JP2007070392A - Araliphatic polycarbonate resin copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic-aliphatic polycarbonate resin copolymer having superior retention stability, color and a low photoelastic constant. <P>SOLUTION: The aromatic-aliphatic polycarbonate resin copolymer is a polycarbonate copolymer obtained by melt-phase polymerization of 5-100 mol% of a dihydroxy compound represented by general formula (1) and 95-0 mol% of a dihydroxy compound represented by general formula (2) with an aromatic diester, wherein aromatic monohydroxy compounds remaining in the resin copolymer is ≤1,000 ppm. In formula (1), R<SB>1</SB>and R<SB>2</SB>are each independently a hydrogen atom, 1-10C alkyl group, 6-10C cycloalkyl group, or 6-10C aryl group. X indicates a 2-6C alkylene group that may be branched, a 6-10C cycloalkylene group, or a 6-10C arylene group. The signs n and m indicate each independently an integer of 1-5. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin having low birefringence.

  Polycarbonate resins are used in various optical materials because of their high transparency and excellent heat resistance and mechanical properties. Among them, optical materials such as optical films, optical discs, optical prisms, and pickup lenses have a large birefringence, and the image formation point of the light transmitted through the material is blurred, causing various problems such as information reading errors. It has been known. Therefore, development of a resin having a small birefringence has been performed.

  For example, wholly aromatic polycarbonate resin copolymers using bisphenols having a fluorene structure with a high polarizability in the side chain direction have been studied (Patent Documents 1 and 2).

  Also, for the purpose of reducing the photoelastic constant, homopolycarbonate resins of ether diols having a fluorene structure having a high polarizability in the side chain direction and a phenol skeleton in the straight chain direction, or copolymers of these with bisphenols (Patent Documents 3 and 4).

  Furthermore, a copolymer of a bisphenol having a fluorene structure having a high polarizability in the side chain direction and an aliphatic cyclic diol having a specific structure has also been proposed (Patent Document 5).

  And, as a polycarbonate resin with little occurrence of birefringence even when extrusion molding, injection molding and stretching, ether diols having a fluorene structure and a phenol skeleton in the linear direction, and aliphatic cyclic diols having a specific structure A copolymer has also been proposed (Patent Document 6).

  These aromatic-aliphatic polycarbonate resin copolymers are expected as optical materials because they have excellent impact resistance, heat resistance, and low photoelastic constant, but are widely used as optical materials. Therefore, further improvement in residence stability and hue has been demanded.

JP-A-6-25398 JP-A-7-109342 JP-A-10-101787 JP-A-10-101786 JP 2000-169573 A JP 2005-146140 A

  An object of the present invention is to provide an aromatic-aliphatic polycarbonate resin having excellent residence stability, hue, and low photoelastic constant at low cost.

（式中、Ｒ_１およびＲ_２は、それぞれ独立に、水素原子、炭素数１〜１０のアルキル基、炭素数６〜１０のシクロアルキル基または炭素数６〜１０のアリール基を表す。Ｘは、分岐していても良い炭素数２〜６のアルキレン基、炭素数６〜１０のシクロアルキレン基または炭素数６〜１０のアリーレン基を示す。ｎおよびｍは、それぞれ独立に１〜５の整数を示す。）

（式中、Ｒ_３は炭素数１〜１０のアルキル基、pは０〜４の整数を示し、トリシクロデカン環の任意の炭素にＲ_３が複数個付いていても良いことを示す。） In view of the above circumstances, the present inventors can reduce the aromatic monohydroxy compound remaining during the aromatic-aliphatic polycarbonate resin copolymerization to a specific amount or less so that a polycarbonate resin having excellent hue and residence stability can be obtained. As a result, the present invention was completed.
That is, the present invention melt-polymerizes 5 to 100 mol% of the dihydroxy compound represented by the general formula (1) and 95 to 0 mol% of the dihydroxy compound represented by the general formula (2) with an aromatic carbonic acid diester. The aromatic-aliphatic polycarbonate resin copolymer is characterized in that the amount of the aromatic monohydroxy compound remaining in the resin copolymer is 1000 ppm or less.

