WO2011071164A1 - ポリカーボネート樹脂組成物及び成形品 - Google Patents
ポリカーボネート樹脂組成物及び成形品 Download PDFInfo
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- WO2011071164A1 WO2011071164A1 PCT/JP2010/072284 JP2010072284W WO2011071164A1 WO 2011071164 A1 WO2011071164 A1 WO 2011071164A1 JP 2010072284 W JP2010072284 W JP 2010072284W WO 2011071164 A1 WO2011071164 A1 WO 2011071164A1
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- polycarbonate resin
- weight
- resin composition
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- dihydroxy compound
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- 0 C*c1ccccc1 Chemical compound C*c1ccccc1 0.000 description 3
- ZWLZHIAKQAANTN-RNFRBKRXSA-N C=[O](CC1)[C@H]2[C@@H]1OCC2 Chemical compound C=[O](CC1)[C@H]2[C@@H]1OCC2 ZWLZHIAKQAANTN-RNFRBKRXSA-N 0.000 description 1
- UBVWYDZEQJSKOY-YSLANXFLSA-N OC1[C@H]2OCC[C@H]2OC1 Chemical compound OC1[C@H]2OCC[C@H]2OC1 UBVWYDZEQJSKOY-YSLANXFLSA-N 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
- C08G64/02—Aliphatic polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a polycarbonate resin composition excellent in weather resistance, hue, transparency, heat resistance, thermal stability, moldability, and mechanical strength, and a molded product thereof.
- Polycarbonate resins are generally composed of bisphenols as monomer components, taking advantage of transparency, heat resistance, mechanical strength, etc., and electrical / electronic parts, automotive parts, medical parts, building materials, films, sheets, bottles It is widely used as so-called engineering plastics in the fields of optical recording media and lenses.
- conventional polycarbonate resins are limited in use outdoors or in the vicinity of lighting devices, because their hue, transparency, and mechanical strength deteriorate when used in places exposed to ultraviolet rays or visible light for a long time. .
- Non-Patent Document 1 a method of adding a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, or a benzoxazine ultraviolet absorber to a polycarbonate resin is widely known (for example, Non-Patent Document 1).
- HALS hindered amine
- a cyclic dihydroxy compound monomer unit having an ether bond in the molecule such as a compound, an alicyclic dihydroxy compound, or isosorbide
- light resistance is improved in principle.
- polycarbonate resins using isosorbide as a monomer obtained from biomass resources are excellent in heat resistance and mechanical strength, so that many studies have been made in recent years (for example, Patent Documents 1 to 7). .
- polycarbonate resin compositions that have an ether bond in the molecule, such as isosorbide, isomannide, isoitide, etc. that do not have a benzene ring structure in the molecular skeleton, benzotriazole, benzophenone, It is widely known to add a cyanoacrylate system (Patent Document 8).
- Non-Patent Document 1 when an ultraviolet absorber as described in Non-Patent Document 1 is added, although the hue after ultraviolet irradiation is improved, the hue, heat resistance, and transparency of the resin are deteriorated in the first place. There were problems such as volatilization during molding and contamination of the mold.
- a polycarbonate resin is obtained.
- a polycarbonate resin obtained using a monomer having no phenolic hydroxyl group as described above is inferior in thermal stability to a polycarbonate resin obtained using a monomer having a phenolic hydroxyl group such as bisphenol A.
- coloring occurs during polymerization or molding that is exposed to high temperatures, and as a result, ultraviolet light and visible light are absorbed, resulting in deterioration of light resistance.
- the object of the present invention is to provide a polycarbonate resin composition excellent in weather resistance, hue, transparency, heat resistance, thermal stability, moldability, and mechanical strength, and a molded product thereof, which solves the above-mentioned conventional problems. There is to do.
- the present inventor has obtained structural units and carbon numbers derived from the dihydroxy compound (a) having a site represented by the following general formula (1) in a part of the structure.
- the present inventors have found that the resin composition has not only excellent light resistance but also excellent hue, transparency, heat resistance, thermal stability, moldability, and mechanical strength, and has reached the present invention.
- R 1 to R 8 in the general formula (2) each independently represent a hydrogen atom or a substituent.
- Y represents a single bond or a divalent group.
- the gist of the present invention resides in the following [1] to [8].
- [1] Derived from a structural unit derived from a dihydroxy compound (a) having a site represented by the following general formula (1) as part of the structure and a dihydroxy compound (b) of an alicyclic hydrocarbon having 11 or less carbon atoms
- R 1 to R 8 in the general formula (2) each independently represent a hydrogen atom or a substituent.
- Y represents a single bond or a divalent group.
- Polycarbonate resin composition [3] The polycarbonate resin composition according to [1] or [2], wherein the dihydroxy compound (a) is a dihydroxy compound represented by the following general formula (3).
- a polycarbonate resin composition excellent in weather resistance, hue, transparency, heat resistance, thermal stability, moldability, and mechanical strength and a molded product thereof can be provided.
- the polycarbonate resin (A) used in the present invention comprises a dihydroxy compound (a) having a part represented by the following general formula (1) in a part of the structure and a dihydroxy compound (b) having an alicyclic hydrocarbon having 11 or less carbon atoms. ) And a carbonic acid diester as raw materials and obtained by polycondensation by a transesterification reaction. That is, the polycarbonate resin (A) used in the present invention is composed of a structural unit derived from the dihydroxy compound (a) having a portion represented by the following general formula (1) in a part of the structure and an alicyclic group having 11 or less carbon atoms. And a structural unit derived from a hydrocarbon dihydroxy compound (b).
- the dihydroxy compound used in the present invention includes a dihydroxy compound (a) having a portion represented by the general formula (1) in a part of the structure, and an alicyclic hydrocarbon dihydroxy compound (b) having 11 or less carbon atoms, If it contains, it will not specifically limit.
- dihydroxy compound (a) having a site represented by the general formula (1) in a part of the structure include oxyalkylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol, -Bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) ) -3-Isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert- Butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylsulfate Nyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylpheny
- anhydrosugar alcohol represented by the dihydroxy compound represented by the following formula (3) and a compound having a cyclic ether structure represented by the following formula (4) are preferable.
- Anhydrosugar alcohols typified by dihydroxy compounds represented by formula (4) are preferred.
- dihydroxy compound represented by the general formula (3) examples include isosorbide, isomannide, and isoidet, which have a stereoisomeric relationship, and these may be used alone or in combination of two or more. It may be used.
- dihydroxy compounds it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of the light resistance of the polycarbonate resin (A).
- Isosorbide obtained by dehydrating condensation of sorbitol produced from starch is most preferable from the viewpoints of availability and production, light resistance, optical properties, moldability, heat resistance, and carbon neutral.
- the alicyclic hydrocarbon dihydroxy compound (b) having 11 or less carbon atoms is a compound having a cyclic structure hydrocarbon skeleton and two hydroxy groups, and the hydroxy group may be directly bonded to the cyclic structure. , And may be bonded to the cyclic structure via a substituent.
- the cyclic structure may be monocyclic or polycyclic.
- hexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, 4-cyclohexene-1,2- Cyclohexene diols such as diol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanedimethanol such as 1,4-cyclohexanedimethanol, 4-cyclohexene-1,2-diol
- cyclohexene dimethanol, 2,3-norbornane dimethanol, norbornane dimethanol such as 2,5-norbornane dimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2, 2-Adamantane All, and the like.
- a dihydroxy compound containing a dihydroxy compound (a) having a site represented by the general formula (1) and a dihydroxy compound (b) of an alicyclic hydrocarbon having 11 or less carbon atoms in a part of the structure It is also possible to obtain effects such as improvement in flexibility of polycarbonate resin (A), improvement in heat resistance, improvement in moldability, and the number of carbon atoms of dihydroxy compound (b) of alicyclic hydrocarbon is a predetermined value. When it is below, it becomes possible to obtain a polycarbonate resin composition excellent in weather resistance and hue.
- the carbon number of the alicyclic hydrocarbon dihydroxy compound (b) is usually 11 or less, preferably 10 or less, more preferably 8 or less.
- the dihydroxy compound used in the present invention may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, heat stabilizer, etc. Since the dihydroxy compound used in the invention is easily altered, it is preferable to include a basic stabilizer.
- Basic stabilizers include group 1 or group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphites in the long-period periodic table (Nomenclature of Organic Chemistry IUPAC Recommendations 2005).
- the basic stabilizer when used as a raw material for producing polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate and quality. In order to deteriorate the initial hue and consequently deteriorate the light resistance of the molded product, it is preferable to remove the basic stabilizer by ion exchange resin or distillation before using it as a raw material for producing the polycarbonate resin.
