WO2011007744A1 - ポリカーボネート樹脂組成物 - Google Patents
ポリカーボネート樹脂組成物 Download PDFInfo
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- WO2011007744A1 WO2011007744A1 PCT/JP2010/061745 JP2010061745W WO2011007744A1 WO 2011007744 A1 WO2011007744 A1 WO 2011007744A1 JP 2010061745 W JP2010061745 W JP 2010061745W WO 2011007744 A1 WO2011007744 A1 WO 2011007744A1
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- polycarbonate resin
- carbonate
- resin composition
- mol
- compound represented
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- 0 *c1cc(C2(c3ccccc3-c3c2cccc3)c(cc2*)cc(*)c2O)cc(*)c1O Chemical compound *c1cc(C2(c3ccccc3-c3c2cccc3)c(cc2*)cc(*)c2O)cc(*)c1O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to moldability, strength and low birefringence obtained by blending a polycarbonate resin derived from a specific dihydroxy compound and a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane. It is related with the polycarbonate resin composition which is excellent in.
- Polycarbonate resin composed of 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A) is a CD due to its excellent transparency, heat resistance, low water absorption, chemical resistance, mechanical properties and dimensional stability. Alternatively, it is widely used for optical materials such as DVD substrates, optical films, optical sheets, various lenses or prisms.
- the polycarbonate resin made of bisphenol A has a large birefringence, it has a drawback that it cannot be used in a field requiring low birefringence.
- acrylic resin, amorphous polyolefin, polycarbonate resin having a special structure, or the like is used in the field where low birefringence is required.
- acrylic resins have the disadvantages of high water absorption and poor dimensional stability, or poor chemical resistance
- amorphous polyolefins have poor impact resistance, poor chemical resistance, and are expensive.
- the molded product does not necessarily have a sufficiently low birefringence, and these resins are used in fields where further low birefringence is required. It cannot be used.
- polycarbonate resin having a special structure for example, a co-polymer derived from 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene and tricyclo [5.2.1.0 2,6 ] decanedimethanol.
- a polymerized polycarbonate resin has been proposed (for example, Patent Document 1).
- An injection-molded product made of this resin exhibits excellent low birefringence, but has a drawback of low impact strength.
- a polycarbonate resin having a special structure for example, a copolymer polycarbonate resin derived from 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and a predetermined dihydroxy compound (for example, patent document) 2)
- the polycarbonate resin composition (for example, patent document 3) and its use (for example, patent document 4) contained in are proposed. These polycarbonate resins have lower birefringence but lower strength than polycarbonate resins made of bisphenol A.
- the present invention is to solve the above-mentioned problems, and to provide a transparent polycarbonate resin composition having high strength and low birefringence.
- a polycarbonate resin composition excellent in low birefringence and strength can be obtained.
- the polycarbonate resin composition can be used for various lenses, pickup lenses, prisms, optical sheets, optical films, light guide plates, and the like as well as transparent protective sheets for polarizing plates, and is extremely useful.
- the present invention relates to a polycarbonate resin composition obtained by blending a predetermined polycarbonate resin (A) and a predetermined polycarbonate resin (B) at a predetermined ratio.
- the polycarbonate resin (A) is obtained by carbonate bonding of 95 to 5 mol% of the dihydroxy compound represented by the general formula (1) and 5 to 95 mol% of the dihydroxy compound represented by the general formula (2) with a carbonic acid diester.
- Polycarbonate resin is obtained by carbonate bonding of 95 to 5 mol% of the dihydroxy compound represented by the general formula (1) and 5 to 95 mol% of the dihydroxy compound represented by the general formula (2) with a carbonic acid diester.
- R 1 and R 2 each represent a hydrogen atom or a methyl group.
- Examples of the compound represented by the general formula (1) include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis. (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-2,6-dimethylphenyl) fluorene and the like are included. Of these, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferably used.
- the compound represented by the general formula (2) is specifically tricyclo [5.2.1.02,6] decanedimethanol.
- the dihydroxy compound constituting the polycarbonate resin (A) is a dihydroxy compound represented by the general formula (1) and a dihydroxy compound represented by the general formula (2).