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. X represents Represents an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, n and m are each independently an integer of 1 to 5 Is shown.)

(In the formula, R ₃ represents an alkyl group having 1 to 10 carbon atoms, p represents an integer of 0 to 4, and a plurality of R ₃ may be attached to any carbon of the tricyclodecane ring.)

  The polycarbonate resin copolymer of the present invention has a high Abbe number, a low photoelastic constant, and an excellent hue and heat resistance. Therefore, various optical lenses such as camera lenses, projector lenses, and pickup lenses, prisms, optical Various optical devices such as disk substrates, optical fibers, optical films and optical filters, and optical materials such as members thereof can be suitably used.

  The polycarbonate resin copolymer according to the present invention is suitable by a known melt polycondensation method in which a dihydroxy compound and an aromatic carbonic diester are reacted in the presence of a mixed catalyst comprising a basic compound catalyst or a transesterification catalyst or both. Can get to.

  Specific examples of the dihydroxy compound represented by the general formula (1) used in the present invention include 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)- Examples include 3-cyclohexylphenyl) fluorene and 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene.

Specific examples of the dihydroxy compound represented by the general formula (2) used in the present invention include tricyclo [5.2.1.0 ^2,6 ] decandimethanol, 4,10-dimethyltricyclo [ 5.2.1.0 ^2,6 ] decandimethanol, 4,4,10,10-tetramethyltricyclo [5.2.1.0 ^2,6 ] decandimethanol, 1,2,3,4 5,6,7,8,9,10-decamethyltricyclo [5.2.1.0 ^2,6 ] decanedimethanol, and the like.

  The ratio of the general formula (1) and the general formula (2) in the present invention is preferably a ratio of 10:90 to 100: 0 as a molar ratio. More preferably, 30:70 to 100: 0 is preferable. Actually, the birefringence is assumed to be the smallest in the vicinity of 47:53, and therefore it is more preferable to use a composition of 45:55 to 50:50.

  The polycarbonate copolymer in the present invention may have any structure of random, block or alternating copolymerization. Furthermore, a small amount of a dihydroxy compound other than the general formula (1) and the general formula (2) may be contained.

Examples of dihydroxy compounds other than those represented by general formula (1) and general formula (2) include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, and bis ( 4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2, 2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, α, α′-bis (4-hydroxyphenyl) -α, α α ′, α′-tetramethyl-m-xylene, α, α′-bis (4-hydroxyphenyl) -α, α, α ′, α′-tetramethyl-p-xylene, pentacyclo [6.5. ^.1,3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane dimethanol, pentacyclo [9.2.1.1 ^4,7 . 0 ^2,10 . 0 ^3,8 ] pentadecane dimethanol, decalin dimethanol, cyclohexane dimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5 ] Compounds such as undecane and isosorbide can be exemplified.

  Examples of the aromatic carbonic acid diester used in the present invention include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferred. The diphenyl carbonate is preferably used in a ratio of 0.97 to 1.10 mol, more preferably 0.98 to 1.05 mol, per 1 mol of the total of dihydroxy compounds.

  Examples of the basic compound catalyst include alkali metal compounds and / or alkaline earth metal compounds, nitrogen-containing compounds, and the like.

  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. These compounds are preferably used, and these compounds can be used alone or in combination.

  Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, acetic acid. Cesium, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, hydrogen phosphate Disodium, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium 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 or the like is used.

  Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate. Strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate, and the like are used.