- the dihydroxy compound used in the present invention has a cyclic ether structure such as isosorbide, it is easily oxidized by oxygen. Therefore, during storage and production, in order to prevent decomposition by oxygen, water should not be mixed, It is important to use an oxygen scavenger or handle under a nitrogen atmosphere.
- isosorbide is oxidized, decomposition products such as formic acid may be generated.
- the resulting polycarbonate resin may be colored, and not only the physical properties may be significantly degraded, but also the polymerization reaction may be affected. In some cases, a high molecular weight polymer cannot be obtained.
- distillation purification In order to obtain the dihydroxy compound used in the present invention which does not contain the above oxidative decomposition product, and in order to remove the above basic stabilizer, it is preferable to perform distillation purification.
- the distillation in this case may be simple distillation or continuous distillation, and is not particularly limited.
- distillation conditions it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen.
- inert gas atmosphere such as argon or nitrogen.
- it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of °C or less.
- the dihydroxy compound used in the present invention is adjusted to a formic acid content in the dihydroxy compound used in the present invention of 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less.
- a dihydroxy compound containing is used as a raw material for producing a polycarbonate resin, it is possible to produce a polycarbonate resin (A) excellent in hue and thermal stability without impairing polymerization reactivity.
- the formic acid content is measured by ion chromatography.
- the polycarbonate resin (A) used in the present invention can be obtained by polycondensation by a transesterification reaction using the above-mentioned dihydroxy compound containing the dihydroxy compound used in the present invention and a carbonic acid diester as raw materials.
- a carbonic acid diester used what is normally represented by following General formula (6) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.
- a 1 and A 2 are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group.
- Examples of the carbonic acid diester represented by the general formula (6) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.
- Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting polycarbonate resin. It is preferable to use what was done.
- the polycarbonate resin (A) used in the present invention produces a polycarbonate resin by transesterifying the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester represented by the general formula (6) as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.
- the transesterification catalyst (hereinafter, sometimes simply referred to as “catalyst” or “polymerization catalyst”) that can be used in the production of the polycarbonate resin (A) used in the present invention is, in particular, a light transmittance at a wavelength of 350 nm or a yellow index. Can affect the value.
- the catalyst used as long as the light resistance, transparency, hue, heat resistance, thermal stability, and mechanical strength of the manufactured polycarbonate resin (A) can satisfy the light resistance,
- a metal compound, a basic boron compound, a basic phosphorus compound, or a basic ammonium of Group 1 or 2 (hereinafter also simply referred to as “Group 1” or “Group 2”) in the long-period periodic table
- Examples thereof include basic compounds such as compounds and amine compounds.
- at least one of a Group 1 metal compound and a Group 2 metal compound is used.
- a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.
- the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.
- Group 1 metal compound examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride , Sodium borohydride, potassium borohydride, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, 2 sodium hydrogen phosphate , 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium pheny
- Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, Examples include strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. From the viewpoint of the hue of the polycarbonate resin obtained, a magnesium compound and / or a calcium compound is more preferable, and a calcium compound is most preferable.
- Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl.
- Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.
- Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphonium salt, and the like.
- Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.
- amine compounds include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.
- the amount of the polymerization catalyst used is preferably 0.1 ⁇ mol to 300 ⁇ mol, more preferably 0.5 ⁇ mol to 100 ⁇ mol per 1 mol of all dihydroxy compounds used in the polymerization. Among them, lithium and two groups in the long-period periodic table are used.
- the metal amount is preferably 0.1 ⁇ mol or more per 1 mol of the total dihydroxy compound. More preferably 0.5 ⁇ mol or more, particularly preferably 0.7 ⁇ mol or more.
- the upper limit is preferably 20 ⁇ mol, more preferably 10 ⁇ mol, particularly preferably 3 ⁇ mol, most preferably 1.5 ⁇ mol, and most preferably 1.0 ⁇ mol.
- the polycarbonate resin (A) used in the present invention is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester represented by the general formula (6), phenol and substituted phenol are used.
- By-product and remaining in the polycarbonate resin (A) are inevitable, but not only phenol and substituted phenol also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance, May cause odor during molding.
- the polycarbonate resin (A) contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction.
- the content of this aromatic monohydroxy compound is preferably 700 ppm by weight or less, more preferably using a horizontal reactor excellent in devolatilization performance or an extruder with a vacuum vent. It is preferably 500 ppm by weight or less, particularly 300 ppm by weight or less. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight or more.
- aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.
- Group 1 metals especially sodium, potassium, and cesium, especially lithium, sodium, potassium, and cesium, may have an adverse effect on the hue when contained in the polycarbonate resin (A) in large quantities.
- the total amount of these in the polycarbonate resin (A) is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less as the amount of metal, because it may be mixed not only from the catalyst to be used, but also from raw materials and reactors. More preferably, it is 0.7 ppm by weight or less.
- the amount of metal in the polycarbonate resin (A) should be measured using a method such as atomic emission, atomic absorption, Inductive Coupled Plasma (ICP) after recovering the metal in the polycarbonate resin by a method such as wet ashing. I can do it.
- a method such as atomic emission, atomic absorption, Inductive Coupled Plasma (ICP) after recovering the metal in the polycarbonate resin by a method such as wet ashing. I can do it.
- the polycarbonate resin (A) used in the present invention is obtained by polycondensation of the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester of the general formula (6) by a transesterification reaction.
- the compound and the carbonic acid diester are preferably mixed uniformly before the transesterification reaction.
- the mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable.
- the lower limit of the mixing temperature is in the above range, the dissolution rate and solubility are good, and problems such as solidification are unlikely to occur.
- the upper limit of the mixing temperature is within the above range, the dihydroxy compound is unlikely to be thermally deteriorated, resulting in a good hue of the polycarbonate resin and does not adversely affect light resistance.
- the operation of mixing the dihydroxy compound containing the dihydroxy compound used in the present invention, which is the raw material of the polycarbonate resin (A) used in the present invention, and the carbonic acid diester represented by the general formula (6) is an oxygen concentration of 10 vol% or less, Is preferably carried out in an atmosphere of 0.0001 vol% to 10 vol%, especially 0.0001 vol% to 5 vol%, particularly 0.0001 vol% to 1 vol%, from the viewpoint of preventing hue deterioration.
- the carbonic acid diester represented by the general formula (6) is 0.90 to less than the dihydroxy compound including the dihydroxy compound used in the present invention used in the reaction.
- the molar ratio is preferably 1.20, and more preferably 0.95 to 1.10. If this molar ratio is at least the above lower limit, the terminal hydroxyl group of the produced polycarbonate resin does not increase, so that the thermal stability of the polymer can be obtained, coloring during molding, the rate of transesterification reaction can be reduced, It is difficult to cause a problem that a high molecular weight product cannot be obtained.
- the molar ratio is not more than the above upper limit, there is no fear that the rate of transesterification will be reduced or it will be difficult to produce a polycarbonate resin (A) having a desired molecular weight.
- the decrease in the transesterification reaction rate may increase the heat history during the polymerization reaction, and may deteriorate the hue and light resistance of the resulting polycarbonate resin.
- the amount of residual carbonic acid diester in the obtained polycarbonate resin (A) is increased. They increase, and these may absorb the ultraviolet rays and deteriorate the light resistance of the polycarbonate resin, which is not preferable.
- the concentration of the carbonic acid diester remaining in the polycarbonate resin (A) used in the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. .
- the polycarbonate resin (A) may contain unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight or more.
- the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst.
- the type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.
- the temperature of the refrigerant introduced into the reflux cooler can be appropriately selected according to the monomer used.
- the temperature of the refrigerant introduced into the reflux cooler is 45 ° C. to 180 ° C. at the inlet of the reflux cooler.
- it is 80 ° C to 150 ° C, and particularly preferably 100 ° C to 130 ° C. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced.
- the refrigerant hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.
- the polycarbonate resin (A) used in the present invention is preferably produced by polymerizing in a plurality of stages using a plurality of reactors using a catalyst.
- the reason for carrying out the polymerization in a plurality of reactors is a polymerization reaction.
- the initial stage since there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate.
- the equilibrium is shifted to the polymerization side. Therefore, it is important to sufficiently distill off the monohydroxy compound produced as a by-product.
- the number of reactors used in the method of the present invention may be at least two or more. However, from the viewpoint of production efficiency, three or more, preferably 3 to 5, and particularly preferably 4 reactors are used. One. In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.
