WO2012133236A1 - ポリカーボネート樹脂の製造方法、ポリカーボネート樹脂、ポリカーボネート樹脂製フィルムおよびポリカーボネート樹脂ペレットの製造方法 - Google Patents
ポリカーボネート樹脂の製造方法、ポリカーボネート樹脂、ポリカーボネート樹脂製フィルムおよびポリカーボネート樹脂ペレットの製造方法 Download PDFInfo
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- WO2012133236A1 WO2012133236A1 PCT/JP2012/057619 JP2012057619W WO2012133236A1 WO 2012133236 A1 WO2012133236 A1 WO 2012133236A1 JP 2012057619 W JP2012057619 W JP 2012057619W WO 2012133236 A1 WO2012133236 A1 WO 2012133236A1
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- polycarbonate resin
- filter
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- 0 *NO[N+]([O-])O* Chemical compound *NO[N+]([O-])O* 0.000 description 1
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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
- C08G64/305—General preparatory processes using carbonates and alcohols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- 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
Definitions
- the present invention relates to a method for efficiently and stably producing a polycarbonate resin which is excellent in thermal stability, hue, and mechanical strength and has few foreign matters.
- Polycarbonate resins generally contain bisphenols as monomer components and take advantage of transparency, heat resistance, mechanical strength, etc., so-called electrical / electronic parts, automotive parts, optical recording media, lenses, and other optical fields. Widely used as engineering plastics.
- Patent Document 1 a method for obtaining a polycarbonate resin while using a special dihydroxy compound as a monomer component and distilling off a monohydroxy compound by-produced by transesterification with a carbonic acid diester under reduced pressure.
- the polycarbonate resin obtained in this way has a problem that foreign matters are mixed in during its production process, etc., and foreign matters are mixed into a molded body molded using the resin, and the commercial value is remarkably lowered. there were. In particular, in optical applications and the like, contamination or coloring of foreign matters has been a particularly serious problem.
- Patent Documents 7 and 8 As a method for reducing the mixing of foreign substances, a method of filtering a resin obtained by polycondensation using a filter is proposed for polycarbonate resins containing bisphenols as monomer components (for example, Patent Documents 7 and 8). .
- a polycarbonate resin containing a special dihydroxy compound other than bisphenol as a monomer component starts to decompose at a lower temperature than a polycarbonate resin containing bisphenol as a monomer component.
- An object of the present invention is to provide a method for efficiently and stably producing a polycarbonate resin that solves the above-mentioned conventional problems and is excellent in thermal stability, hue, and mechanical strength and has few foreign matters. is there.
- the present inventor polycondensed by a transesterification reaction using a catalyst, a specific dihydroxy compound and a carbonic acid diester as raw material monomers, and obtained polycarbonate resin.
- the inventors have found a method for stably producing polycarbonate resin pellets that are excellent in mechanical strength and hue and have few foreign matters by filtering the polycarbonate resin under specific conditions.
- the gist of the present invention resides in the following [1] to [23].
- [1] A method for producing a polycarbonate resin in which a polycarbonate resin obtained by polycondensation of a dihydroxy compound and a carbonic acid diester is filtered using a filter and then solidified by cooling. It contains at least a dihydroxy compound having a site represented by the general formula (1), the mesh opening of the filter is 50 ⁇ m or less, and the temperature of the polycarbonate resin after filtration using the filter is 200 ° C. or more and less than 280 ° C.
- a method for producing a polycarbonate resin, comprising filtering the polycarbonate resin as described above.
- the melt viscosity at a shear rate of 91.2 sec ⁇ 1 measured at 240 ° C. is 500 Pa ⁇ s to 3000 Pa ⁇ s [1] to [4] ]
- the filter is stored in a container, and a value obtained by dividing the internal volume (m 3 ) of the storage container by the flow rate (m 3 / min) of the polycarbonate resin to be filtered is 2 to 10 minutes.
- the polycarbonate resin before filtration is supplied from the lower part of the storage container of the filter, and the polycarbonate resin after filtration is discharged from the upper part of the storage container. Of producing a polycarbonate resin.
- the polycondensation is performed using a catalyst, and the catalyst is at least one metal compound selected from the group consisting of a metal of Group 2 of the long-period periodic table and lithium [1]. Thru
- the screw of the extruder is composed of a plurality of elements, and at least one of the elements is a kneading disk, and the total length of the kneading disk is 20% of the total length of the screw.
- a polycarbonate resin having a yellow index value of 30 or less obtained by the production method according to any one of [1] to [20].
- the present invention is excellent in mechanical strength and hue, and has a small amount of foreign matter, such as an injection molding field such as an electric / electronic part or an automobile part, a film or sheet field, a bottle or container field, and a camera lens or a finder lens.
- Lens applications such as CCD or CMOS lenses, retardation films used for liquid crystal or plasma displays, diffusion sheets, films such as polarizing films, sheets, optical disks, optical materials, optical components, dyes or charge transfer agents, etc. It is possible to efficiently and stably produce polycarbonate resin pellets having performance applicable to a wide range of fields such as binder use for fixing the resin.
- FIG. 1 is a process diagram showing an example of a manufacturing process according to the present invention.
- the method for producing a polycarbonate resin pellet of the present invention is a method for producing a polycarbonate resin in which a polycarbonate resin obtained by polycondensation of a dihydroxy compound and a carbonic acid diester is filtered using a filter and then solidified by cooling.
- the compound includes at least a dihydroxy compound having a site represented by the following general formula (1) in a part of the structure, the opening of the filter is 50 ⁇ m or less, and the temperature of the resin after filtration using the filter is It is characterized by filtering so as to be 200 ° C. or higher and lower than 280 ° C.
- ⁇ Raw material monomers and polymerization catalyst> (Dihydroxy compound)
- a carbonic acid diester and a dihydroxy compound are used as raw material monomers, but at least one of the dihydroxy compounds has a part of the structure having a site represented by the above general formula (1) It is a dihydroxy compound (hereinafter sometimes referred to as “the dihydroxy compound of the present invention”). That is, the dihydroxy compound of the present invention refers to a compound containing at least two hydroxyl groups and at least the structural unit of the general formula (1).