  Specific examples of nitrogen-containing compounds include alkyl, aryl, groups, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Secondary ammoniums such as quaternary ammonium hydroxides, triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2 -Imidazoles such as phenylimidazole and benzimidazole, or ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, Tetrabutylammonium tetraphenylborate, basic or basic salts such as tetraphenyl ammonium tetraphenylborate, or the like is 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 performed at a temperature of 120 to 220 ° C., preferably 160 to 200 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours, at a pressure of normal pressure to 200 Torr. Let Next, the temperature is gradually raised to the final temperature of 230 to 260 ° C. over 1 to 3 hours, and the pressure is gradually reduced to 1 Torr or less of the final pressure, and the reaction is continued. Finally, the polycondensation reaction proceeds at a temperature of 230 to 260 ° C. under a reduced pressure of 1 Torr or less, and when the viscosity reaches a predetermined viscosity, the pressure is restored with nitrogen to complete the reaction. The reaction time of 1 Torr or less is 0.1 to 2 hours, and the total reaction time is 1 to 6 hours, usually 2 to 5 hours.

  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.

  The aromatic-aliphatic polycarbonate resin copolymer of the present invention can have excellent thermal stability and hydrolysis stability by removing or deactivating the catalyst. In general, a method of neutralizing a transesterification catalyst such as an alkali metal compound or an alkaline earth metal compound by adding a known acidic substance is preferably carried out. Specific examples of these substances include phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphoric acid, phenylphosphine, phenylphosphinic acid, phenylphosphonic acid, diphenylphosphate, diphenylphosphite, diphenylphosphine, diphenylphosphine oxide, Diphenylphosphinic acid, monomethyl acid phosphate, monomethyl acid phosphite, dimethyl acid phosphate, dimethyl acid phosphite, monobutyl acid phosphate, monobutyl acid phosphite, dibutyl acid phosphate, dibutyl acid phosphite, monostearyl acid phosphate, distearyl acid Phosphorus-containing acidic compounds such as phosphate, p-toluenesulfonic acid, methyl p-toluenesulfonate, p-tolue Ethyl sulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, pentyl p-toluenesulfonate, hexyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, p-toluenesulfone And aromatic sulfonic acid compounds such as phenethyl acid and naphthyl p-toluenesulfonate.

  The addition amount of the phosphorus-containing acidic compound and aromatic sulfonic acid compound is 1/5 to 20 times the neutralization equivalent to the alkali metal compound and / or alkaline earth metal compound catalyst, preferably 1/2 to 10 If the amount is less than this, the desired effect cannot be obtained, and if it is excessive, the heat-resistant physical properties and mechanical properties are lowered, which is not suitable.

  As a catalyst deactivator other than the above, an aromatic sulfonic acid phosphonium salt can also be suitably used. For example, benzenesulfonic acid tetrabutylphosphonium salt, p-toluenesulfonic acid tetrabutylphosphonium salt, butylbenzenesulfonic acid tetrabutylphosphonium salt, octylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfone Acid tetramethylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrahexylphosphonium salt, and the like.

  The addition amount of the aromatic sulfonic acid phosphonium salt is 1 to 300 ppm, preferably 10 to 100 ppm with respect to the aromatic-aliphatic polycarbonate resin copolymer. However, the heat resistance and mechanical properties are not suitable, which is not suitable.

  The catalyst deactivation is performed at 150 to 300 ° C., preferably 200 to 280 ° C., at a normal pressure or lower, preferably 1,333 Pa or lower, with a horizontal kneader or a multi-vent equipped with paddle blades, lattice blades or glasses blades. It is carried out by an apparatus such as a double screw extruder. When adding a catalyst deactivator as a master batch, select the base resin and the concentration of the deactivator contained in the base resin and extrusion conditions so that an appropriate amount of the deactivator can be uniformly kneaded. I do. An aromatic polycarbonate resin may be used as the base resin, but when an aromatic polycarbonate resin having a higher melt viscosity than the aromatic-aliphatic polycarbonate copolymer is used, the aromatic-aliphatic is taken into account in consideration of the shear heat generation. It is desirable that the addition amount is 10% by weight or less, preferably 5% by weight or less with respect to 100% by weight of the polycarbonate resin copolymer. An aromatic polycarbonate resin having a weight average molecular weight of 10,000 or more is used so as not to impair the excellent hue and heat resistance of the obtained aromatic-aliphatic polycarbonate resin copolymer.