- the polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be added directly to the polymerization tank. From the viewpoint of supply stability and polymerization control, the polymerization catalyst is supplied to the polymerization tank.
- a catalyst supply line is installed in the middle of the raw material line before being fed, and preferably supplied as an aqueous solution. If the temperature of the polymerization reaction is too low, the productivity is lowered and the thermal history of the product is increased. If it is too high, not only the monomer is volatilized, but also the decomposition and coloring of the polycarbonate resin may be promoted.
- the reaction in the first stage is carried out at 140 ° C. to 270 ° C., preferably 180 ° C. to 240 ° C., more preferably 200 ° C. to 230 ° C., and 110 kPa—
- the generated monohydroxy compound is removed from the reaction system at a pressure of 1 kPa, preferably 70 kPa to 5 kPa, more preferably 30 kPa to 10 kPa (absolute pressure) for 0.1 hour to 10 hours, preferably 0.5 hour to 3 hours. Carried out while distilling.
- the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system.
- the maximum internal temperature in all reaction stages is less than 250 ° C., particularly from 225 ° C. It is preferable that it is 245 degreeC.
- it is necessary to use a horizontal reactor with excellent plug flow and interface renewability at the final stage of polymerization. preferable.
- the monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.
- the polycarbonate resin (A) used in the present invention is usually cooled and solidified after polycondensation as described above, and pelletized with a rotary cutter or the like.
- the method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, or from the final polymerization reactor in a molten state, uniaxial or biaxial extrusion.
- the resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again
- a method may be mentioned in which resin is supplied to a biaxial extruder, melt-extruded, cooled and solidified, and pelletized.
- the residual monomer under reduced pressure devolatilization and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded.
- the melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin (A), but is usually 150 ° C. to 300 ° C., preferably 200 ° C. to 270 ° C., more preferably 230 ° C. to 260 ° C. is there.
- melt kneading temperature is lower than 150 ° C.
- melt viscosity of the polycarbonate resin (A) is high, the load on the extruder is increased, and the productivity is lowered.
- temperature is higher than 300 ° C., the thermal deterioration of the polycarbonate becomes severe, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.
- the filter installation position is preferably on the downstream side of the extruder, and the foreign matter removal size (opening) of the filter is preferably 100 ⁇ m or less as the filtration accuracy for 99% removal. In particular, in the case of disagreeing with the entry of minute foreign matters for film use etc., it is preferably 40 ⁇ m or less, more preferably 10 ⁇ m or less.
- Extrusion of the polycarbonate resin (A) used in the present invention is preferably a clean room having a higher degree of cleanliness than Class 7 as defined in JIS B 9920 (2002), more preferably a clean room in order to prevent foreign matter from being mixed after extrusion. It is desirable to implement in. Moreover, when cooling the extruded polycarbonate resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air.
- the opening of the filter to be used is preferably 10 ⁇ m to 0.45 ⁇ m as 99% removal filtration accuracy.
- the molecular weight of the polycarbonate resin (A) used in the present invention thus obtained can be represented by a reduced viscosity, and the reduced viscosity is usually 0.30 dL / g or more, preferably 0.35 dL / g or more.
- the upper limit of the reduced viscosity is more preferably 1.20 dL / g or less and 1.00 dL / g or less, and still more preferably 0.80 dL / g or less.
- the reduced viscosity of the polycarbonate resin (A) is not less than the above lower limit, the mechanical strength of the molded product can be sufficiently obtained, and if it is not more than the above upper limit, the fluidity at the time of molding does not decrease, and productivity and molding Improves.
- the reduced viscosity is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ⁇ 0.1 ° C., using methylene chloride as a solvent, precisely preparing a polycarbonate concentration of 0.6 g / dL.
- the lower limit of the concentration of the terminal group represented by the following general formula (7) in the polycarbonate resin (A) used in the present invention is usually 20 ⁇ eq / g or more, preferably 40 ⁇ eq / g or more, particularly preferably 50 ⁇ eq / g.
- the upper limit is usually 160 ⁇ eq / g or less, preferably 140 ⁇ eq / g or less, particularly preferably 100 ⁇ eq / g or less.
- the concentration of the end group represented by the following general formula (7) is too high, even if the hue at the time of polymerization or molding is good, the hue after exposure to ultraviolet rays may be deteriorated. Thermal stability may be reduced.
- the concentration of the terminal group represented by the following general formula (7) In order to control the concentration of the terminal group represented by the following general formula (7), the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention as a raw material and the carbonic acid diester represented by the general formula (6) is set. In addition to controlling, a method for controlling the kind and amount of the catalyst at the time of the transesterification reaction, the polymerization pressure and the polymerization temperature can be used.
- C the number of moles of H bonded to the aromatic ring in the polycarbonate resin (A) used in the present invention is (C) and the number of moles of H bonded to other than the aromatic ring is (D), it is bonded to the aromatic ring.
- the ratio of the number of moles of H to the number of moles of total H is expressed as C / (C + D).
- C / (C + D) is preferably 0.1 or less, and more preferably 0.05 or less. Particularly preferably, it is 0.02 or less, preferably 0.01 or less.
- C / (C + D) can be quantified by 1 H-NMR.
- the polycarbonate resin used in the present invention can be formed into a molded product by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method.
- the polycarbonate resin (A) used in the present invention is, as necessary, a heat stabilizer, a neutralizer, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, and a lubricant before performing various moldings.
- Additives such as lubricants, plasticizers, compatibilizers, and flame retardants can also be mixed with a tumbler, super mixer, floater, V-type blender, nauter mixer, Banbury mixer, extruder or the like.
- the glass transition temperature of the polycarbonate resin (A) is preferably 75 ° C. or higher and 105 ° C. or lower, more preferably 80 ° C. or higher and 105 ° C. or lower, and more preferably 85 ° C. or higher and 105 ° C. or lower. preferable.
- the aromatic polycarbonate resin (B) used in the present invention is a polycarbonate resin in which structural units derived from a dihydroxy compound are linked by a carbonate bond, and is represented by the following general formula (2) as a structural unit derived from a dihydroxy compound. It has a structural unit.
- R 1 to R 8 in the general formula (2) each independently represent a hydrogen atom or a substituent.
- Y represents a single bond or a divalent group.
- substituent of R 1 to R 8 in the general formula (2) include an alkyl group having 1 to 10 carbon atoms which may have a substituent, and 1 to carbon atoms which may have a substituent. 10 alkoxy groups, halogen groups, halogenated alkyl groups having 1 to 10 carbon atoms, or aromatic groups having 6 to 20 carbon atoms which may have a substituent. Among these, an alkyl group having 1 to 10 carbon atoms which may have a substituent or an aromatic group having 6 to 20 carbon atoms which may have a substituent is preferable.
- the divalent group represented by Y is an alkylene group having a chain structure having 1 to 6 carbon atoms which may have a substituent, and an optionally substituted carbon group having 1 carbon atom.
- the substituent is not particularly limited as long as the effects of the present invention are not inhibited, but usually has a molecular weight of 200 or less.
- an aryl group is preferable, and a phenyl group is particularly preferable.
- the aromatic polycarbonate resin (B) used in the present invention may be a homopolymer or a copolymer.
- the aromatic polycarbonate resin (B) is a copolymer
- all the structural units derived from the dihydroxy compound are A polycarbonate resin having the largest number of structural units derived from the dihydroxy compound represented by the formula (1), more preferably the dihydroxy compound represented by the general formula (1) with respect to all the structural units derived from the dihydroxy compound.
- a polycarbonate resin having a structure derived from is used in an amount of 50 mol% or more, more preferably 70 mol% or more, particularly preferably 90 mol% or more.
- the aromatic polycarbonate resin (B) may have a branched structure, a linear structure, or a mixture of a branched structure and a linear structure. Furthermore, the aromatic polycarbonate resin (B) used in the present invention may contain a structural unit derived from a dihydroxy compound having a site represented by the general formula (1). However, a polycarbonate resin having a structure different from that of the polycarbonate resin (A) is used when it contains a structural unit derived from a dihydroxy compound having a site represented by the general formula (1).
- the structural unit derived from the dihydroxy compound constituting the aromatic polycarbonate resin (B) used in the present invention is obtained by removing a hydrogen atom from the hydroxyl group of the dihydroxy compound.
- Specific examples of the corresponding dihydroxy compound include the following. 4,4′-biphenol, 2,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy-1,1′-biphenyl, 3,3′-dimethyl-2,4′-dihydroxy-1 , 1′-biphenyl, 3,3′-di- (t-butyl) -4,4′-dihydroxy-1,1′-biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4 ′ -Dihydroxy-1,1'-biphenyl, 3,3 ', 5,5'-tetra- (t-butyl) -4,4'-dihydroxy-1,1'-biphenyl, 2,2', 3,3 Biphenyl compounds such as'
- Halogenated bisphenol compounds such as 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane.