- the ratio of the dihydroxy compound represented by the general formula (1) is 5 to 95 mol%, and the dihydroxy compound represented by the general formula (2) is 95 to 5 mol%. More preferably, the compound represented by the general formula (1) is 10 to 70 mol%, and the compound represented by the general formula (2) is 90 to 30 mol%. More preferably, the compound represented by the general formula (1) is 15 to 60 mol%, and the compound represented by the general formula (2) is 85 to 40 mol%. More preferably, the compound represented by the general formula (1) is 25 to 45 mol%, and the compound represented by the general formula (2) is 75 to 55 mol%.
- the glass transition temperature is lowered and the heat resistance is lowered, which is not preferable. Moreover, since the glass transition temperature will become high when the dihydroxy compound represented by General formula (1) exceeds 95 mol%, the fluidity
- the polycarbonate resin (A) is obtained by polymerizing the dihydroxy compound represented by the general formula (1) and the dihydroxy compound represented by the general formula (2) by a known melt polycondensation method in the presence of a carbonic acid diester and a catalyst. Can do. Details of the manufacturing method will be described later.
- the polycarbonate resin (A) may be any polycarbonate resin including random, block, and alternating copolymer structures.
- the polycarbonate resin (A) contains only units of the dihydroxy compound represented by the general formula (1), the dihydroxy compound represented by the general formula (2), and the carbonic acid diester compound, and is substantially derived from other monomers. Does not include units.
- the polycarbonate resin (B) is obtained by carbonate-bonding a dihydroxy compound represented by the general formula (3), that is, 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A) with a carbonic acid diester or phosgene. Polycarbonate resin.
- the polycarbonate resin (B) is preferably a homopolymer composed of bisphenol A, but is not limited to this, and a small amount of bisphenols other than bisphenol A may be copolymerized as long as the physical properties are not impaired.
- the polycarbonate resin (B) can be obtained by polymerizing a dihydroxy compound represented by the general formula (3) by a melt polycondensation method or a phosgene method (interface method). Details of the manufacturing method will be described later.
- the polycarbonate resin composition of this invention may contain 2 or more types of polycarbonate resin (A) and (B), respectively. In that case, (A) and (B) in the formula (100 ⁇ (A)) / ((A) + (B)) are respectively two or more types of polycarbonate resins (A) and (B). It means the total weight.
- the preferred polystyrene-converted weight average molecular weight (Mw) of the polycarbonate resin (A) used in the resin composition of the present invention is 20,000 to 300,000, more preferably 35,000 to 150,000. If the Mw is smaller than 20,000, the blend resin composition becomes brittle, which is not preferable. When Mw is larger than 300,000, the melt viscosity becomes high and the blending conditions become strict, which is not preferable. Furthermore, the injection molding conditions of the resin composition become strict, and silver is generated in the molded product.
- the preferred polystyrene-converted weight average molecular weight (Mw) of the polycarbonate resin (B) used in the resin composition of the present invention is 15,000 to 250,000, more preferably 20,000 to 110,000. If Mw is less than 15,000, the blended resin composition becomes brittle, which is not preferable. When Mw is larger than 250,000, the melt viscosity becomes high and the blending conditions become strict, which is not preferable. Furthermore, the injection molding conditions of the resin composition become strict and silver is generated in the molded product, which is not preferable.
- the polystyrene-converted weight average molecular weight difference ( ⁇ Mw) between the polycarbonate resins (A) and (B) used in the resin composition of the present invention is preferably 0 to 120,000, more preferably 0 to 80, 000.
- ⁇ Mw exceeds 120,000, the difference in viscosity between (A) and (B) is remarkably increased, so that the compatibility is deteriorated and the transparency of the resin composition is lowered.
- the polystyrene-converted weight average molecular weight (Mw) of the resin composition of the present invention obtained by blending the polycarbonate resins (A) and (B) at a predetermined ratio is preferably 10,000 to 80,000. More preferably, it is 25,000-60,000. The above range is preferable because the moldability is good.
- the glass transition temperature (Tg) of the resin composition of the present invention is 95 to 180 ° C., more preferably 105 to 170 ° C.
- Tg is lower than 95 ° C.
- the operating temperature range becomes narrow, which is not preferable.
- it exceeds 180 ° C. the molding conditions become severe, which is not preferable.