- the dihydroxy compound of the present invention is not particularly limited as long as it has a site represented by the above general formula (1) in a part of its structure.
- oxyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; 9,9-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
- diethylene glycol, triethylene glycol, or polyethylene glycol is preferable from the viewpoints of availability, handling, reactivity during polymerization, and hue of the obtained polycarbonate resin.
- cyclic sugar structures such as anhydrous sugar alcohols represented by the dihydroxy compound represented by the following general formula (5) or spiroglycol represented by the following general formula (6) [preferably, A compound having a moiety represented by the general formula (1) that is part of a cyclic ether structure] is preferred.
- examples of the dihydroxy compound represented by the general formula (5) include isosorbide, isomannide, and isoide which are related to stereoisomers. These may be used individually by 1 type and may be used in combination of 2 or more type.
- dihydroxy compounds it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of the hue of the polycarbonate resin.
- isosorbide obtained by dehydrating and condensing sorbitol produced from various starches that are abundant as plant-derived resources is easy to obtain and manufacture, light resistance, optical properties, moldability From the viewpoint of heat resistance and carbon neutral, it is most preferable.
- a constituent unit derived from a dihydroxy compound other than the above-described dihydroxy compound of the present invention (hereinafter sometimes referred to as “other dihydroxy compound”) is included as a raw material monomer. Good.
- dihydroxy compounds from the viewpoint of the hue of the polycarbonate resin, it is selected from the group consisting of dihydroxy compounds having no aromatic ring structure in the molecular structure, that is, aliphatic dihydroxy compounds and alicyclic dihydroxy compounds. It is preferred to use at least one compound.
- 1,3-propanediol, 1,4-butanediol or 1,6-hexanediol is particularly preferable.
- 1,4-cyclohexanedimethanol or tricyclodecane dimethanol is particularly preferable. Among these, 1,4-cyclohexanedimethanol is preferable from the viewpoint of improving the polymerization reactivity and toughness.
- the ratio of the structural unit derived from the dihydroxy compound of the present invention to the structural unit derived from all dihydroxy compounds is preferably 20 mol% or more, more preferably 30 mol% or more, and particularly preferably 50 mol% or more. Preferably there is.
- the proportion of structural units derived from other dihydroxy compounds is preferably less than 80 mol%, more preferably 70 mol% or less, with respect to structural units derived from all dihydroxy compounds. It is particularly preferred that
- the dihydroxy compound of the present invention may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer or heat stabilizer.
- a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer or heat stabilizer.
- a basic stabilizer since the dihydroxy compound of the present invention is easily altered under acidic conditions, it is preferable to contain a basic stabilizer when stored before use.
- Examples of the basic stabilizer include hydroxides, carbonates, phosphates, phosphites, hypophosphites of group 1 or group 2 metals in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005).
- Phosphate, borate and fatty acid salt tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide , Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylpheny Basic ammonium compounds such as ammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide; and 4-aminopyridine, 2-amino
- the content of these stabilizers in the dihydroxy compound of the present invention is not particularly limited, but if it is too small, the effect of preventing alteration of the dihydroxy compound of the present invention may not be obtained. It may lead to modification of the compound. Therefore, the stabilizer content is usually preferably 0.0001% by weight to 1% by weight, more preferably 0.001% by weight to 0.1% by weight, based on the dihydroxy compound of the present invention. .
- the dihydroxy compound of the present invention has a cyclic ether structure such as isosorbide, it is easily oxidized by oxygen. Therefore, during storage or production, in order to prevent decomposition by oxygen, water should not be mixed, and It is preferable to use an oxygen scavenger or handle under a nitrogen atmosphere.
- decomposition products such as formic acid may be generated. If isosorbide containing these decomposition products is used as a raw material for the production of polycarbonate resin, it may lead to coloration of the resulting polycarbonate resin, and may not only significantly deteriorate the physical properties but also affect the polymerization reaction. In some cases, a high molecular weight polymer cannot be obtained.
- a polycarbonate resin can be obtained by polycondensation by a transesterification reaction using a dihydroxy compound containing the dihydroxy compound of the present invention described above and a carbonic acid diester as raw materials.
- Examples of the carbonic acid diester used in the present invention include those represented by the following general structural formula (7). These carbonic acid diesters may be used alone or in combination of two or more.
- a 1 and A 2 are substituted or unsubstituted aliphatic groups having 1 to 18 carbon atoms or substituted or unsubstituted aromatic groups, and A 1 and A 2 are the same. May be different.
- a 1 and A 2 are preferably a substituted or unsubstituted aromatic hydrocarbon group, more preferably an unsubstituted aromatic hydrocarbon group.
- substituent of the aliphatic hydrocarbon group include an ester group, an ether group, a carboxylic acid, an amide group, and a halogen.
- substituent of the aromatic hydrocarbon group include alkyl groups such as a methyl group and an ethyl group.
- Examples of the carbonic acid diester represented by the general formula (7) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Among them, preferred is diphenyl carbonate or substituted diphenyl carbonate, and particularly preferred is diphenyl carbonate.
- 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.
- a polycarbonate resin can be obtained by polycondensing a dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester by a transesterification reaction.
- the dihydroxy compound and carbonic acid diester as raw materials can be transesterified even if they are dropped independently into the reaction vessel, but they can also be mixed uniformly before the transesterification.
- the mixing temperature is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and the upper limit is preferably 250 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 130 ° C. or lower is preferable.
- the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification. If the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated, resulting in deterioration of the hue of the polycarbonate resin obtained, which may adversely affect light resistance or heat resistance.
- the oxygen concentration in the operating environment in which the dihydroxy compound containing the dihydroxy compound of the present invention as a raw material and the carbonic acid diester are mixed is preferably 10 vol% or less, more preferably 0.0001 vol% to 10 vol%, and in particular 0 It is preferable to carry out in an atmosphere of 0.0001 vol% to 5 vol%, particularly 0.0001 vol% to 1 vol% from the viewpoint of preventing hue deterioration.