- preferred dihydroxy compounds are bis- (4-hydroxy-3,5-dimethylphenyl) methane, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, 1 , 1-bis- (4-hydroxyphenyl) ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis -(4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, bis- (4-hydroxyphenyl) phenylmethane, 1,1-bis- (4-hydroxy Phenyl) -1-phenylethane, 1,1-bis- (4-hydroxyphenyl) -1-phenylpropan
- bis- (4-hydroxyphenyl) methane bis- (4-hydroxy-3-methylphenyl) methane, bis- (4-hydroxy-3,5-dimethylphenyl) methane, 2,2-bis -(4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis- (4-hydroxy-3,5-dimethylphenyl) propane, 1,1 -Bis- (4-hydroxyphenyl) cyclohexane is preferred.
- the production method of the aromatic polycarbonate resin (B) used in the present invention may be any conventionally known method such as a phosgene method, a transesterification method, or a pyridine method.
- a method for producing an aromatic polycarbonate resin (B) by a transesterification method will be described below.
- the transesterification method is a production method in which a dihydroxy compound and a carbonic acid diester are added with a basic catalyst, and further an acidic substance that neutralizes the basic catalyst is added, and melt transesterification condensation polymerization is performed.
- the dihydroxy compound include the biphenyl compounds and bisphenol compounds exemplified above.
- carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. Is mentioned. Of these, diphenyl carbonate is particularly preferably used.
- the viscosity average molecular weight of the aromatic polycarbonate resin (B) used in the present invention is usually 8,000 or more and 30,000 or less, preferably 10,000 or more and 25,000, from the balance of mechanical properties and molding processability.
- the range is as follows.
- the reduced viscosity of the aromatic polycarbonate resin (B) was measured at a temperature of 20.0 ° C. ⁇ 0.1 ° C. using methylene chloride as a solvent and the polycarbonate concentration was precisely adjusted to 0.60 g / dl. Usually, it is 0.23 dl / g or more and 0.72 dl / g or less, preferably 0.27 dl / g or more and 0.61 dl / g or less.
- the aromatic polycarbonate resin (B) may be used alone or in combination of two or more.
- the polycarbonate resin composition in the present invention preferably has a single glass transition temperature from the viewpoint of maintaining the transparency of the polycarbonate resin composition and the polycarbonate resin molded product.
- the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the polycarbonate resin composition only need to be different types, and the polycarbonate resin (A) preferably has a ring structure, Among these, those containing isosorbide as a dihydroxy compound having a site represented by the general formula (1) in a part of the structure are particularly preferable.
- the polycarbonate resin composition in the present invention includes a structural unit derived from a dihydroxy compound (a) having a site represented by the following general formula (1) in a part of the structure and a dihydroxy compound (b) of an alicyclic hydrocarbon. It is a polycarbonate resin composition containing a polycarbonate resin (A) containing a derived structural unit and an aromatic polycarbonate resin (B).
- R 1 to R 8 in the general formula (2) each independently represent a hydrogen atom or a substituent.
- Y represents a single bond or a divalent group.
- the proportion of the structural unit derived from the alicyclic hydrocarbon dihydroxy compound (b) in the polycarbonate resin (A) is usually 35 mol% or more, preferably 40 mol% or more. Preferably it is 50 mol% or more, Most preferably, it is 55 mol% or more. On the other hand, it is preferably 90 mol% or less, more preferably 80 mol% or less, and particularly preferably 70 mol% or less.
- the ratio of the aromatic polycarbonate resin (B) in the polycarbonate resin composition comprising the polycarbonate resin (A) and the aromatic polycarbonate resin (B) is preferably 20% by weight or more, preferably 30% by weight. More preferably, it is 50% by weight or more, particularly preferably 55% by weight or more. On the other hand, it is preferably 90% by weight or less, more preferably 80% by weight or less, and particularly preferably 70% by weight or less.
- the polycarbonate resin composition and the polycarbonate resin molded article of the present invention can be blended with resins other than polycarbonate resins and additives other than resins.
- resins other than polycarbonate resins that are compounded for the purpose of further improving and adjusting molding processability and various physical properties include resins such as polyester resins, polyethers, polyamides, polyolefins, polymethyl methacrylates, and core-shell types. And rubber-like modifiers such as graft-type or linear random and block copolymers.
- the amount of the resin other than the polycarbonate resin is 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferable to mix
- a heat stabilizer can be blended in order to prevent a decrease in molecular weight and a deterioration in hue during molding.
- the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.
- triphenyl phosphite tris (nonylphenyl) phosphite, tris (2 , 4-Di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylene bis (4,6-di-) tert -Butylphenyl)
- heat stabilizers may be used alone or in combination of two or more.
- the amount of the heat stabilizer is 0.0001 parts by weight or more and 1 part by weight or less based on 100% by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention.
- By blending the heat stabilizer within such a range it is possible to prevent a decrease in molecular weight or discoloration of the resin without causing bleeding of the additive.
- antioxidants generally known for the purpose of antioxidant can be mix
- antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, 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)
- the amount of the antioxidant is 0.0001 parts by weight or more and 1 part by weight or less based on 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. Is preferably blended at a ratio of 0.0005 parts by weight or more and 0.5 parts by weight or less, more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. Further preferred. By blending the antioxidant in such a range, the oxidation deterioration of the resin can be prevented without causing the bleeding of the antioxidant on the surface of the molded body and the deterioration of the mechanical properties of various molded products.
- an ultraviolet absorber can be blended.
- examples of such an ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzo Triazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′- And methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3-benzoxazin-4-one), and the like.
- the melting point of the ultraviolet absorber is particularly preferably in the range of 120 to 250 ° C.
- an ultraviolet absorber having a melting point of 120 ° C. or higher is used, fogging due to gas on the surface of the molded article is reduced and improved.
- the blending amount of the ultraviolet absorber is a ratio of 0.0001 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. Is preferably blended at a ratio of 0.0005 parts by weight or more and 0.5 parts by weight or less, more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. Further preferred. Within such a range, the weather resistance of the resin composition and the molded article can be improved without causing bleeding of the ultraviolet absorbent on the surface of the molded article of the ultraviolet absorbent and deterioration of mechanical properties of various molded articles.
- a hindered amine light stabilizer can be mix
- Such hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidylamin
- the amount of the hindered amine light stabilizer is 0.001 part by weight or more and 1 part by weight or less based on 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferable to mix
- the polycarbonate resin composition of the present invention can be molded without causing bleeding of the hindered amine light stabilizer on the surface of the polycarbonate resin composition and deterioration of mechanical properties of various molded products.
- the weather resistance of the molded product formed can be improved.
- the polycarbonate resin composition of the present invention preferably further contains a release agent in order to further improve the releasability from the mold during melt molding.
- Release agents include higher fatty acids, higher fatty acid esters of mono- or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, natural petroleum waxes such as paraffin wax, and montan wax. Natural coal wax, olefin wax, silicone oil, organopolysiloxane and the like can be mentioned, and higher fatty acid and higher fatty acid ester of monohydric or polyhydric alcohol are particularly preferable.
- a partial ester or a total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable.
- Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbite, stearyl stearate, behenic acid monoglyceride, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate Sorbitan monostearate, 2-ethylhexyl stearate and the like.
- the higher fatty acid is preferably a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms.
- saturated fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.
- One of these release agents may be used alone, or two or more thereof may be mixed and used.
- the content of the releasing agent is preferably 0.0001 parts by weight or more, more preferably 0.001 parts by weight, based on 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. 01 parts by weight or more, particularly preferably 0.1 parts by weight or more, on the other hand, preferably 2 parts by weight or less, more preferably 1 part by weight or less, particularly preferably 0.5 parts by weight or less.
- the timing and method of adding the release agent to be blended with the polycarbonate resin composition there are no particular limitations on the timing and method of adding the release agent to be blended with the polycarbonate resin composition.
- the polycarbonate resin is produced by the transesterification method, when the polymerization reaction is completed; the polycarbonate resin melted during mixing of the polycarbonate resin and other compounding agents regardless of the polymerization method.
- a method of directly mixing or kneading the release agent with a polycarbonate resin; a high-concentration masterbatch prepared using a small amount of a polycarbonate resin or other resin and the release agent can also be added. .
- a polycarbonate resin molded product obtained by molding the above-described polycarbonate resin composition is obtained.