- the polycarbonate resin (A) can be produced by a known melt polycondensation method in which dihydroxy compounds represented by the general formulas (1) and (2) are present in the presence of a carbonic acid diester and a catalyst.
- the carbonic acid diester examples 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 preferably used.
- the carbonic acid diester is preferably used in a ratio of 0.98 to 1.20 mol, more preferably 0.99 to 1.10 mol, relative to a total of 1 mol of the dihydroxy compound.
- Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
- organic acid salts such as alkali metal and / or alkaline earth metal compounds, inorganic salts, oxides, hydroxides, hydrides or alkoxides, quaternary ammonium hydroxides and salts thereof, and amines. Etc. are preferably used, and these compounds can be used alone or in combination.
- alkali metal compound examples include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, carbonate Cesium, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate Cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt of bisphenol A, dipotassium salt, cesium Salts, dilithium salts, the sodium salt of phenol, potassium salt, cesium salt, lithium salt or the like is used.
- alkaline earth metal compound examples 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.
- nitrogen-containing compounds include alkyls, aryls, groups, and the like such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide.
- Secondary ammoniums such as 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, Tiger butylammonium tetraphenylborate, basic or basic salts such as tetraphenyl ammonium tetraphenylborate, or the like is used.
- zinc, tin, zirconium and lead salts are preferably used, and these can be used alone or in combination.
- transesterification catalyst examples 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 a by-product by transesterification under normal pressure or reduced pressure under heating.
- the reaction is generally carried out in a multistage process of two or more stages.
- the first stage reaction is carried out 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.
- the reaction temperature is raised while raising the degree of vacuum of the reaction system to react the dihydroxy compound with the carbonic acid diester.
- the pressure is reduced to 1 mmHg or less at a temperature of 200 to 350 ° C. for 0.3 to 10 hours Perform a condensation 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. A horizontal type or an extruder type equipped with a screw may be used, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer.
- the catalyst is removed or deactivated in order to maintain thermal stability and hydrolysis stability.
- a method of deactivating a catalyst by adding a known acidic substance is preferably performed.
- these substances include esters such as butyl benzoate and dodecyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid, butyl p-toluenesulfonate, and p-toluene.
- Aromatic sulfonic acid esters such as hexyl sulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, phenethyl p-toluenesulfonate, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, phosphorous acid Triphenyl, monophenyl phosphite, diphenyl phosphite, monoethyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, mono-n-butyl phosphite, phosphorous Phosphorous esters such as di-n-hexyl acid, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate P
- 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.
- 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.
- An example of a method for producing the polycarbonate resin (B) according to the present invention will be described.
- An example of the method for producing the polycarbonate resin (B) is a method in which a dihydroxy compound and a carbonic acid diester are melt polycondensed in the presence of a basic compound catalyst. This production method is in accordance with the production method of the polycarbonate resin (A). However, it is preferable not to use a transition metal-based transesterification catalyst for the production of the polycarbonate resin (B).
- Another example of the method for producing the polycarbonate resin (B) is a method of interfacial polymerization in which a dihydroxy compound is reacted with phosgene in the presence of a solvent, a terminal terminator and an acid binder. In this production method, a dihydroxy compound and a terminal terminator are usually dissolved in an aqueous solution of an acid binder and reacted in the presence of an organic solvent.
- alkali metal hydroxides such as pyridine, sodium hydroxide or potassium hydroxide are preferably used.
- a solvent a methylene chloride, chloroform, chlorobenzene, xylene etc. are used suitably, for example.
- a tertiary amine such as triethylamine or a quaternary ammonium salt such as tetra-n-butylammonium bromide is used as a catalyst.
- terminal terminator used for adjusting the degree of polymerization
- monofunctional hydroxy compounds such as phenol, p-tert-butylphenol, p-cumylphenol, and long-chain alkyl-substituted phenol are used.
- an antioxidant such as sodium sulfite or sodium hydrosulfite may be added.
- the reaction is usually carried out in the range of 0 to 150 ° C, preferably 5 to 40 ° C. While the reaction time depends on the reaction temperature, it is generally 0.5 min-10 hr, preferably 1 min-2 hr. Moreover, it is preferable to maintain the pH of the reaction system at 10 or more during the reaction.