- the carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.20, more preferably 0.95 to 1, based on all dihydroxy compounds including the dihydroxy compound of the present invention used in the reaction. .10, more preferably 0.97 to 1.03, particularly preferably 0.99 to 1.02.
- the molar ratio When the molar ratio is decreased, the terminal hydroxyl group of the produced polycarbonate resin is increased, the thermal stability of the polymer is deteriorated, coloring is caused at the time of molding, the rate of the transesterification reaction is decreased, and the desired high molecular weight.
- the body may not be obtained.
- the rate of transesterification decreases, the production of polycarbonate having a desired molecular weight becomes difficult, the amount of residual carbonic diester in the polycarbonate resin increases, and during extrusion or molding In some cases, gas may be generated.
- the decrease in the transesterification reaction rate may increase the thermal history during the polymerization reaction and may deteriorate the hue of the resulting polycarbonate resin.
- the amount of residual carbonic diester in the obtained polycarbonate resin increases, which becomes a gas at the time of molding and causes molding defects. Bleed out from the product, which is not preferable.
- the concentration of the diester carbonate remaining in the polycarbonate resin pellet obtained by the method of 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.
- a transesterification catalyst (hereinafter simply referred to as “catalyst”). Or “polymerization catalyst”) can be present.
- the transesterification catalyst can particularly affect the thermal stability of the polycarbonate resin, or the yellow index (YI) value representing the hue.
- the transesterification catalyst used is not limited as long as it satisfies the thermal stability and hue of the polycarbonate resin.
- a metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and a group 1 or group 2 in the long-period periodic table
- Examples include basic compounds such as amine compounds.
- Group 1 metal compounds and / or Group 2 metal compounds are used. More preferably, it is a metal compound of a metal selected from the group consisting of a long-period group 2 metal and lithium.
- the group 1 metal compound and / or the group 2 metal compound is usually used in the form of a hydroxide or a salt such as carbonate, carboxylate or phenol salt. From the viewpoint of easiness, a hydroxide, carbonate or acetate is preferred, and acetate is preferred 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, and carbonic acid.
- Group 2 metal compound examples include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate.
- a magnesium compound, a calcium compound or a barium compound is preferable, and at least one metal compound selected from the group consisting of a magnesium compound and a calcium compound is further preferable, and most preferably calcium, from the viewpoint of polymerization activity and the hue of the polycarbonate resin obtained.
- a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination with the group 1 metal compound and / or the group 2 metal compound.
- a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination with the group 1 metal compound and / or the group 2 metal compound.
- a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound can be used in combination with the group 1 metal compound and / or the group 2 metal compound.
- it since it may volatilize during the polymerization reaction and cause trouble, it is particularly preferable to use only the Group 1 metal compound and / or the Group 2 metal compound.
- Examples of the basic boron compound that can be used in combination include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, and triethyl.
- Sodium salt, potassium salt, lithium salt, calcium salt, barium salt, magnesium salt and strontium such as phenylboron, tributylbenzylboron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron and butyltriphenylboron Examples include salts.
- Examples of the basic phosphorus compound that can be used in combination include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts. .
- Examples of the basic ammonium compound that can be used in combination include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, and trimethyl.
- Phenylammonium hydroxide triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltrimethyl Phenyl Nmo onium hydroxide and butyltriphenyl ammonium hydroxide, and the like.
- Examples of the amine compounds that can be used in combination 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 catalyst used is preferably from 0.1 ⁇ mol to 300 ⁇ mol, more preferably from 0.5 ⁇ mol to 100 ⁇ mol, still more preferably from 0.5 ⁇ mol to 50 ⁇ mol, and even more preferably from 0.1 ⁇ mol to 300 ⁇ mol per 1 mol of all dihydroxy compounds used.
- the amount is 5 ⁇ mol to 20 ⁇ mol, and particularly preferably 1 ⁇ mol to 5 ⁇ mol.
- the amount of metal is preferably usually 0.1 ⁇ mol or more per 1 mol of all dihydroxy compounds used, Preferably it is 0.5 ⁇ mol or more, particularly preferably 0.7 ⁇ mol or more.
- the upper limit is usually preferably 20 ⁇ mol, more preferably 10 ⁇ mol, still more preferably 3 ⁇ mol, particularly preferably 1.5 ⁇ mol, and most preferably 1.0 ⁇ mol.
- the total amount of these compounds in the polycarbonate resin is usually preferably 1 ppm by weight or less, more preferably 0.8 ppm by weight or less, and even more preferably 0.7 ppm by weight or less as the amount of metal. .
- the amount of metal in the polycarbonate resin can be measured using a method such as atomic emission, atomic absorption, or Inductively 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, or Inductively Coupled Plasma (ICP) after recovering the metal in the polycarbonate resin by a method such as wet ashing. I can do it.
- ICP Inductively Coupled Plasma
- the catalyst may be added directly to the reactor, or may be added to a raw material adjusting tank in which a dihydroxy compound and a carbonic acid diester are mixed in advance, and then present in the reactor. You may add in the piping which supplies a raw material.
- the method for obtaining a polycarbonate resin by polycondensation of the dihydroxy compound and the carbonic acid diester may be carried out in multiple stages using a plurality of reactors in the presence of the catalyst.
- the reaction format may be any of batch, continuous, or a combination of batch and continuous.
- the continuous type is preferable from the viewpoint of stabilizing the quality.
- the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate.
- a polymer having a predetermined molecular weight or terminal group cannot be obtained, and as a result, the object of the present invention may not be achieved.
- a reflux condenser for the polymerization reactor in order to suppress the amount of monomer to be distilled off, and the effect is particularly great in a reactor in the early stage of polymerization where there are many unreacted monomer components.
- the temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used.
- the temperature of the refrigerant introduced into the reflux condenser is preferably 45 to 180 ° C. at the inlet of the reflux condenser, more preferably 80 to 150 ° C., and particularly preferably 100 to 140 ° C.
- the temperature of the refrigerant is too high, the amount of reflux is reduced and the effect is reduced. On the other hand, if the temperature is too low, the distillation efficiency of the monohydroxy compound that should be distilled off tends to be reduced.