- the molding method of the polycarbonate resin molded product is not particularly limited, but the polycarbonate resin (A), the aromatic polycarbonate resin (B) and, if necessary, other raw materials such as resins and additives are directly mixed, and an extruder or an injection. Either put into a molding machine and mold, or melt and mix the raw materials using a twin-screw extruder, extrude into a strand shape to produce pellets, and then put these pellets into an extruder or injection molding machine Can be mentioned.
- the polycarbonate resin molded article of the present invention is excellent in light resistance and transparency, it can be used for road sound insulation walls, arcade ceiling sheets, arcade ceiling plates, facility roofs, facility wall materials, and the like.
- a specific device is used and a specific filter or the like is used to mainly emit light having a wavelength of 300 nm or more and 1100 nm or less, a black panel temperature of 63 ° C., and a relative humidity of 50.
- a sample is irradiated for 500 hours at a discharge voltage of 50 V and a discharge current of 60 A using a sunshine carbon arc in an environment where the rainfall spraying time per hour is 12 minutes.
- the difference from the YI) value is preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less.
- Example 1 After dry blending PC1 and PC3 at a weight ratio of 80:20, the mixture was extruded at a resin temperature of 250 ° C. using a twin screw extruder (TEX30HSS-32) manufactured by Nippon Steel Works, and cooled and solidified with water. Then, it pelletized with the rotary cutter. After the pellets were dried at 80 ° C. for 10 hours in a nitrogen atmosphere, the pellets were supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.) under the conditions of a resin temperature of 250 ° C., a mold temperature of 60 ° C., and a molding cycle of 40 seconds. An injection-molded plate (width 60 mm ⁇ length 60 mm ⁇ thickness 3 mm) was molded. Table 1 shows the results of measuring the total light transmittance and YI of the obtained sample.
- TEX30HSS-32 twin screw extruder manufactured by Nippon Steel Works
- Example 2 Samples were prepared and evaluated in the same manner as in Example 1 except that PC1 and PC3 were mixed at a mixing weight ratio of 60:40. The results are shown in Table 1.
- Example 3 Samples were prepared and evaluated in the same manner as in Example 1 except that PC1 and PC3 were mixed at a mixing weight ratio of 40:60. The results are shown in Table 1.
- Example 1 Samples were prepared and evaluated in the same manner as in Example 1 except that PC2 and PC3 were mixed at a mixing weight ratio of 80:20. The results are shown in Table 1.
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Abstract
Description
しかしながら、従来のポリカーボネート樹脂は、長時間紫外線や可視光に曝露される場所で使用すると、色相や透明性、機械的強度が悪化するため、屋外や照明装置の近傍での使用に制限があった。又、種々成形品として使用する場合、溶融成形時に離型性が悪く、透明材料や光学材料等に用いることが困難であるという問題があった。
従来のポリカーボネート樹脂に使用されるビスフェノール化合物は、ベンゼン環構造を有するために紫外線吸収が大きく、このことがポリカーボネート樹脂の耐光性悪化を招くため、分子骨格中にベンゼン環構造を持たない脂肪族ジヒドロキシ化合物や脂環式ジヒドロキシ化合物、イソソルビドのように分子内にエーテル結合を持つ環状ジヒドロキシ化合物モノマーユニットを使用すれば、原理的には耐光性が改良されることが期待される。中でも、バイオマス資源から得られるイソソルビドをモノマーとしたポリカーボネート樹脂は、耐熱性や機械的強度が優れていることから、近年数多くの検討がなされるようになってきた(例えば、特許文献1~7)。
即ち、本発明の要旨は下記[1]~[8]に存する。
[1]構造の一部に下記一般式(1)で表される部位を有するジヒドロキシ化合物(a)に由来する構成単位と炭素数11以下の脂環式炭化水素のジヒドロキシ化合物(b)に由来する構成単位とを含むポリカーボネート樹脂(A)と、下記一般式(2)で表される芳香族ポリカーボネート樹脂(B)とを含むポリカーボネート樹脂組成物。
[2]ポリカーボネート樹脂組成物から成形された厚さ3mmの成形体の初期のイエローインデックス(YI)値と、成形体をブラックパネル温度63℃、相対湿度50%、1時間当たりの降雨スプレー時間12分の環境下にて、サンシャインカーボンアークを用い、放電電圧50V、放電電流60Aで、500時間照射処理した後における、イエローインデックス(YI)値との差が10以下である[1]に記載のポリカーボネート樹脂組成物。
[3]前記ジヒドロキシ化合物(a)が、下記一般式(3)で表されるジヒドロキシ化合物である[1]または[2]に記載のポリカーボネート樹脂組成物。
[5]前記ポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、ヒンダードアミン系光安定剤0.001重量部以上1重量部以下を更に含む[1]から[4]のいずれかに記載のポリカーボネート樹脂組成物。
[6]前記ポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、酸化防止剤0.0001重量部以上1重量部以下を更に含む[1]から[5]のいずれかに記載のポリカーボネート樹脂組成物。
[7]前記ポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、離型剤0.0001重量部以上2重量部以下を更に含む[1]から[6]のいずれかに記載のポリカーボネート樹脂組成物。
[8][1]から[7]のいずれかに記載のポリカーボネート樹脂組成物を成形して得られるポリカーボネート樹脂成形品。
本発明で用いるポリカーボネート樹脂(A)は、構造の一部に下記一般式(1)で表される部位を有するジヒドロキシ化合物(a)と炭素数11以下の脂環式炭化水素のジヒドロキシ化合物(b)とを含むジヒドロキシ化合物(以下、単に「ジヒドロキシ化合物」と称することがある)と炭酸ジエステルとを原料として、エステル交換反応により重縮合させて得られる。すなわち、本発明で用いるポリカーボネート樹脂(A)は、構造の一部に下記一般式(1)で表される部位を有するジヒドロキシ化合物(a)に由来する構成単位と炭素数11以下の脂環式炭化水素のジヒドロキシ化合物(b)に由来する構成単位とを含む。