- the production method of the polycarbonate resin composition of the present invention is not particularly limited, for example, [1] A method of mixing each of the polycarbonate resins (A) and (B) and kneading them with a kneader, [2] A method of adding and kneading solid (B) to molten (A), [3] A method of adding and kneading solid (A) to molten (B), [4] A method of mixing and kneading the molten resins (A) and (B), It can be produced by any of the methods.
- the kneading may be either a continuous type or a batch type.
- the kneader is preferably an extruder if it is a continuous type, and is preferably used for a lab plast mill or a kneader if it is a batch type.
- the catalyst deactivator and the resin to be blended may be kneaded at the same time, or the catalyst deactivator may be kneaded after blending. However, in this case, it is necessary to keep it within a range where chemical resistance is not impaired by randomization by transesterification.
- the polycarbonate resin composition of the present invention there is a method in which the polycarbonate resins (A) and (B) are dissolved in a solvent, poured into a mold, and then the solvent is evaporated.
- the solvent methylene chloride, chloroform, cresol and the like are used.
- the additive can be dissolved and added at the same time.
- the polycarbonate resin composition of the present invention may contain an antioxidant, a release agent, an ultraviolet absorber, a fluidity modifier, a reinforcing agent, a crystal nucleating agent, a dye, an antistatic agent, an antibacterial agent, or the like as necessary. It may be added. These additives may be added in advance to each or one of the polycarbonate resins (A) and (B) before kneading, or they may be added and kneaded at the same time during blend kneading. It may be kneaded after mixing. However, it is preferable that the polycarbonate resin composition of the present invention does not substantially contain polycarbonates other than the polycarbonate resins (A) and (B).
- the polycarbonate resin composition of the present invention has a low birefringence, and can be used for the production of various lenses, pickup lenses, prisms, optical sheets, optical films, light guide plates, etc., including a transparent protective sheet for polarizing plates. Useful. These optical parts are usually required to have a birefringence of 700 nm or less, and a bending strength of 60 MPa or more from the viewpoint of workability and durability.
- the polycarbonate resin composition of the present invention satisfies these characteristics.
- Example 1 9.9 kg of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (21.5 mol (33.6 mol%)), 8.32 g of tricyclo [5.2.1.0 2.6 ] decanedimethanol (42.4 mol (66.4 mol%)), diphenyl carbonate 13.81 g (64.5 mol), and sodium hydrogen carbonate 5 ⁇ 10 ⁇ 5 g (6 ⁇ 10 ⁇ 7 mol) were stirred and distilled apparatus. The reactor was placed in a 50 liter reactor, and heated to 215 ° C. over 1 hour under a nitrogen atmosphere of 760 Torr and stirred.
- the degree of vacuum was adjusted to 150 Torr over 15 minutes, and the transesterification reaction was carried out by maintaining for 20 minutes under the conditions of 215 ° C. and 150 Torr. Further, the temperature was raised to 240 ° C. at a rate of 37.5 ° C./hr, and maintained at 240 ° C. and 150 Torr for 10 minutes. Thereafter, the pressure was adjusted to 120 Torr over 10 minutes and maintained at 240 ° C. and 120 Torr for 70 minutes. Thereafter, the pressure was adjusted to 100 Torr over 10 minutes and held at 240 ° C. and 100 Torr for 10 minutes. Further, the polymerization reaction was carried out under stirring at 25 ° C.
- Example 2 The same operation as in Example 1 was performed except that 6 kg of the polycarbonate resin pellet (A) in Example 1 and 4 kg of the polycarbonate resin “Iupilon S-3000” made of bisphenol A were kneaded. . Mw was 55600. When the bending strength and birefringence were measured, the birefringence was as low as 440 nm and the bending strength was as strong as 83 MPa.
- Example 3 The same operation as in Example 1 was performed, except that 5 kg of the polycarbonate resin pellet (A) and 5 kg of the polycarbonate resin “Iupilon S-3000” made of bisphenol A were kneaded. Mw was 54000. When the bending strength and birefringence were measured, the birefringence was as low as 670 nm and the bending strength was as strong as 86 MPa.