- the refrigerant include warm water, steam, and heat medium oil, and steam or heat medium oil is preferable.
- the catalyst is used for polymerization in multiple stages using a plurality of reactors.
- the reason for carrying out the polymerization in a plurality of reactors is that at the initial stage of the polymerization reaction, since there are many monomers contained in the reaction liquid, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate. In the latter stage of the polymerization reaction, it is important to sufficiently distill off the by-produced monohydroxy compound in order to shift the equilibrium to the polymerization side, and desirable polymerization reaction conditions differ between the initial stage and the latter stage. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of polymerization reactors arranged in series.
- the number of reactors used in the polymerization in the present invention is preferably at least two, more preferably three or more, and still more preferably 3 to 5 from the viewpoint of production efficiency. And particularly preferably four.
- reaction conditions can be set in each reactor, and the temperature and pressure are continuously changed in each reactor. May be.
- the polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or directly to the polymerization tank. From the viewpoint of supply stability and polymerization control, the polymerization catalyst is added to the polymerization tank.
- a catalyst supply pipe may be installed in the middle of the raw material pipe before being supplied, and is preferably supplied as an aqueous solution.
- the productivity is lowered or the thermal history of the product is increased. If the temperature is too high, not only the monomer is volatilized but also decomposition or coloring of the polycarbonate resin may be promoted. .
- the maximum internal temperature of the polymerization reactor is preferably 140 to 270 ° C., more preferably 170 to 240 ° C., still more preferably 180 to 210 ° C., and preferably 110 to 1 kPa, more
- the monohydroxy compound produced as a by-product is removed from the reaction system under a pressure of 70 to 5 kPa, more preferably 30 to 10 kPa (absolute pressure), preferably 0.1 to 10 hours, more preferably 0.5 to 3 hours. Carried out while distilling.
- the reaction in the first stage in the present invention refers to a reaction in a reactor at the uppermost stream of the process in a reactor in which 5% by weight or more of a monohydroxy compound distilled through the entire polymerization reaction is distilled. .
- 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.
- it is 2 kPa or less, more preferably 1 kPa or less, preferably 210 ° C. or more, more preferably 220 ° C. or more, preferably 270 ° C. or less, more preferably 250 ° C. or less, more preferably 240 ° C. or less, preferably 0 1-10 hours, more preferably 1-6 hours, particularly preferably 0.5-3 hours.
- the maximum internal temperature in all reaction steps is preferably less than 260 ° C, more preferably less than 250 ° C, In particular, the temperature is preferably less than 245 ° C.
- the internal temperature indicates the temperature of the process liquid, and is usually measured by a thermometer using a thermocouple or the like provided in the reactor.
- a thermometer using a thermocouple or the like provided in the reactor.
- the yellow index (YI) value representing the hue tends to increase when the polymerization temperature is increased and the polymerization time is excessively prolonged.
- the monohydroxy compound distilled off as a by-product in the reaction is preferably used as a raw material for fuel or chemicals from the viewpoint of effective utilization of resources.
- the polycarbonate resin of the present invention is filtered using a filter after performing the above-mentioned polycondensation reaction.
- the polycarbonate resin obtained by polycondensation is introduced into an extruder and then discharged from the extruder in order to remove low molecular weight components contained in the polycarbonate resin or to add and knead a heat stabilizer or the like. Is preferably filtered using a filter.
- Examples of the method for filtering the polycarbonate resin obtained by polycondensation as described above using a filter include the following methods.
- a polycarbonate resin is extracted from the final polymerization reactor in a molten state using a gear pump or a screw, and filtered through the filter.
- Polycarbonate resin is supplied from a final polymerization reactor to a uniaxial or biaxial extruder in a molten state, melt extruded, filtered through the filter, cooled and solidified in the form of a strand, and pelletized with a rotary cutter or the like.
- Polycarbonate resin is supplied to a single-screw or twin-screw extruder in a molten state without being solidified from the final polymerization reactor, melt-extruded, then cooled and solidified in the form of a strand, pelletized, and the pellet is extruded again.
- the polycarbonate resin is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands without passing through an extruder, and once pelletized, then the pellets are supplied to a single or twin screw extruder and melted. After extruding, it is filtered by the filter, cooled and solidified in the form of a strand, and pelletized.
- the resin in order to minimize the heat history and suppress thermal degradation such as deterioration of hue or molecular weight, the resin is put into a single or twin screw extruder in a molten state without solidifying from the final polymerization reactor.
- a method of feeding, melting and extruding, feeding to the filter using a gear pump, filtering, discharging from a die, cooling and solidifying in the form of a strand, and pelletizing with a rotary cutter or the like is preferable.
- Isosorbide is used as a dihydroxy compound of the present invention as a raw material monomer
- 1,4-cyclohexanedimethanol (CHDM) is used as another dihydroxy compound
- diphenyl carbonate (DPC) is used as a carbonic acid diester
- calcium acetate is used as a polymerization catalyst. It shall be.
- a DPC melt prepared at a predetermined temperature in a nitrogen gas atmosphere is continuously supplied from the raw material supply port 1a to the raw material mixing tank 2a.
- the ISB melt and the CHDM melt measured in a nitrogen gas atmosphere are continuously supplied to the raw material mixing tank 2a from the raw material supply ports 1b and 1c, respectively. And these are mixed by the stirring blade 3a within the raw material mixing tank 2a, and a raw material mixing melt is obtained.
- the obtained raw material mixture melt is continuously supplied to the first vertical stirring reaction tank 6a via the raw material supply pump 4a and the raw material filtration filter 5a. Further, the raw material catalyst is continuously supplied as an aqueous solution from the catalyst supply port 1d in the middle of the raw material mixed melt transfer pipe.
- a first vertical stirring reaction tank 6a, a second vertical stirring reaction tank 6b, a third vertical stirring reaction tank 6c, and a fourth horizontal stirring reaction tank 6d are provided in series. It is done. In each reactor, the liquid level is kept constant, a polycondensation reaction is performed, and the polymerization reaction liquid discharged from the bottom of the first vertical stirring reaction tank 6a continues to the second vertical stirring reaction tank 6b.