本発明で用いるジヒドロキシ化合物としては、構造の一部に前記一般式(1)で表される部位を有するジヒドロキシ化合物(a)と炭素数11以下の脂環式炭化水素のジヒドロキシ化合物(b)とを含むものであれば特に限定されるものではない。構造の一部に前記一般式(1)で表される部位を有するジヒドロキシ化合物(a)としては、具体的には、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコールなどのオキシアルキレングリコール類、9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレン、9,9-ビス(4-(2-ヒドロキシエトキシ)-3-メチルフェニル)フルオレン、9,9-ビス(4-(2-ヒドロキシエトキシ)-3-イソプロピルフェニル)フルオレン、9,9-ビス(4-(2-ヒドロキシエトキシ)-3-イソブチルフェニル)フルオレン、9,9-ビス(4-(2-ヒドロキシエトキシ)-3-tert-ブチルフェニル)フルオレン、9,9-ビス(4-(2-ヒドロキシエトキシ)-3-シクロヘキシルフェニル)フルオレン、9,9-ビス(4-(2-ヒドロキシエトキシ)-3-フェニルフェニル)フルオレン、9,9-ビス(4-(2-ヒドロキシエトキシ)-3,5-ジメチルフェニル)フルオレン、9,9-ビス(4-(2-ヒドロキシエトキシ)-3-tert-ブチル-6-メチルフェニル)フルオレン9,9-ビス(4-(3-ヒドロキシ-2,2-ジメチルプロポキシ)フェニル)フルオレン等、側鎖に芳香族基を有し、主鎖に芳香族基に結合したエーテル基を有する化合物、下記一般式(3)で表されるジヒドロキシ化合物に代表される無水糖アルコール、並びに下記式(4)および下記式(5)で表されるスピログリコール等の環状エーテル構造を有する化合物が挙げられるが、中でも、入手のし易さ、ハンドリング、重合時の反応性、得られるポリカーボネート樹脂(A)の色相の観点から、ジエチレングリコール、トリエチレングリコール等のオキシアルキレングリコール類、および環状エーテル構造を有する化合物が好ましく、環状エーテル構造を有する化合物のなかでも複数の環構造を有するものが好ましい。また、耐熱性の観点からは、下記式(3)で表されるジヒドロキシ化合物に代表される無水糖アルコール、および下記式(4)で表される環状エーテル構造を有する化合物が好ましく、特には下記式(4)で表されるジヒドロキシ化合物に代表される無水糖アルコールが好ましい。
これらのジヒドロキシ化合物のうち、芳香環構造を有しないジヒドロキシ化合物を用いることがポリカーボネート樹脂(A)の耐光性の観点から好ましく、中でも植物由来の資源として豊富に存在し、容易に入手可能な種々のデンプンから製造されるソルビトールを脱水縮合して得られるイソソルビドが、入手及び製造のし易さ、耐光性、光学特性、成形性、耐熱性、カーボンニュートラルの面から最も好ましい。
本発明で用いるポリカーボネート樹脂(A)は、上述した本発明で用いるジヒドロキシ化合物を含むジヒドロキシ化合物と炭酸ジエステルを原料として、エステル交換反応により重縮合させて得ることができる。
用いられる炭酸ジエステルとしては、通常、下記一般式(6)で表されるものが挙げられる。これらの炭酸ジエステルは、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
前記一般式(6)で表される炭酸ジエステルとしては、例えば、ジフェニルカーボネート、ジトリルカーボネート等の置換ジフェニルカーボネート、ジメチルカーボネート、ジエチルカーボネート及びジ-t-ブチルカーボネート等が例示されるが、好ましくはジフェニルカーボネート、置換ジフェニルカーボネートであり、特に好ましくはジフェニルカーボネートである。なお、炭酸ジエステルは、塩化物イオンなどの不純物を含む場合があり、重合反応を阻害したり、得られるポリカーボネート樹脂の色相を悪化させたりする場合があるため、必要に応じて、蒸留などにより精製したものを使用することが好ましい。
本発明で用いるポリカーボネート樹脂(A)は、上述のように本発明で用いるジヒドロキシ化合物を含むジヒドロキシ化合物と前記一般式(6)で表される炭酸ジエステルをエステル交換反応させてポリカーボネート樹脂を製造する。より詳細には、エステル交換させ、副生するモノヒドロキシ化合物等を系外に除去することによって得られる。この場合、通常、エステル交換反応触媒存在下でエステル交換反応により重縮合を行う。
用いられる触媒としては、製造されたポリカーボネート樹脂(A)の耐光性、透明性、色相、耐熱性、熱安定性、及び機械的強度のうち、とりわけて耐光性を満足させ得るものであれば、限定されないが、長周期型周期表における1族または2族(以下、単に「1族」、「2族」とも表記する。)の金属化合物、塩基性ホウ素化合物、塩基性リン化合物、塩基性アンモニウム化合物、アミン系化合物等の塩基性化合物が挙げられる。好ましくは1族金属化合物及び2族金属化合物のうち少なくとも一方が使用される。
また、1族金属化合物及び/又は2族金属化合物の形態としては通常、水酸化物、又は炭酸塩、カルボン酸塩、フェノール塩といった塩の形態で用いられるが、入手のし易さ、取扱いの容易さから、水酸化物、炭酸塩、酢酸塩が好ましく、色相と重合活性の観点からは酢酸塩が好ましい。
塩基性アンモニウム化合物としては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルエチルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド、トリメチルフェニルアンモニウムヒドロキシド、トリエチルメチルアンモニウムヒドロキシド、トリエチルベンジルアンモニウムヒドロキシド、トリエチルフェニルアンモニウムヒドロキシド、トリブチルベンジルアンモニウムヒドロキシド、トリブチルフェニルアンモニウムヒドロキシド、テトラフェニルアンモニウムヒドロキシド、ベンジルトリフェニルアンモニウムヒドロキシド、メチルトリフェニルアンモニウムヒドロキシド、ブチルトリフェニルアンモニウムヒドロキシド等が挙げられる。
また、1族金属、中でもナトリウム、カリウム、セシウムは、特にはリチウム、ナトリウム、カリウム、セシウムは、ポリカーボネート樹脂(A)中に多く含まれると色相に悪影響を及ぼす可能性があり、該金属は使用する触媒からのみではなく、原料や反応装置から混入する場合があるため、ポリカーボネート樹脂(A)中のこれらの合計量は、金属量として、通常1重量ppm以下、好ましくは0.8重量ppm以下、より好ましくは0.7重量ppm以下である。
本発明で用いるポリカーボネート樹脂(A)は、本発明で用いるジヒドロキシ化合物を含むジヒドロキシ化合物と前記一般式(6)の炭酸ジエステルとをエステル交換反応により重縮合させることによって得られるが、原料であるジヒドロキシ化合物と炭酸ジエステルは、エステル交換反応前に均一に混合することが好ましい。
このモル比率が上記下限以上であれば、製造されたポリカーボネート樹脂の末端水酸基が増加しないので、ポリマーの熱安定性得られ、成形時に着色を招いたり、エステル交換反応の速度が低下したり、所望する高分子量体が得られないといった不具合が生じ難い。
本発明で用いるポリカーボネート樹脂(A)は、触媒を用いて、複数の反応器を用いて多段階で重合させて製造することが好ましいが、重合を複数の反応器で実施する理由は、重合反応初期においては、反応液中に含まれるモノマーが多いために、必要な重合速度を維持しつつ、モノマーの揮散を抑制してやることが重要であり、重合反応後期においては、平衡を重合側にシフトさせるために、副生するモノヒドロキシ化合物を十分留去させることが重要になるためである。このように、異なった重合反応条件を設定するには、直列に配置された複数の重合反応器を用いることが、生産効率の観点から好ましい。
本発明において、反応器が2つ以上であれば、その反応器中で、更に条件の異なる反応段階を複数持たせる、連続的に温度・圧力を変えていくなどしてもよい。
副生したモノヒドロキシ化合物は、資源有効活用の観点から、必要に応じ精製を行った後、炭酸ジフェニルやビスフェノールA等の原料として再利用することが好ましい。
本発明で用いるポリカーボネート樹脂(A)は、上述の通り重縮合後、通常、冷却固化させ、回転式カッター等でペレット化される。
押出機中の、溶融混練温度は、ポリカーボネート樹脂(A)のガラス転移温度や分子量に依存するが、通常150℃~300℃、好ましくは200℃~270℃、更に好ましくは230℃~260℃である。溶融混練温度が150℃より低いと、ポリカーボネート樹脂(A)の溶融粘度が高く、押出機への負荷が大きくなり、生産性が低下する。300℃より高いと、ポリカーボネートの熱劣化が激しくなり、分子量の低下による機械的強度の低下や着色、ガスの発生を招く。
また、押出されたポリカーボネート樹脂を冷却しチップ化する際は、空冷、水冷等の冷却方法を使用するのが好ましい。空冷の際に使用する空気は、ヘパフィルター等で空気中の異物を事前に取り除いた空気を使用し、空気中の異物の再付着を防ぐのが望ましい。水冷を使用する際は、イオン交換樹脂等で水中の金属分を取り除き、さらにフィルターにて、水中の異物を取り除いた水を使用することが望ましい。用いるフィルターの目開きは、99%除去の濾過精度として10μm~0.45μmであることが好ましい。
ポリカーボネート樹脂(A)の還元粘度が上記下限以上であれば成形品の機械的強度が十分に得られ好ましく、上記上限以下であれば、成形する際の流動性が低下せず、生産性や成形性が向上する。
また、本発明で用いるポリカーボネート樹脂(A)は、種々の成形を行う前に、必要に応じて、熱安定剤、中和剤、紫外線吸収剤、離型剤、着色剤、帯電防止剤、滑剤、潤滑剤、可塑剤、相溶化剤、難燃剤等の添加剤を、タンブラー、スーパーミキサー、フローター、V型ブレンダー、ナウターミキサー、バンバリーミキサー、押出機などで混合することもできる。