  The polystyrene-converted weight average molecular weight of the aromatic-aliphatic polycarbonate resin copolymer of the present invention is preferably 20,000 to 200,000, more preferably 35,000 to 100,000. When the weight average molecular weight in terms of polystyrene is 20,000 or less, the mechanical strength is lowered, and when it is 200,000 or more, the fluidity is deteriorated and the molding conditions become severe, which is not preferable.

  The glass transition temperature of the aromatic-aliphatic polycarbonate resin copolymer of the present invention is preferably 95 ° C. or higher and 165 ° C. or lower, more preferably 105 ° C. or higher and 165 ° C. or lower. When the glass transition temperature is lower than 95 ° C., the heat resistance is deteriorated and the use environment is limited. On the other hand, if the glass transition temperature is higher than 165 ° C., the fluidity deteriorates and the molding conditions become severe, so that it is not preferable.

The aromatic monohydroxy compound remaining in the aromatic-aliphatic polycarbonate resin copolymer in the present invention is desirably 1000 ppm or less, preferably 500 ppm or less, and more preferably 200 ppm or less. The ppm here is based on weight.
If it is more than this, coloring and molecular weight reduction will occur at high temperature, and excellent moldings cannot be obtained due to coloring, silver streak, foaming, mold contamination, etc. even during molding.

  Usually, an aromatic monohydroxy compound is contained in the aromatic-aliphatic polycarbonate resin copolymer produced by the transesterification method. As a method of reducing these, it is carried out by a method of extracting with a solvent or a method of devolatilization with a horizontal kneader equipped with paddle blades, lattice blades or glasses blades, a multi-vent twin screw extruder or a thin film evaporator. Is done.

In many cases, the method of extracting with a solvent complicates the process and causes the remaining solvent to become a problem. Therefore, a devolatilization process using an extruder with a simple process and low cost is effective. The aromatic-aliphatic copolymer polycarbonate produced by melt polycondensation is introduced into an extruder while it is in a molten state immediately after completion of the reaction, and after deactivation of the catalyst, a pressure of 13,333 Pa or less by at least one or more vents. It is desirable to perform devolatilization under reduced pressure.
After completion of the reaction, it is better that the time until the catalyst is deactivated by introduction into an extruder and addition of an acidic compound is better, and depolymerization occurs when the catalyst remains active at a high temperature for a long time. A compound is not preferable.
Further, the number of vents for performing the devolatilization treatment is 1 or more, preferably 2 or more, and it is desirable to set the pressure to 13,333 Pa or less, preferably 1,333 Pa or less because the low molecular weight compound can be efficiently devolatilized. The lower limit is 10 Pa due to restrictions on the apparatus. At this time, it is also effective to perform devolatilization by injecting pure water or a suitable solvent into the resin as a devolatilization aid.
It is desirable to control the temperature of the resin in the extruder to 250 ° C. or lower, preferably 240 ° C. or lower. If it is higher than this, low molecular weight compounds are likely to be generated due to thermal decomposition, etc. Not.
It is effective that after the catalyst is deactivated, it is cooled once and then devolatilized by an extruder in the same manner without any problem.

  The process tends to be complicated due to the need for solvent recovery and the like, but the amount of low-molecular compounds contained in the resin can be greatly reduced by a method of extraction using a solvent. After the polycarbonate is added to the solvent, it is dissolved under stirring at a temperature of 20 to 100 ° C. for about 1 to 3 hours and then precipitated by cooling or the like, and thereafter treated by a method such as ordinary solid-liquid separation and drying. The ratio of polycarbonate to solvent is usually preferably about 1 to 10 times.

  In the present invention, it is desirable to add various known additives to the aromatic-aliphatic polycarbonate resin copolymer according to the purpose within a range that does not impair the physical properties together with the specific compound.