- the third vertical stirring reaction tank 6c is successively supplied to the fourth horizontal stirring reaction tank 6d in order, and the polycondensation reaction proceeds.
- the reaction conditions in each reactor are preferably set so as to become high temperature, high vacuum, and low stirring speed as the polycondensation reaction proceeds.
- Max blend blades 7a, 7b and 7c are provided in the first vertical stirring reaction tank 6a, the second vertical stirring reaction tank 6b and the third vertical stirring reaction tank 6c, respectively.
- the fourth horizontal stirring reaction tank 6d is provided with a biaxial glasses-type stirring blade 7d. Since the reaction liquid to be transferred becomes highly viscous after the third vertical stirring reaction tank 6c, a gear pump 4b is provided.
- the amount of supplied heat may be particularly large, so that the internal heat exchangers 8a and 8b are respectively provided so that the heat medium temperature does not become excessively high. Is provided.
- distilling tubes 11a, 11b, 11c, and 11d for discharging by-products generated by the polycondensation reaction are attached to these four reactors, respectively.
- reflux condensers 9a and 9b and reflux pipes 10a and 10b are provided in order to return a part of the distillate to the reaction system.
- the reflux ratio can be controlled by appropriately adjusting the pressure of the reactor and the heat medium temperature of the reflux condenser.
- the distillation pipes 11a, 11b, 11c, and 11d are connected to condensers 12a, 12b, 12c, and 12d, respectively, and each reactor is in a predetermined depressurized state by a decompression device 13a, 13b, 13c, and 13d. To be kept.
- by-products such as phenol (monohydroxy compound) are continuously liquefied and recovered from the condensers 12a, 12b, 12c, and 12d attached to the respective reactors.
- a cold trap (not shown) is provided downstream of the condensers 12c and 12d attached to the third vertical stirring reaction tank 6c and the fourth horizontal stirring reactor 6d, respectively, so that by-products are continuously present. Solidified and recovered.
- the reaction liquid raised to a predetermined molecular weight is extracted from the fourth horizontal stirring reaction tank 6d and transferred to the extruder 15a by the gear pump 4c.
- the extruder 15a is equipped with a vacuum vent to remove residual low molecular components in the polycarbonate. Further, an antioxidant, a light stabilizer, a colorant, a release agent, or the like is added as necessary.
- Resin is supplied to the filter 15b by the gear pump 4d from the extruder 15a, and foreign matter is filtered.
- the resin that has passed through the filter 15b is extracted in a strand form from the die 15c, cooled with water in the strand cooling tank 16a, and then pelletized by the strand cutter 16b.
- the polycarbonate resin pellets thus obtained are pneumatically transported by the air blower 16c and sent to the product hopper 16d.
- a predetermined amount of product is packed in the product bag 16f by the measuring instrument 16e.
- the form of the extruder is not limited, but a uniaxial or biaxial extruder is used. Among them, a twin screw extruder is preferable for improving the devolatilization performance described later or for uniform kneading of the additive. In this case, the rotation direction of the shaft may be different or the same, but the same direction is preferable from the viewpoint of kneading performance. Not only can the supply of polycarbonate resin to the filter be stabilized by the use of an extruder, but also devolatilization or kneading of additives can be carried out simultaneously.
- vent ports may be one or plural, but preferably two or more.
- additives such as a thermal stabilizer, a release agent, or a colorant, which will be described later, can be kneaded using the extruder.
- the rotational speed of a shaft (hereinafter sometimes referred to as a screw) provided in the extruder is preferably 300 rpm or less, more preferably 250 rpm or less, More preferably, it is 200 rpm or less.
- the number of rotations of the screw is too small, not only may the devolatilization performance deteriorate, or the additive kneading performance deteriorates, but the throughput per unit time decreases, resulting in deterioration of productivity. Therefore, it is preferably 50 rpm or more, more preferably 70 rpm or more.
- the peripheral speed of the screw is appropriately determined by the screw diameter and the rotational speed of the extruder, but in order to suppress thermal deterioration such as coloring or molecular weight reduction due to heat generated by shearing of the polycarbonate resin, Usually, it is preferably 1.0 m / second or less, more preferably 0.6 m / second or less, and particularly preferably 0.4 m / second or less.
- the peripheral speed becomes too small, venting up during vacuum devolatilization tends to occur, or devolatilization performance or additive dispersion performance tends to decrease. Therefore, it is usually preferably 0.05 m / second or more. More preferably, it is 0.1 m / second or more.
- the screw of an extruder is composed of a plurality of elements (screw elements) in order to give various functions, and generally only a spiral screw (flight) mainly for the purpose of transporting resin.
- Consists of a full flight consisting of a kneading disk for resin kneading, a seal ring for resin sealing, etc., depending on the purpose, reverse flight with a screw in the direction opposite to the resin transport direction is also used It is done.
- the configuration of these screw elements is not limited, but it is preferable to have a kneading disk.
- the total length of the kneading disk is 20% of the total length of the screw. % Or less, more preferably 15% or less, and most preferably 10% or less.
- the total length of the kneading disk is too short, the performance during devolatilization or kneading of the additive may be deteriorated. It is preferably 3% or more of the length, and more preferably 5% or more.
- the kneading disk includes a forward feed type, an orthogonal type, and a reverse feed type with respect to the resin transport direction, and can be appropriately selected according to the viscosity of the resin used or the required performance.
- the material of the screw element it is preferable to increase the surface nickel content or the like to keep the iron content low, or to treat the surface hardness with TiN or CrN.
- the temperature of the resin when the polycarbonate resin is supplied in the molten state to the extruder is preferably 200 ° C. or higher, particularly 210 ° C. or higher, particularly 220 ° C. or higher. Further, the upper limit is preferably less than 250 ° C., more preferably less than 245 ° C., particularly preferably less than 240 ° C.
- the temperature of the polycarbonate resin supplied to the extruder is too low, not only the melt viscosity of the polycarbonate resin becomes too high and the supply may become unstable, but also the shear heat generation in the extruder increases and the polycarbonate resin When the temperature is too high, the polycarbonate resin is likely to be deteriorated, and the hue or molecular weight is decreased, or the mechanical strength is accordingly decreased.