- Example 4 9,9-bis (4-hydroxy-3-methylphenyl) fluorene 6.05 kg (16.0 mol (25.0 mol%)), tricyclo [5.2.1.0 2.6 ] decanedimethanol 9.41 kg (47.93 mol (75.0 mol%))
- Example 1 Polycarbonate obtained by polymerization in Example 1, adding diethyl phosphite to 10 times mol of sodium hydrogen carbonate in the resin and adding 300 ppm of glycerin monostearate to the resin and kneading at 260 ° C. with an extruder. The bending strength and birefringence were measured. The birefringence was as low as 1 nm, but the bending strength was as low as 11 Mpa.
- Example 2 In Example 1, the same operation as in Example 1 was performed, except that 9 kg of the polycarbonate resin pellet (A) and 1 kg of the polycarbonate resin “Iupilon S-3000” pellet made of bisphenol A were kneaded. Mw was 60600. When the bending strength and birefringence were measured, the birefringence was as low as 15 nm, but the bending strength was as low as 15 MPa.
- Example 3 The same operation as in Example 1 was performed except that 6 kg of the polycarbonate resin pellet (A) and 4 kg of the polycarbonate resin “Iupilon S-3000” pellet made of bisphenol A were kneaded in Example 1. Mw was 52000. When the bending strength and birefringence were measured, the bending strength was as strong as 90 MPa, but the birefringence was as large as 1010 nm.
- the molar ratio of the dihydroxy compound of the formula (1) to the carbonic acid diester compound of the formula (2) in the polycarbonate resin A is 15-60 mol% for the former and 85-40 mol for the latter. % was found to be preferred.
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Abstract
Description
ポリカーボネート樹脂(A)は、一般式(1)で表されるジヒドロキシ化合物95~5モル%、及び一般式(2)で表されるジヒドロキシ化合物5~95モル%を炭酸ジエステルによりカーボネート結合させてなるポリカーボネート樹脂である。
なお、本発明のポリカーボネート樹脂組成物は、ポリカーボネート樹脂(A)及び(B)をそれぞれ2種類以上含有していてもよい。その場合は、式(100×(A))/((A)+(B))中の(A)及び(B)はそれぞれ、2種類以上のポリカーボネート樹脂(A)及び(B)のそれぞれの合計の重量を意味する。
ポリカーボネート樹脂(A)は、一般式(1)及び(2)で表されるジヒドロキシ化合物を、炭酸ジエステル及び触媒の存在下、公知の溶融重縮合法により製造することができる。
ポリカーボネート樹脂(B)の製造方法の一例は、ジヒドロキシ化合物と炭酸ジエステルとを塩基性化合物触媒の存在下、溶融重縮合させる方法である。この製造法は、ポリカーボネート樹脂(A)の製造方法に準じるものであるが、但し、ポリカーボネート樹脂(B)の製造には、遷移金属系のエステル交換触媒を用いないのが好ましい。
ポリカーボネート樹脂(B)の製造方法の他の例は、ジヒドロキシ化合物を溶媒および末端停止剤および酸結合剤の存在下、ホスゲンと反応させる界面重合させる方法である。この製造方法では、通常、酸結合剤の水溶液にジヒドロキシ化合物および末端停止剤を溶解し、有機溶媒の存在下に反応させる。