  Examples of the antioxidant include triphenyl phosphite, tris (4-methylphenyl) phosphite, tris (4-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (2-methyl- 4-ethylphenyl) phosphite, tris (2-methyl-4-t-butylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,6-di-t -Butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite, bis (monononylphenyl) pentaerythritol-di-phos Phyto, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol-di-phosphite, bis (2, 4-di-t-butyl-5-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-dimethylphenyl) octyl phosphite, 2,2-methylenebis (4-t-butyl- 6-methylphenyl) octyl phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (4,6-dimethylphenyl) hexyl phosphite, 2,2 -Methylenebis (4,6-di-t-butylphenyl) hexyl phosphite, 2,2-methylenebis (4,6-di-) Phosphite compounds such as -butylphenyl) stearyl phosphite; pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [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, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate ], 9,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris [2-methyl-4- (3,5-di-t-butyl- Hindered phenolic compounds such as 4-hydroxyphenylpropionyloxy) -5-t-butylphenyl] butane; 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2 -ON etc. are mentioned. These may be used alone or in combination of two or more.

  The amount of these antioxidants added is 0.005 to 0.1% by weight, preferably 0.01 to 0.08% by weight, based on 100% by weight of the aromatic-aliphatic polycarbonate resin copolymer. Preferably, the content is 0.01 to 0.05% by weight, and if it is less than this, the desired effect cannot be obtained, and if it is excessive, the heat-resistant physical properties and mechanical properties are lowered, which is not suitable.

  Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole. 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- ( 3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy -5'-t-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H -Benzotriazol-2-yl) phenol]], 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-di Examples include hydroxobenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone. These may be used alone or in combination of two or more.

  As the mold release agent, commonly used ones may be used, such as natural, synthetic paraffins, silicone oil, polyethylene wax, beeswax, stearic acid, stearic acid monoglyceride, stearyl stearate, palmitic acid monoglyceride, behenine. Examples include fatty acid esters such as acid behenine, pentaerythritol distearate, and pentaerythritol tetrastearate. These may be used alone or in combination of two or more.

  Other flame retardants, antistatic agents, pigments, dyes and the like can be used alone or in combination as required.

There is no restriction on the timing of addition of these additives to the aromatic-aliphatic polycarbonate resin copolymer, for example, a method of adding the resin while it is in a molten state after completion of the polycondensation reaction, or one-end cooling pelletization. A method such as re-melting and mixing afterwards may be mentioned, but a method of adding the resin while it is in a molten state after completion of the polycondensation reaction is preferable because it can reduce the heat history.
The addition method is not limited, and examples thereof include a method of directly charging and mixing into a polymerization reactor, and a method of kneading using a single screw or twin screw extruder.
Examples of the form of addition include a method of adding as it is without diluting, a method of diluting and adding to a soluble solvent, a method of adding in the form of a master batch, and the like, but there is no particular limitation.
Although there is no restriction | limiting in particular also about the timing of addition, It is preferable to add simultaneously with a catalyst deactivator or after a catalyst deactivator addition. When using an extruder, especially when pure water or a solvent is used as a devolatilization aid for low molecular weight compounds, depending on the additive used, the additive is also removed together with hydrolysis or devolatilization aid, It is desirable to add after devolatilization. When using an additive having relatively low heat resistance, it is effective to add it at the end of the extruder as much as possible in order to reduce the heat history at high temperatures.

  As the optical polycarbonate in the present invention, a blend material obtained by adding an aromatic polycarbonate resin to an aromatic-aliphatic polycarbonate resin copolymer subjected to catalyst deactivation treatment can also be used.