- the temperature of the polycarbonate resin supplied to the extruder is controlled by a method such as controlling the internal temperature of the final polymerization reactor, controlling the temperature of the piping supplying the polycarbonate resin to the extruder, or installing a heat exchanger. can do.
- the temperature of the polycarbonate resin discharged from the extruder is preferably less than 280 ° C, more preferably less than 270 ° C, and particularly preferably less than 260 ° C.
- the polycarbonate resin discharged from the extruder is 280 ° C. or higher, the polycarbonate resin is likely to be deteriorated, which tends to cause a deterioration in hue, a decrease in molecular weight, or a decrease in mechanical strength associated therewith.
- the temperature of the polycarbonate resin discharged from the extruder becomes too low, the melt viscosity of the polycarbonate resin is high, the load on the extruder increases, screw rotation becomes unstable, and the motor is overloaded. Therefore, it is preferably 220 ° C. or higher, more preferably 230 ° C. or higher, and particularly preferably 240 ° C. or higher.
- the melt viscosity will decrease, and the shearing heat generation will tend to be suppressed accordingly.However, if the temperature of the polycarbonate resin itself is high, the deterioration tends to occur, the hue deteriorates or the molecular weight decreases, or accompanying it. Since there is a tendency to cause a decrease in mechanical strength, it is not easy to perform extrusion by preventing deterioration of a polycarbonate resin having high viscosity that is inferior in thermal stability.
- the temperature of the polycarbonate resin discharged from the extruder is usually controlled by the temperature of the polycarbonate resin to be supplied or the temperature of the heater attached to the barrel, but the amount of polycarbonate resin supplied to the extruder or the temperature of the extruder Since this may vary depending on the number of screw rotations, it is preferable to control these conditions together.
- filter In the present invention, filtration is performed with a filter in order to remove foreign matters such as burns or gels in the polycarbonate resin obtained by polycondensation. Among them, it is possible to remove residual monomers or by-product phenol by decompression devolatilization, and to extrude polycarbonate resin with an extruder and filter with a filter in order to mix additives such as heat stabilizer or mold release agent. preferable.
- Examples of the form of the filter include known ones such as a candle type, a pleat type, and a leaf disk type.
- a leaf disk type that can provide a large filtration area with respect to the storage container of the filter is preferable, and a plurality of combinations are preferably used so that a large filtration area can be obtained.
- the leaf disk type filter is configured by combining a holding member (also referred to as a retainer) with a filtering member (hereinafter also referred to as a medium), and the filters (in some cases, a plurality or a plurality of filters). ) Used in the form of a unit (sometimes called a filter unit) stored in a containment vessel.
- a type in which a plurality of aperture media are overlapped so that the differential pressure (pressure loss) of the filter is small and the apertures become finer in order from the resin intrusion direction is preferable.
- a type obtained by sintering metal powder it is also possible to use a type obtained by sintering metal powder.
- the opening of the filter is 50 ⁇ m or less as a 99% filtration accuracy, preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less.
- the filtration accuracy of 99% is 1 ⁇ m or more. Is preferred.
- the aperture defined as 99% filtration accuracy is the value of ⁇ when the ⁇ value represented by the following formula (8) determined in accordance with ISO 16889 (2008) is 100.
- ⁇ (number of particles on the primary side larger than ⁇ ⁇ m) / (number of particles on the secondary side larger than ⁇ ⁇ m) (8) (Here, the primary side is before filtration with a filter, and the secondary side is after filtration.)
- the material of the filter media is not limited as long as it has the strength and heat resistance necessary for resin filtration, but stainless steel such as SUS316 or SUS316L with a low iron content is particularly preferable.
- non-woven fabric type can be used in addition to regular weaving portions such as plain weave, twill weave, plain tatami mat or twill mat weave.
- a non-woven fabric type having a high gel-capturing ability, particularly a type in which steel wires constituting the non-woven fabric are sintered and fixed is preferable.
- the filter contains an iron component
- the resin tends to deteriorate during filtration at a high temperature exceeding 200 ° C. Therefore, as described above, in the case of stainless steel, the iron content is small. In addition, it is preferable to passivate it before use.
- the passivation treatment for example, a method in which the filter is immersed in an acid such as nitric acid, or an acid is passed through the filter to form a passivated surface, roasting in the presence of water vapor or oxygen ( Heating), a method using these in combination, and the like are mentioned, and it is preferable to perform both nitric acid treatment and roasting.
- the temperature when the filter is roasted is preferably 350 ° C. to 500 ° C., more preferably 350 ° C. to 450 ° C., and the roasting time is usually preferably 3 hours to 200 hours, More preferably, it is 5 hours to 100 hours.
- the temperature of roasting is too low or the time is too short, the formation of passivity is insufficient, and the polycarbonate resin tends to deteriorate during filtration.
- the temperature of roasting is too high or the time is too long, the filter media may be severely damaged and the required filtration accuracy may not be achieved.
- the concentration of nitric acid when the filter is treated with nitric acid is usually preferably 5 to 50% by weight, more preferably 10 to 30% by weight, and the temperature during the treatment is usually 5 ° C. It is preferably from -100 ° C, more preferably from 50 ° C to 90 ° C, and the treatment time is usually preferably from 5 minutes to 120 minutes, more preferably from 10 minutes to 60 minutes.
- the concentration of nitric acid is too low, the processing temperature is too low, or the processing time is too short, the formation of passives will be insufficient, the concentration of nitric acid will be too high, the processing temperature will be too high, or the processing time will be If it is too long, the filter media will be severely damaged and the required filtration accuracy may not be achieved.
- the filter is stored in a containment container because it facilitates filtration under pressure.
- the material of the storage container is not limited as long as it has strength and heat resistance that can withstand resin filtration, but is preferably a stainless steel such as SUS316 or SUS316L with a low iron content. If the iron content is large, the polycarbonate resin may be deteriorated as described above.
- the storage container of the filter may be arranged such that the supply port and the discharge port of polycarbonate resin are arranged substantially horizontally, arranged substantially vertically, or arranged obliquely.
