49:51.

Example 2
A polycarbonate copolymer was synthesized in the same manner as in Example 1 except that the amount of BPEF used in Example 1 was 10.96 parts by weight and the amount of hydroquinone used was 8.26 parts by weight. The polycarbonate copolymer had a molar ratio of BPEF to hydroquinone of 25:75.

Example 3
A polycarbonate copolymer was synthesized in the same manner as in Example 1 except that the amount of BPEF used in Example 1 was 2.19 parts by weight and the amount of hydroquinone used was 10.46 parts by weight. The polycarbonate copolymer had a molar ratio of BPEF to hydroquinone of 5:95.

Example 4
A polycarbonate copolymer was synthesized in the same manner as in Example 1 except that the amount of BPEF used in Example 1 was 10.96 parts by weight and the amount of resorcinol used was 8.26 parts by weight. The polycarbonate copolymer had a molar ratio of BPEF to resorcinol of 25:75.

Example 5
A polycarbonate copolymer was synthesized in the same manner as in Example 1 except that the amount of BPEF used in Example 1 was 10.96 parts by weight and the amount of catechol used was 8.26 parts by weight. The polycarbonate copolymer had a molar ratio of BPEF to catechol of 25:75.

Example 6
A polycarbonate copolymer was synthesized in the same manner as in Example 1 except that the amount of BPEF used in Example 1 was 21.49 parts by weight and the amount of naphthalene diol was 8.17 parts by weight. The polycarbonate copolymer had a molar ratio of BPEF to naphthalenediol of 49:51.

Example 7
A polycarbonate copolymer was synthesized in the same manner as in Example 1 except that the amount of BPEF used in Example 1 was 10.96 parts by weight and the amount of naphthalene diol was 8.17 parts by weight. The polycarbonate copolymer had a molar ratio of BPEF to naphthalenediol of 25:75.

Example 8
A polycarbonate copolymer was synthesized in the same manner as in Example 1 except that the amount of BPEF used in Example 1 was 2.19 parts by weight and the amount of naphthalene diol was 15.22 parts by weight. The polycarbonate copolymer had a molar ratio of BPEF to naphthalenediol of 5:95.

Example 9
The amount of BPEF used in Example 1 is 8.77 parts by weight, the amount of hydroquinone is 7.71 parts by weight, 2,2-bis (4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as “BPA”). A polycarbonate copolymer was synthesized in the same manner as in Example 1 except that the amount was 2.28 parts by weight. The polycarbonate copolymer had a molar ratio of BPEF, hydroquinone and BPA of 20:70:10.

Comparative Example 1
BPEF 26.31 parts, hydroquinone 4.40 parts, diphenyl carbonate 22.06 parts, sodium hydroxide 4.00 × 10 ⁻⁵ parts and tetramethylammonium hydroxide 4.56 × 10 ⁻³ parts by weight The mixture was placed in a 10-liter reactor equipped with a distillation apparatus, heated to 180 ° C. over 30 minutes under a nitrogen atmosphere of 101 kPa, and stirred.
Thereafter, the degree of vacuum was adjusted to 20 kPa over 20 minutes, the temperature was raised to 240 ° C. at a rate of 15.0 ° C./hr, and the temperature was maintained at 240 ° C. and 20 kPa for 10 minutes. Thereafter, the pressure was reduced from 20 kPa to 0.13 kPa or less over 80 minutes. Further, the polymerization reaction was carried out with stirring for 20 minutes under the conditions of 240 ° C. and 0.13 kPa or less. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and then 2.92 × 10 ⁻³ parts by weight of tetrabutylphosphonium dodecylbenzenesulfonate was added to deactivate the catalyst. Thereafter, the produced polycarbonate copolymer was extracted while pelletizing. The polycarbonate copolymer had a molar ratio of BPEF to hydroquinone of 60:40.

Comparative Example 2
A hydroquinone homopolycarbonate was synthesized in the same manner as in Comparative Example 1 except that the amount of BPEF used in Comparative Example 1 was 0.00 parts by weight and the amount of hydroquinone used was 11.01 parts by weight.

Comparative Example 3
A homopolycarbonate of naphthalenediol was synthesized in the same manner as in Comparative Example 1, except that the amount of BPEF used in Comparative Example 1 was 0.00 part by weight and the amount of naphthalenediol used was 16.02 parts by weight.