As the kneading method, the catalyst-deactivation-treated aromatic-aliphatic polycarbonate resin copolymer pellets and aromatic polycarbonate resin pellets may be introduced into the extruder and kneaded, or the molten aromatic immediately after completion of the reaction. -After introducing the aliphatic polycarbonate resin copolymer into the extruder and deactivating the catalyst, the aromatic polycarbonate resin may be added and kneaded, but the latter method is more preferable because shearing heat generation can be suppressed. .
In particular, when an aromatic polycarbonate resin having a higher melt viscosity than an aromatic-aliphatic polycarbonate resin copolymer is added, the resin temperature rises due to shearing heat generation, resulting in a decrease in molecular weight due to thermal decomposition, production of a low molecular weight compound, In addition, it is desirable to add the aromatic polycarbonate resin to the aromatic-aliphatic polycarbonate resin copolymer in which the catalyst is sufficiently deactivated to suppress coloring.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention does not receive a restriction | limiting at all to a following example. In addition, evaluation of the obtained aromatic-aliphatic polycarbonate resin copolymer was performed by the following method.

In the examples, physical property values were measured by the following methods.
(1) Molecular weight GPC (apparatus: Shodex GPC system 21H, detector: Shodex RI-71S, column: Shodex K-805L 4) was used and measured as polystyrene equivalent molecular weight (weight average molecular weight: Mw). Chloroform was used as a developing solvent.
(2) Quantitative determination of phenol A polycarbonate sample weighed in was dissolved in dichloromethane and gradually added to excess methanol with stirring to reprecipitate the resin. After sufficiently stirring, the precipitate was filtered off, and the liquid obtained by concentrating the filtrate with an evaporator was quantified by GC analysis.
(3) Solution hue (YI value)
A sample of 8.0 g was dissolved in 80 ml of methylene chloride, and the YI value (yellow index) was measured using a 5.0 cm quartz glass cell. As a color difference meter, a spectro color meter: SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used.
(4) Residence stability (dYI value)
9.0 g of the sample was taken in a test tube and dried for 2 hours under a nitrogen atmosphere at 100 ° C. using SCRYICS: DRY BLOCKBATH AL-301, and then a residence test was conducted for 2 hours under a nitrogen atmosphere at 240 ° C. After returning the sample to room temperature, the sample was dissolved in 90 ml of methylene chloride, the YI value (yellow index) was measured using a 5.0 cm quartz glass cell, and the difference (dYI) from the YI value of the sample before the residence test was evaluated. did. As a color difference meter, a spectro color meter: SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. was used.

Synthesis Example 1 (Aromatic-aliphatic polycarbonate resin copolymer)
Raw material molar ratio (diphenyl) in a first vertical stirring polymerization tank (hereinafter referred to as the first polymerization tank; reaction conditions: 133.32 Pa, 130 ° C., stirring speed 160 rpm) in a nitrogen gas atmosphere substantially free of oxygen. 5 μmol of sodium hydrogen carbonate as a catalyst with respect to the total mol of BPEF and TCDDM, and DPC so that carbonate (DPC) / (bisphenoxyethanol fluorene (BPEF) + tricyclodecanedimethanol (TCDDM)) is 1.02. And BPEF are continuously fed to the first polymerization tank at a flow rate of 45.1 kg / h at a constant ratio (DPC / BPEF (molar ratio) = 2.525). The TCDDM is continuously supplied at a flow rate of 4 kg / h, and the polymer at the bottom of the tank is set so that the average residence time in the first polymerization tank is 70 minutes. The liquid level was kept constant while controlling the valve opening degree provided in the discharge line, and the polymerization liquid (prepolymer) discharged from the tank bottom continued to the second, third and fourth vertical polymerization tanks. In addition, the fifth horizontal polymerization tank (manufactured by Hitachi, Ltd .: Lattice blade polymerization machine (trade name)) is successively and continuously supplied to produce an aromatic-aliphatic copolymer polycarbonate at 50 kg / h from the fifth horizontal polymerization tank. did.
The liquid level was controlled so that the average residence time of each tank was 60 minutes for the second tank, 30 minutes for each of the third and fourth vertical polymerization tanks, and 90 minutes for the fifth horizontal polymerization tank. The resulting phenol was also distilled off.
The polymerization conditions of the second to fifth polymerization tanks are the second polymerization tank (210 ° C., 17.5 Pa, stirring speed 160 rpm) and the third polymerization tank (225 ° C., 25 Pa, stirring speed 75 rpm), respectively. It was set as the tank (245 degreeC, 25 Pa, stirring speed 5rpm).
The resulting aromatic-aliphatic copolymer polycarbonate resin had a weight average molecular weight of 64,100.