本発明に用いる芳香族ポリカーボネート樹脂(B)は、ジヒドロキシ化合物に由来する構成単位をカーボネート結合で連結したポリカーボネート樹脂であって、ジヒドロキシ化合物に由来する構成単位として、下記一般式(2)で表される構成単位を有する。
上記一般式(2)中のR1~R8の置換基としては、置換基を有していてもよい炭素数1~10のアルキル基、置換基を有していてもよい炭素数1~10のアルコキシ基、ハロゲン基、炭素数1~10のハロゲン化アルキル基、または置換基を有していてもよい炭素数6~20の芳香族基示す。これらの中でも、置換基を有していてもよい炭素数1~10のアルキル基、または置換基を有していてもよい炭素数6~20の芳香族基が好ましい。上記一般式(2)中のYの2価基としては、置換基を有していてもよい炭素数1~6の鎖状構造のアルキレン基、置換基を有していてもよい炭素数1~6の鎖状構造のアルキリデン基、置換基を有していてもよい炭素数3~6の環状構造のアルキレン基、置換基を有していてもよい炭素数3~6の環状構造のアルキリデン基、-O-、-S-、-CO-または-SO2-があげられる。ここで、置換基としては、本発明の効果を阻害されない限りにおいて、特に限定されないが、通常、分子量が200以下のものである。また、炭素数1~6の鎖状構造のアルキレン基が有する置換基としては、アリール基が好ましく、特にはフェニル基が好ましい。
4,4’-ビフェノール、2,4’-ビフェノール、3,3’-ジメチル-4,4’-ジヒドロキシ-1,1’-ビフェニル、3,3’-ジメチル-2,4’-ジヒドロキシ-1,1’-ビフェニル、3,3’-ジ-(t-ブチル)-4,4’-ジヒドロキシ-1,1’-ビフェニル、3,3’,5,5’-テトラメチル-4,4’-ジヒドロキシ-1,1’-ビフェニル、3,3’,5,5’-テトラ-(t-ブチル)-4,4’-ジヒドロキシ-1,1’-ビフェニル、2,2’,3,3’,5,5’-ヘキサメチル -4,4’-ジヒドロキシ-1,1’-ビフェニル等のビフェニル化合物。
これらの中で好ましいジヒドロキシ化合物は、ビス-(4-ヒドロキシ-3,5-ジメチルフェニル)メタン、ビス-(4-ヒドロキシフェニル)メタン、ビス-(4-ヒドロキシ-3-メチルフェニル)メタン、1,1-ビス-(4-ヒドロキシフェニル)エタン、2,2-ビス-(4-ヒドロキシフェニル)プロパン、2,2-ビス-(4-ヒドロキシ-3-メチルフェニル)プロパン、2,2-ビス-(4-ヒドロキシ-3,5-ジメチルフェニル)プロパン、1,1-ビス-(4-ヒドロキシフェニル)シクロヘキサン、ビス-(4-ヒドロキシフェニル)フェニルメタン、1,1-ビス-(4-ヒドロキシフェニル)-1-フェニルエタン、1,1-ビス-(4-ヒドロキシフェニル)-1-フェニルプロパン、ビス-(4-ヒドロキシフェニル)ジフェニルメタン、2-ヒドロキシフェニル(4-ヒドロキシフェニル)メタン、2,2-(2-ヒドロキシフェニル)(4-ヒドロキシフェニル)プロパン、があげられる。
本発明におけるポリカーボネート樹脂組成物は、構造の一部に下記一般式(1)で表される部位を有するジヒドロキシ化合物(a)に由来する構成単位と脂環式炭化水素のジヒドロキシ化合物(b)に由来する構成単位とを含むポリカーボネート樹脂(A)と、芳香族ポリカーボネート樹脂(B)とを含むポリカーボネート樹脂組成物である。
本発明のポリカーボネート樹脂組成物及びポリカーボネート樹脂成形品は、ポリカーボネート樹脂以外の樹脂や、樹脂以外の添加剤を配合することも出来る。
成形加工性や諸物性のさらなる向上・調整を目的として配合する、ポリカーボネート樹脂以外の樹脂の具体例としては、ポリエステル系樹脂、ポリエーテル、ポリアミド、ポリオレフィン、ポリメチルメタクリレート等の樹脂やコア-シェル型、グラフト型又は線状のランダム及びブロック共重合体のようなゴム状改質剤などが挙げられる。前記ポリカーボネート樹脂以外の樹脂の配合量としては、本発明で用いるポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、1重量部以上、30重量部以下の割合で配合することが好ましく、3重量部以上、20重量部以下の割合で配合することがより好ましく、5重量部以上、10重量部以下の割合で配合することがさらに好ましい。
本発明のポリカーボネート樹脂組成物及びポリカーボネート樹脂成形品には、成形時における分子量の低下や色相の悪化を防止するために熱安定剤を配合することができる。かかる熱安定剤としては、亜リン酸、リン酸、亜ホスホン酸、ホスホン酸およびこれらのエステル等が挙げられ、具体的には、トリフェニルホスファイト、トリス(ノニルフェニル)ホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、ビス(2,6-ジ-tert-ブチル-4-メチルフェニル) ペンタエリスリトールジホスファイト、2,2-メチレンビス(4,6-ジ-tert-ブチルフェニル) オクチルホスファイト、ビス(ノニルフェニル) ペンタエリスリトールジホスファイト、ビス(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、トリブチルホスフェート、トリエチルホスフェート、トリメチルホスフェート、トリフェニルホスフェート、ジフェニルモノオルソキセニルホスフェート、ジブチルホスフェート、ジオクチルホスフェート、ジイソプロピルホスフェート、4,4’-ビフェニレンジホスフィン酸テトラキス(2,4-ジ-tert-ブチルフェニル)、ベンゼンホスホン酸ジメチル、ベンゼンホスホン酸ジエチル、ベンゼンホスホン酸ジプロピル等が挙げられる。なかでも、トリスノニルフェニルホスファイト、トリメチルホスフェート、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、ビス(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト、およびベンゼンホスホン酸ジメチルが好ましく使用される。
また、本発明のポリカーボネート樹脂組成物及びポリカーボネート樹脂成形品には、酸化防止の目的で通常知られた酸化防止剤を配合することができる。かかる酸化防止剤としては、例えばペンタエリスリトールテトラキス(3-メルカプトプロピオネート) 、ペンタエリスリトールテトラキス(3-ラウリルチオプロピオネート)、グリセロール-3-ステアリルチオプロピオネート、トリエチレングリコール-ビス[3-(3-tert-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート]、1,6-ヘキサンジオール-ビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、ペンタエリスリトール-テトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)ベンゼン、N,N-ヘキサメチレンビス(3,5-ジ-tert-ブチル-4-ヒドロキシ-ヒドロシンナマイド)、3,5-ジ-tert-ブチル-4-ヒドロキシ-ベンジルホスホネート-ジエチルエステル、トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)イソシアヌレート、4,4’-ビフェニレンジホスフィン酸テトラキス(2,4-ジ-tert-ブチルフェニル)、3,9-ビス{1,1-ジメチル-2-[β-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ]エチル}-2,4,8,10-テトラオキサスピロ(5,5)ウンデカン等の1種又は2種以上が挙げられる。前記酸化防止剤の配合量は、本発明で用いるポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、0.0001重量部以上、1重量部以下の割合で配合することが好ましく、0.0005重量部以上、0.5重量部以下の割合で配合することがより好ましく、0.001重量部以上、0.2重量部以下の割合で配合することがさらに好ましい。かかる範囲で酸化防止剤を配合することにより、成形体表面への酸化防止剤のブリード、各種成形品の機械特性低下を生じることなく、樹脂の酸化劣化を防止することができる。
本発明のポリカーボネート樹脂組成物及びポリカーボネート樹脂成形品の耐候性をさらに向上する目的で、紫外線吸収剤を配合することができる。かかる紫外線吸収剤としては、例えば2-(2’-ヒドロキシ-5’-tert-オクチルフェニル) ベンゾトリアゾール、2-(3-tert-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール、2-(5-メチル-2-ヒドロキシフェニル)ベンゾトリアゾール、2-[2-ヒドロキシ-3,5-ビス(α,α-ジメチルベンジル)フェニル]-2H-ベンゾトリアゾール、2,2’-メチレンビス(4-クミル-6-ベンゾトリアゾールフェニル)、2,2’-p-フェニレンビス(1,3-ベンゾオキサジン-4-オン)等が挙げられる。紫外線吸収剤の融点としては、特に120~250℃の範囲にあるものが好ましい。融点が120℃ 以上の紫外線吸収剤を使用すると、成形品表面のガスによる曇りが減少し改善される。具体的には、2-(2'-ヒドロキシ-5'-メチルフェニル)ベンゾトリアゾール、2-(2 '-ヒドロキシ-3'-tert-ブチル-5'-メチルフェニル) -5-クロロベンゾトリアゾール、2-[2'-ヒドロキシ-3'-(3",4",5",6"-テトラヒドロフタルイミドメチル)-5'-メチルフェニル]ベンゾトリアゾール、2,2-メチレンビス[4-(1,1,3,3-テトラメチルブチル)-6-(2H-ベンゾトリアゾール-2-イル)フェノール、2-(2-ヒドロキシ-3,5-ジクミルフェニル)ベンゾトリアゾールなどのベンゾトリアゾール系紫外線吸収剤が使用され、これらのうちでも、特に、2-(2-ヒドロキシ-3,5-ジクミルフェニル)ベンゾトリアゾール、2,2-メチレンビス[4-(1,1,3,3-テトラメチルブチル) -6-(2H-ベンゾトリアゾール-2-イル)フェノールが好ましい。これらの紫外線吸収剤は1種を単独で用いてもよく、2種以上を併用してもよい。 前記紫外線吸収剤の配合量は、本発明で用いるポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、0.0001重量部以上、1重量部以下の割合で配合することが好ましく、0.0005重量部以上、0.5重量部以下の割合で配合することがより好ましく、0.001重量部以上、0.2重量部以下の割合で配合することがさらに好ましい。かかる範囲で紫外線吸収剤成形品表面への紫外線吸収剤のブリード、各種成形品の機械特性低下を生じることなく、樹脂組成物及び成形品の耐候性を向上することができる。