〔1〕ポリカーボネート樹脂(A)と(B)のそれぞれの固体を混合し、混練機により混練する方法、
〔2〕溶融状態の(A)に、固体の(B)を添加して混練する方法、
〔3〕溶融状態の(B)に、固体の(A)を添加して混練する方法、
〔4〕溶融状態の(A)と(B)の樹脂を混合して混練する方法、
のいずれの方法によって製造することもできる。混練は、連続式、バッチ式のどちらでもよい。混練機は、連続式ならば押出し機が好適であり、バッチ式ならばラボプラストミル、ニーダー好適に使用される。なお、溶融重縮合法によって製造したポリカーボネート樹脂を用いる場合には、混練時のエステル交換反応を避ける見地から、触媒失活後に混練を行うことが望ましい。しかし、触媒失活剤とブレンド相手の樹脂とを同時に練り込んでもブレンド後に触媒失活剤を練り込んでも構わない。ただし、この場合には、エステル交換反応によるランダム化によって耐薬品性が損なわれない範囲に止める必要がある。
但し、本発明のポリカーボネート樹脂組成物は、ポリカーボネート樹脂(A)及び(B)以外のポリカーボネート類を実質的に含有しないのが好ましい。
1)ポリスチレン換算重量平均分子量(Mw):GPCを用い、クロロホルムを展開溶媒として、既知の分子量(分子量分布=1)の標準ポリスチレンを用いて検量線を作成した。この検量線に基づいて、GPCのリテンションタイムから算出した。
2)ガラス転移温度(Tg):示差熱走査熱量分析計セイコー電子工業(株)製のSSC-5200(DSC)により10℃/minで測定した。
3)曲げ弾性率:ポリカーボネート樹脂ペレットを120℃24時間乾燥した後、射出成形機住友重機製SG-150によりシリンダー温度255℃で射出成形した試験片を用い、ASTM-D0790に従い測定した。
4)複屈折率:複屈折(リターデーション)は、以下の方法で測定した。
4-1)キャストフィルムの作製
それぞれの実施例で得られた樹脂をジクロロメタンに5重量%濃度で溶解し、水平を確認したキャスト板に流延した。キャスト板に適宜覆いをすることで蒸発量を調整しながら、ジクロロメタンを揮発させ、厚さ100μmの透明な樹脂フィルムを得た。
4-2)フィルムの延伸
得られたフィルムを5cm×5cmに切断し、ガラス転移温度(Tg)より10℃高い温度、延伸速度15mm/分で、延伸倍率1.5倍まで引き伸ばした。
4-3)複屈折の測定
得られた延伸フィルムの複屈折(リターデーション)を(株)溝尻光学工業所製のエリプソメーターを用いて波長633nmについて測定した。
9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン 8.14kg(21.5モル(33.6モル%))、トリシクロ[5.2.1.02.6]デカンジメタノール 8.32g(42.4モル(66.4モル%))、ジフェニルカーボネート 13.81g(64.5モル)、及び炭酸水素ナトリウム 5×10-5g(6×10-7モル)を攪拌機及び留出装置付きの50リットル反応器に入れ、窒素雰囲気760Torrの下、1時間かけて215℃に加熱し撹拌した。
その後、15分かけて減圧度を150Torrに調整し、215℃、150Torrの条件下で20分間保持しエステル交換反応を行った。さらに37.5℃/hrの速度で240℃まで昇温し、240℃、150Torrで10分間保持した。その後、10分かけて120Torrに調整し、240℃、120Torrで70分間保持した。その後、10分かけて100Torrに調整し、240℃、100Torrで10分間保持した。更に40分かけて1Torr以下とし、240℃、1Torr以下の条件下で25分間撹拌下重合反応を行った。反応終了後、反応器内に窒素を吹き込み加圧にし、生成したポリカーボネート樹脂をペレタイズしながら抜き出した。得られたポリカーボネート樹脂のMwは62300、Tgは142℃であった。
また、Mwは58940であった。曲げ強度と複屈折を測定したところ、複屈折は250nmと低く、曲げ強度も79MPaと強かった。
実施例1において、ポリカーボネート樹脂ペレット(A)6kgと、ビスフェノールAからなるポリカーボネート樹脂“ユ-ピロンS-3000”のペレット4kgとを用いて混練した以外は、実施例1と同様の操作を行った。Mwは55600であった。曲げ強度と複屈折を測定したところ、複屈折は440nmと低く、曲げ強度も83MPaと強かった。
実施例1において、ポリカーボネート樹脂ペレット(A)5kgとビスフェノールAからなるポリカーボネート樹脂“ユ-ピロンS-3000”のペレット5kgとを用いて混練した以外は、実施例1と同様の操作を行った。Mwは54000であった。曲げ強度と複屈折を測定したところ、複屈折は670nmと低く、曲げ強度も86MPaと強かった。
9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン 6.05kg(16.0モル(25.0モル%))、トリシクロ[5.2.1.02.6]デカンジメタノール 9.41kg(47.93モル(75.0モル%))ジフェニルカーボネート 13.81g(64.5モル)、及び炭酸水素ナトリウム 5×10-5g(6×10-7モル)を使用する以外は実施例1同様に重合を行い、ポリカーボネート樹脂ペレットを得た。得られたポリカーボネート樹脂のMwは65300、Tgは116℃であった。