Comparative Example 4
38.15 g of BPEF, 2.97 g of BPA, diphenyl carbonate; 22.06 g, and 5.04 × 10 ⁻⁵ g of sodium hydrogen carbonate were placed in a 50 liter reactor equipped with a stirrer and a distiller, and the nitrogen atmosphere was 101 kPa over 1 hour. Heated to 215 ° C. and stirred.
Thereafter, the degree of vacuum was adjusted to 20 kPa over 15 minutes, and the transesterification reaction was carried out by maintaining for 20 minutes under the conditions of 215 ° C. and 20 kPa. Further, the temperature was raised to 240 ° C. at a rate of 37.5 ° C./hr, and held at 240 ° C. and 20 kPa for 10 minutes. Then, it adjusted over 10 minutes and hold | maintained at 240 degreeC and 13 kPa for 70 minutes. Then, it adjusted to 13 kPa over 10 minutes, and hold | maintained at 240 degreeC and 13 kPa for 10 minutes. Furthermore, it was made 0.13 kPa or less over 40 minutes, and the polymerization reaction was performed with stirring for 10 minutes under the conditions of 240 ° C. and 0.13 kPa or less. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced polycarbonate resin was extracted while being pelletized. The polycarbonate copolymer had a molar ratio of BPEF to BPA of 87:13.

In Examples 1 to 9 and Comparative Examples 1 to 4, absorption from a carbonate bond was confirmed in the vicinity of 1760 cm ^{−1 by} IR measurement. Moreover, since it was one peak resulting from Tg obtained from DSC measurement, it was confirmed that the copolymer was a random copolymer.

Examples 1-9, Comparative Examples 1-4
After the prepared polycarbonate copolymer was vacuum-dried at 120 ° C. for 24 hours, 0.050% bis (2,4-dicumylphenyl) pentaerythritol diphosphite and 0.10% pentaerythritol tetrastearate were added, Pelletization was performed using a vented φ30 mm single screw extruder. Then, using the SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. and a double convex lens having a diameter of 7.9 mm and a thickness of 3.0 mm and an N-20C injection molding machine manufactured by JSW under the following molding conditions. A molded piece having a thickness of 1.0 mm, a width of 1.0 cm, and a length of 2.0 cm was injection molded. The lens was sandwiched between two polarizing plates and evaluated by visually observing light leakage from behind using a direct Nicol method. The evaluation was as follows: A: Almost no light leakage, B: Slight light leakage was observed, B: Slight light leakage was observed, X: Light leakage was remarkable. Moreover, the total light transmittance was measured using the said molded piece. The results are shown in Table 1.

  In Examples 1 to 9, molded products obtained with Tg in an appropriate range are excellent in heat resistance and workability. Further, since it has a high refractive index and small optical distortion, it is suitable as a lens. Among them, Examples 6, 7 and 8 have particularly high refractive index and are good, and Example 8 has the highest refractive index and Tg and is suitable for a heat-resistant lens. On the other hand, Comparative Example 1 has a low Tg and refractive index, Comparative Example 2 has a large optical distortion, and Comparative Example 3 has an excessively high Tg and is inferior in molding processability. Comparative Example 4 has a low refractive index, and the range of use as a lens is limited.

  The optical lens made of the polycarbonate copolymer of the present invention is extremely useful because it can be used in fields where expensive high-refractive index glass lenses have conventionally been used, such as cameras, telescopes, binoculars, and television projectors.

Claims (8)

Dihydroxy compound represented by general formula (1) in all hydroxy compounds and general formula (2)
Or the ratio of the sum total of the dihydroxy compound represented by General formula (3) is 100 to 70%, and the ratio of General formula (1): General formula (2) or General formula (3) is 5% by molar ratio. that's all~
Less than 50%: A polycarbonate copolymer constituted in a range of 95% or less to more than 50%.

(In the formula, R1, R2, R3 and R4 each independently represent 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 carbon atoms. -20 cycloalkoxyl group, aryl group having 6-20 carbon atoms, or 6-2 carbon atoms
0 aryloxy group. X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms. n and m are integers of 1-10. )

(Wherein, R5 and R6, are each independently hydrogen atom.)

(Wherein, R7 and R8, are each independently hydrogen atom.) Dihydroxy compound represented by general formula (1) in all hydroxy compounds and general formula (2)
Or the ratio of the sum total of the dihydroxy compound represented by General formula (3) is 100 to 80%, and the ratio of General formula (1): General formula (2) or General formula (3) is 5% by molar ratio. that's all~
The polycarbonate copolymer of Claim 1 comprised in less than 50%: 95% or less-more than 50%. The polycarbonate copolymer according to claim 1 or 2, wherein the compound represented by the general formula (2) is at least one selected from the group consisting of hydroquinone, resorcinol, and catechol. The polycarbonate copolymer according to claim 1 or 2, wherein the compound represented by the general formula (3) is 2,6-naphthalenediol. In the compound represented by the general formula (1), R1, R2, R3 and R4 are a hydrogen atom, X
Is an ethylene group, n = 1 and m = 1, The polycarbonate copolymer of any one of Claims 1-4. The polycarbonate copolymer according to any one of claims 1 to 5, which has a refractive index of 1.64 to 1.67 and a glass transition temperature of 155 ° C to 180 ° C. The polycarbonate resin according to any one of claims 1 to 6, wherein 0.7 g of the polymer is dissolved in 100 ml of methylene chloride and the specific viscosity measured at 20 ° C is 0.12 to 0.55. Polymer. The optical lens formed from the polycarbonate copolymer of any one of Claims 1-7.