また、本発明のポリカーボネート樹脂組成物及びポリカーボネート樹脂成形品の耐候性をさらに向上する目的で、ヒンダードアミン系光安定剤を配合することができる。かかるヒンダードアミン系光安定剤としては、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス-(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、ポリ[[6-(1,1,3,3-テトラメチルブチル)アミノ-1,3,5-トリアジン-2,4-ジイル][(2,2,6,6-テトラメチル-4-ピペリジル)イミノ]ヘキサメチレン[(2,2,6,6-テトラメチル-4-ピペリジル)イミノ]]、N,N’-ビス(3-アミノプロピル)エチレンジアミン-2,4-ビス[N-ブチル-N-(1,2,2,6,6-ペンタメチル-4-ピペリジルアミノ)-6-クロロ-1,3,5-トリアジン縮合物、ジブチルアミン・1,3,5-トリアジン・N,N’-ビス(2,2,6,6)-テトラメチル-4-ピペリジル-1、6-ヘキサメチレンジアミンとN-(2,2,6,6-テトラメチル-4-ピペリジル)ブチルアミンの重縮合物等が挙げられる。なかでもビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス-(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケートが好ましい。
本発明のポリカーボネート樹脂組成物は溶融成形時の金型からの離型性をより向上させるために、更に離型剤を含有していることが好ましい。離型剤としては、高級脂肪酸、一価または多価アルコールの高級脂肪酸エステル、蜜蝋等の天然動物系ワックス、カルナバワックス等の天然植物系ワックス、パラフィンワックス等の天然石油系ワックス、モンタンワックス等の天然石炭系ワックス、オレフィン系ワックス、シリコーンオイル、オルガノポリシロキサン等が挙げられ、高級脂肪酸、一価または多価アルコールの高級脂肪酸エステルが特に好ましい。
本実施の形態では、上述したポリカーボネート樹脂組成物を成形してなるポリカーボネート樹脂成形品が得られる。ポリカーボネート樹脂成形品の成形方法は特に限定されないが、ポリカーボネート樹脂(A)、芳香族ポリカーボネート樹脂(B)及び、必要に応じてその他の樹脂や添加剤等の原料を直接混合し、押出機或いは射出成形機に投入して成形するか、または、前記原料を、二軸押出機を用いて溶融混合し、ストランド形状に押出してペレットを作製した後、このペレットを押出機或いは射出成形機に投入して成形する方法を挙げることができる。また、本発明のポリカーボネート樹脂成形品は、耐光性、透明性に優れているため、道路遮音壁、アーケード天井シート、アーケード天井プレート、施設屋根、施設壁材等に使用することができる。
以下において、ポリカーボネート樹脂、ポリカーボネート樹脂組成物、成形品等の物性ないし特性の評価は次の方法により行った。
(1)還元粘度の測定
ポリカーボネート樹脂のサンプルを、溶媒として塩化メチレンを用いて溶解し、0.6g/dLの濃度のポリカーボネート溶液を調製した。森友理化工業社製ウベローデ型粘度管を用いて、温度20.0℃±0.1℃で測定を行い、溶媒の通過時間t0と溶液の通過時間tから次式より相対粘度ηrelを求め、
ηrel=t/t0
相対粘度から次式より比粘度ηspを求めた。
ηsp=(η-η0)/η0=ηrel-1
比粘度を濃度c(g/dL)で割って、還元粘度ηsp/cを求めた。この値が高いほど分子量が大きい。
JIS K7105(1981年)に準拠し、分光色差計(日本電色工業社製SE2000)を使用し、C光源透過法にて射出成形片(幅60mm×長さ60mm×厚さ3mm)のイエローインデックス(YI)値を測定した。YI値が小さい程、黄色味がなく品質が優れることを示す。
JIS K7105(1981年)に準拠し、ヘイズメーター(日本電色工業社製NDH2000)を使用し、D65光源にて射出成形片の全光線透過率を測定した。
JIS B7753(2007年)に準拠してスガ試験機社製サンシャインウェザーメーターS80を用いて、サンシャインカーボンアーク(ウルトラロングライフカーボン4対)光源で放電電圧50V、放電電流60Aに設定し、照射及び表面スプレ(降雨)にてブラックパネル温度63℃、相対湿度50%の条件下、射出成形片の平板(幅60mm×長さ60mm×厚さ3mm)の正方形の面に対して、500時間照射処理を行った。表面スプレー(降雨)時間は、12分/1時間とした。ガラスフィルターはAタイプを用いた。照射処理後のYIと全光線透過率を測定し、さらに500時間処理後のYIと処理前のYIとの差を求めた。
PC1:
イソソルビドに由来する構成単位/1,4-シクロヘキサンジメタノールに由来する構成単位=40/60モル%、還元粘度 0.63dl/g
PC2:
イソソルビドに由来する構成単位/9,9-〔4-(2-ヒドロキシエトキシ)フェニル〕フルオレンに由来する構成単位=70/30モル%、還元粘度 0.57dl/g
PC3:
三菱エンジニアリングプラスチックス社製ノバレックス7022J(2,2-ビス-(4-ヒドロキシフェニル)プロパンに由来する構造のみを有する芳香族ポリカーボネート樹脂,粘度平均分子量22,000)
PC1、及び、PC3を重量比80:20の割合でドライブレンドした後、日本製鋼所社製2軸押出機(TEX30HSS-32)を用いて、樹脂温度250℃で押し出し、水で冷却固化させた後、回転式カッターでペレット化した。ペレットを、窒素雰囲気下、80℃で10時間乾燥した後に、射出成形機(日本製鋼所社製J75EII型)に供給し、樹脂温度250℃、金型温度60℃、成形サイクル40秒間の条件で、射出成形板(幅60mm×長さ60mm×厚さ3mm)を成形した。得られたサンプルについて、全光線透過率、YIの測定を行なった結果を表1に示す。
PC1、及び、PC3を混合重量比60:40の割合で混合した以外は実施例1と同様の方法でサンプルの作製、評価を行なった。結果を表1に示す。
PC1、及び、PC3を混合重量比40:60の割合で混合した以外は実施例1と同様の方法でサンプルの作製、評価を行なった。結果を表1に示す。
PC2、及び、PC3を混合重量比80:20の割合で混合した以外は実施例1と同様の方法でサンプルの作製、評価を行なった。結果を表1に示す。
Claims (8)
- 前記ポリカーボネート樹脂組成物から成形された厚さ3mmの成形体の初期のイエローインデックス(YI)値と、該成形体をブラックパネル温度63℃、相対湿度50%、1時間当たりの降雨スプレー時間12分の環境下にて、サンシャインカーボンアークを用い、放電電圧50V、放電電流60Aで、500時間照射処理した後における、イエローインデックス(YI)値との差が10以下である請求項1に記載のポリカーボネート樹脂組成物。
- 前記ポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、紫外線吸収剤0.0001重量部以上1重量部以下を更に含む請求項1から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。
- 前記ポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、ヒンダードアミン系光安定剤0.001重量部以上1重量部以下を更に含む請求項1から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。
- 前記ポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、酸化防止剤0.0001重量部以上1重量部以下を更に含む請求項1から5のいずれか1項に記載のポリカーボネート樹脂組成物。
- 前記ポリカーボネート樹脂(A)と前記芳香族ポリカーボネート樹脂(B)との混合物100重量部に対して、離型剤0.0001重量部以上2重量部以下を更に含む請求項1から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。
- 請求項1から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を成形して得られるポリカーボネート樹脂成形品。
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WO2011071166A1 (ja) * | 2009-12-10 | 2011-06-16 | 三菱化学株式会社 | ポリカーボネート樹脂組成物及び成形品 |
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EP2511341A1 (en) | 2012-10-17 |
US20120232198A1 (en) | 2012-09-13 |
EP2511341A4 (en) | 2015-07-08 |
CN102712805A (zh) | 2012-10-03 |
KR20120115234A (ko) | 2012-10-17 |
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