また、Mwは52000であった。曲げ強度と複屈折を測定したところ、複屈折は680nmと低く、曲げ強度も78MPaと強かった。
実施例1において重合し、亜リン酸ジエチルを樹脂中の炭酸水素ナトリウムの10倍モル、グリセリンモノステアレートを樹脂に対して300ppmを添加して押出機により260℃で混練して得られたポリカーボネートの曲げ強度と複屈折を測定した。複屈折は1nmと非常に低かったが、曲げ強度が11Mpaと強度が低かった。
実施例1において、ポリカーボネート樹脂ペレット(A)9kgとビスフェノールAからなるポリカーボネート樹脂“ユ-ピロンS-3000”ペレット1kgとを用いて混練した以外は、実施例1と同様の操作を行った。Mwは60600であった。曲げ強度と複屈折を測定したところ、複屈折は15nmと非常に低かったが、曲げ強度が15MPaと強度が低かった。
実施例1において、ポリカーボネート樹脂ペレット(A)6kgとビスフェノールAからなるポリカーボネート樹脂“ユ-ピロンS-3000”ペレット4kgとを用いて混練した以外は、実施例1と同様の操作を行った。Mwは52000であった。曲げ強度と複屈折を測定したところ、曲げ強度が90MPaと強度が強かったが、複屈折は1010nmと大きかった。
9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン 12.10kg(32.0モル(50.0モル%))、トリシクロ[5.2.1.02.6]デカンジメタノール 6.28kg(32.0モル(50.0モル%))ジフェニルカーボネート 13.81g(64.5モル)、及び炭酸水素ナトリウム 5×10-5g(6×10-7モル)を使用する以外は実施例1同様に重合を行い、ポリカーボネート樹脂ペレットを得た。得られたポリカーボネート樹脂のMwは61300、Tgは133℃であった。
また、Mwは53000であった。曲げ強度と複屈折を測定したところ、複屈折は実施例1~4と同程度に低かった(680nm)が、曲げ強度が実施例1~4と比較して劣っていた(10MPa)。即ち、曲げ強度の観点では、ポリカーボネート樹脂A中の、式(1)のジヒドロキシ化合物と式(2)の炭酸ジエステル化合物とのモル比率は、前者が15~60モル%、後者が85~40モル%であるのが好ましいことがわかった。
Claims (9)
- 一般式(1)中、R1が水素原子である請求項1に記載のポリカーボネート樹脂組成物。
- ポリカーボネート樹脂(A)及び(B)を、(100×(A))/((A)+(B))が50~80%の重量比率でブレンドして得られる請求項1又は2に記載のポリカーボネート樹脂組成物。
- ポリカーボネート樹脂(A)中、一般式(1)で表される化合物のモル比率が15~60モル%、及び一般式(2)で表される化合物のモル比率が85~40モル%である請求項1~3のいずれか1項に記載のポリカーボネート樹脂組成物。
- 炭酸ジエステルが、ジフェニルカーボネート、ジトリールカーボネート、ビス(クロロフェニル)カーボネート、m-クレジルカーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、又はジシクロヘキシルカーボネートである請求項1~4のいずれか1項に記載のポリカーボネート樹脂組成物。
- 炭酸ジエステルが、ジフェニルカーボネートである請求項1~4のいずれか1項に記載のポリカーボネート樹脂組成物。
- ポリカーボネート樹脂(A)のポリスチレン換算平均分子量(Mw)が20,000~300,000であり、ポリカーボネート樹脂(B)のポリスチレン換算平均分子量(Mw)が15,000~250,000である請求項1~6のいずれか1項に記載のポリカーボネート樹脂組成物。
- ポリカーボネート樹脂(A)とポリカーボネート樹脂(B)のポリスチレン換算平均分子量(Mw)の差ΔMwが、0~120,000である請求項1~7のいずれか1項に記載のポリカーボネート樹脂組成物。
- ガラス転移点が95~180℃である請求項1~8のいずれか1項に記載のカーボネート樹脂組成物。
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JP2016216690A (ja) * | 2015-05-26 | 2016-12-22 | 帝人株式会社 | ポリカーボネート樹脂組成物および光学フィルム |
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KR101741280B1 (ko) | 2017-05-29 |
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US9163116B2 (en) | 2015-10-20 |
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