Example 1
An aromatic-aliphatic polycarbonate resin copolymer was produced by the method of Synthesis Example 1, and the polymer (Mw = 64,100) discharged from the fifth horizontal polymerization tank was continuously supplied in a molten state at 35 kg / h. At speed,
1125885797796_0
3 vent type twin screw extruder (46 mmφ twin screw extruder manufactured by Kobe Steel, Ltd .; barrel number 11, barrel temperature 240 ° C.) and the vent port (17) closest to the resin supply port (20) The catalyst deactivator, which will be described later, is supplied by a side feed compactor (16) at a supply rate of 0.7 kg / h to the resin in the form of a masterbatch, and then kneaded and decompressed at 266 Pa with three vents. After devolatilization, foreign matters were removed with a 10 μm resin filter and pelletized with water.
The composition of the master batch is a powder of aromatic polycarbonate (BPA type polycarbonate; weight average molecular weight Mw = 51,000) [Mitsubishi Gas Chemical Co., Ltd .: Iupilon S-3000 (interface method product: trade name)]. The amount of p-toluenesulfonate n-butyl (manufactured by Tokyo Chemical Industry Co., Ltd .; hereinafter referred to as pTSB) is 9 times the neutralization equivalent of sodium bicarbonate [18 μmol / mol (BPEF And TCDDM in total 1 mol)].
Table 1 shows the evaluation results of the obtained pellets.

Example 2
The same procedure as in Example 1 was performed except that the degree of vacuum at the vent portion of the extruder was 1,333 Pa. The evaluation results are shown in Table 1.

Comparative Example 1
The catalyst was deactivated and the resin was purified in the same manner as in Example 1 except that the degree of vacuum at the vent was changed as shown in Table 1. The evaluation results are shown in Table 1.

Comparative Example 2
The catalyst was deactivated and the resin was purified in the same manner as in Example 1 except that the first vent and the second vent of the extruder in FIG. 1 were closed and the degree of vacuum of the third vent was 266 Pa. The evaluation results are shown in Table 1.

The schematic of the extruder used in Examples 1, 2 and Comparative Examples 1, 2 is shown.

Explanation of symbols

1: twin screw extruder 2: feed barrel 3: C1 barrel 4: C2 barrel 5: C3 barrel 6: C4 barrel 7: C5 barrel 8: C6 barrel 9: C7 barrel 10: C8 barrel 11: C9 barrel 12: C10 barrel 13: Gear pump 14: Polymer filter 15: Die head 16: Side feed compactor 17: First vent 18: Second vent 19: Third vent 20: Resin supply port

Claims (3)

Polycarbonate resin copolymer obtained by melt polymerizing 5 to 100 mol% of the dihydroxy compound represented by the general formula (1) and 95 to 0 mol% of the dihydroxy compound represented by the general formula (2) with an aromatic carbonic acid diester. An aromatic-aliphatic polycarbonate resin copolymer, wherein the amount of the aromatic monohydroxy compound remaining in the resin copolymer is 1000 ppm or less.

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. X represents Represents an optionally branched alkylene group having 2 to 6 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, n and m are each independently an integer of 1 to 5 Is shown.)

(In the formula, R ₃ represents an alkyl group having 1 to 10 carbon atoms, p represents an integer of 0 to 4, and a plurality of R ₃ may be attached to any carbon of the tricyclodecane ring.) The aromatic-aliphatic polycarbonate resin copolymer according to claim 1, wherein R ₁ and R ₂ are hydrogen atoms, n and m are 1, X is an alkylene group having 2 carbon atoms, and p is 0. . The optical polycarbonate according to claim 1 or 2, having a refractive index of 1.54 to 1.64.

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