- the supply port of the polycarbonate resin is disposed at the lower part of the filter storage container and the discharge port is disposed at the upper part.
- the differential pressure of the filter may increase and the filter may be damaged. If it is too large, the polycarbonate resin will be deteriorated during filtration, so it is preferably 1 minute to 20 minutes, more preferably 2 minutes to 10 minutes, and even more preferably 2 minutes to 5 minutes.
- the temperature of the polycarbonate resin before filtration supplied to the filter is preferably less than 280 ° C, more preferably less than 270 ° C, particularly preferably less than 265 ° C, and particularly preferably less than 260 ° C. .
- the temperature before filtration with the filter becomes too low, the melt viscosity of the polycarbonate resin is high, the load on the filter increases, and the filter may be damaged.
- ° C or higher more preferably 230 ° C or higher, particularly preferably 240 ° C or higher.
- the temperature of the polycarbonate resin after filtration is 200 ° C. or higher, preferably 220 ° C. or higher, more preferably 230 ° C. or higher. If the temperature of the polycarbonate resin after filtration using the filter is too low, the melt viscosity becomes high and the extruded strands are not stable and tend to be difficult to be pelletized with a rotary cutter or the like. There is.
- the temperature of the polycarbonate resin after filtration is less than 280 ° C, preferably less than 270 ° C, more preferably less than 265 ° C, and still more preferably less than 260 ° C. If the temperature of the polycarbonate resin after filtration using the filter is too high, the polycarbonate resin is likely to be thermally deteriorated, which tends to cause a deterioration in hue, a molecular weight, or a mechanical strength associated therewith.
- Examples of the resin temperature after the filtration include a method in which the resin discharged from the filter is taken out and directly measured, and a method in which a sensor is installed inside the pipe of the filter outlet channel and the like.
- the temperature of the discharged resin may be the resin temperature after filtration according to the present invention.
- a sensor is installed inside the pipe of the filter outlet channel, and the temperature of the resin discharged from a die installed near the filter outlet is measured. Both methods can also be implemented.
- the filter unit is usually provided with a heater composed of a plurality of blocks on the outside thereof for temperature control, but if the set temperature is too high, the polycarbonate resin may be deteriorated. It is set to 280 ° C. or lower, more preferably 260 ° C. or lower, particularly preferably 250 ° C. or lower.
- the melt viscosity becomes high and it is difficult to filter with a filter. Therefore, it is usually preferably 150 ° C. or higher, more preferably 180 ° C. or higher, particularly preferably 200 ° C. or higher.
- a pipe for guiding the polycarbonate resin discharged from the filter unit to the die is usually provided with a heater outside thereof, but since the polycarbonate resin may be deteriorated if its set temperature is too high, it is usually preferable. It is set to 280 ° C. or lower, more preferably 260 ° C. or lower, particularly preferably 250 ° C. or lower.
- the melt viscosity becomes high and the pressure loss in the piping increases, so that it is usually preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and particularly preferably 200 ° C. or higher.
- the residence time of the polycarbonate resin from the outlet of the filter unit to the die is long, the polycarbonate resin may be deteriorated. Therefore, it is usually preferably 1 to 30 minutes, more preferably 3 to 20 minutes.
- the temperature of the polycarbonate resin discharged from the die through filtration with the filter is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, further preferably 230 ° C. or higher,
- the upper limit is preferably less than 280 ° C, more preferably less than 270 ° C, even more preferably less than 265 ° C, and particularly preferably less than 260 ° C.
- the melt viscosity becomes high and the extruded strands are not stable and may be difficult to pelletize with a rotary cutter or the like There is sex.
- the temperature is too high, thermal degradation of the polycarbonate resin is likely to occur, which may lead to a deterioration in hue, a decrease in molecular weight, or a decrease in mechanical strength associated therewith.
- the temperature is usually preferably 280 ° C. or less, more preferably 260 ° C. or less, particularly preferably. Set to 250 ° C or lower.
- the melt viscosity becomes high and the pressure loss in the piping increases, so that it is usually preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and particularly preferably 200 ° C. or higher.
- the processing amount of the polycarbonate resin in the extruder, the rotational speed or peripheral speed of the screw, or the configuration of the element or the like can be selected as described above. Become important.
- the difference between the temperature of the polycarbonate resin before being filtered by the filter and the temperature of the polycarbonate resin after the filtration is preferably within 50 ° C, more preferably within 30 ° C, most preferably Preferably it is within 10 degreeC.
- the terminal double bond of the polycarbonate resin obtained by polycondensation by the transesterification reaction before being supplied to the filter is filtered using the filter at X ⁇ eq / g.
- the terminal double bond of the polycarbonate resin constituting the polycarbonate resin pellet obtained by discharging in the form of a strand and cooling using a cutter is Y ⁇ eq / g
- the following formula (2) is preferably satisfied.
- YX ⁇ 8 More preferably, YX ⁇ 8, particularly preferably YX ⁇ 5.
- YX By setting YX to 10 or less, it is possible to suppress the generation of coloring components that are considered to be derived from the double bond, and to suppress the generation of gas in or around the filter, so that the strand discharge is stable. It is preferable because it is easy to be pelletized with a cutter.
- Y is preferably 50 ⁇ eq / g or less, more preferably 30 ⁇ eq / g, and particularly preferably 20 ⁇ eq / g. If Y is too large, the polycarbonate resin pellets may be colored.
- the reduced viscosity ( ⁇ sp / c) of the polycarbonate resin before being supplied to the filter is filtered using A, the filter, discharged from the die in the form of a strand, and cooled. Thereafter, when the reduced viscosity ( ⁇ sp / c) of the polycarbonate resin pellet obtained using a cutter is B, it is preferable to satisfy the following formula (3). 0.8 ⁇ B / A ⁇ 1.1 (3)
- B / A By setting B / A to more than 0.8, it is possible to suppress the generation of a coloring component or a coloring precursor that is considered to be generated by a side reaction, which is preferable.
- B / A ⁇ 1.0 when the reduced viscosity rises in the polymer filter, the generation of foreign matters such as gel or burnt rises, and therefore it is more preferable that B / A ⁇ 1.0. A method for measuring the reduced viscosity will be described later.
- B / a it is possible to suppress the generation of a coloring component or a coloring precursor that is considered to be generated by a side reaction, which is preferable.
- B / a ⁇ 1.0 it is more preferable that B / a ⁇ 1.0.
- the temperature of the polycarbonate resin in the final reactor In order to bring the change in the reduced viscosity in the polymer filter or the extruder into the above range, the temperature of the polycarbonate resin in the final reactor, the temperature of the polycarbonate resin entering the polymer filter, the temperature of the polycarbonate resin discharged from the polymer filter, Selection of throughput per unit time or opening of polymer filter, temperature control or residence time from polymer filter to die, when using an extruder, temperature of polycarbonate resin supplied to the extruder, discharge from the extruder It is important to select the temperature of the polycarbonate resin to be used, the devolatilization pressure, the presence or absence of water injection, the amount of water injection, the rotation speed or peripheral speed of the screw, or the element configuration.
- class 7 as defined in JIS B 9920 (2002), more preferably, in order to prevent foreign matter from being mixed from the outside air. It is preferable to carry out in a clean room with higher cleanliness than class 6.
- the polycarbonate resin filtered by the filter is cooled and solidified, and pelletized by a rotary cutter or the like, and it is preferable to use a cooling method such as air cooling or water cooling when pelletizing.
- the air used for air cooling is preferably air from which foreign matter in the air has been removed in advance with a hepa filter or the like to prevent reattachment of foreign matter in the air.
- water cooling it is preferable to use water from which metal in water has been removed with an ion exchange resin or the like, and further, foreign matter in water has been removed with the filter.
- the opening of the filter to be used is preferably 10 to 0.45 ⁇ m in terms of filtration accuracy with 99.9% removal.
- a heat stabilizer a neutralizing agent, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, a lubricant, a lubricant, a plasticizer, a phase, which are generally known in the extruder.
- a solubilizer or a flame retardant may be added and kneaded.
- the shape of the raw material filtration filter may be any type such as basket type, disk type, leaf disk type, tube type, flat cylindrical type, or pleated cylindrical type, among which compact and has a large filtration area.
- a pleated type that can be taken is preferred.
- the filter medium constituting the raw material filter may be any of metal wind, laminated metal mesh, metal nonwoven fabric, porous metal plate, etc., but from the viewpoint of filtration accuracy, a laminated metal mesh or metal nonwoven fabric is preferred, and metal A type in which a nonwoven fabric is sintered and fixed is preferable.
- metal or resin ceramics can be used. From the viewpoint of heat resistance and color reduction, a metal filter having an iron content of 80% or less. Among them, stainless steel such as SUS304, SUS316, SUS316L, or SUS310S is preferable.
- the filter in the unit on the upstream side is preferably used.
- C is preferably larger than D (C> D) in at least one combination.
- the opening of the raw material filtration filter is not particularly limited, but in at least one of the raw material filtration filters, the filtration accuracy of 99.9% is preferably 10 ⁇ m or less, and the filter unit constituting the raw material filtration filter includes In the case of a plurality of arrangements, it is preferably 8 ⁇ m or more, more preferably 10 ⁇ m or more on the most upstream side, and preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less on the most downstream side.
- the opening of the said raw material filtration filter said here is determined based on the above-mentioned ISO16889 (2008).
- the temperature of the raw material fluid when the raw material is passed through the raw material filtration filter there is no restriction on the temperature of the raw material fluid when the raw material is passed through the raw material filtration filter, but if it is too low, the raw material is solidified, and if it is too high, there is a problem such as thermal decomposition. ⁇ 200 ° C., more preferably 100 ° C. to 150 ° C.
- any of the raw materials to be used may be filtered, or all of the raw materials may be filtered.
- the method is not limited, and the dihydroxy compound and the carbonic acid diester are not limited.
- the raw material mixture may be filtered, or may be mixed after separately filtering.
- the reaction liquid in the middle of a polycondensation reaction can also be filtered with the filter similar to the said raw material filtration filter.
- the yellow index value of the polycarbonate resin pellet obtained by the method of the present invention is preferably 70 or less, more preferably 30 or less, particularly preferably 15 or less, and most preferably 10 or less. In order to lower the yellow index value, as described above, it is necessary to appropriately select the monomer preparation conditions, the polymerization reaction conditions, the filtration conditions, and the extrusion conditions or screw elements when using an extruder.
- the reduced viscosity measured using the Ubbelohde viscosity tube at a concentration of 0.6 g / dL and a temperature of 20.0 ° C. ⁇ 0.1 ° C. in methylene chloride using the polycarbonate resin pellet of the present invention is 0.3 dL / g or more. Preferably, it is 0.35 dL / g or more, more preferably 0.4 or more.
- the upper limit of the reduced viscosity is preferably 1.2 dL / g or less, more preferably 0.8 dL / g or less, and particularly preferably 0.7 dL / g or less.
- the mechanical strength of the molded product may be small, and if it is too large, the fluidity during molding tends to decrease, which tends to reduce productivity or moldability, as well as filtration or Deterioration during extrusion may be severe.
- the melt viscosity at a shear rate of 91.2 sec ⁇ 1 measured at 240 ° C. is preferably 500 Pa ⁇ s or more, more preferably 800 Pa ⁇ s or more, particularly Preferably, it is 1000 Pa ⁇ s or more, and the upper limit thereof is preferably 3000 Pa ⁇ s or less, more preferably 2000 Pa ⁇ s or less.
- melt viscosity is too low, the mechanical strength of the molded product tends to be inferior. If it is too high, as described above, shear heat generation in the filter or the extruder increases, and the deterioration during filtration or extrusion may become severe. There is. In addition, since the melt viscosity varies depending on the molecular structure in addition to the molecular weight, it is important to select these according to the required performance and control them within the above range.
- the glass transition temperature when measured with a differential scanning calorimeter (DSC) using the polycarbonate resin pellets obtained by the method of the present invention is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, more preferably 90 ° C. or higher. If the glass transition temperature is too low, the heat resistance is inferior, so the use as a molded product is limited.
- the melt viscosity at the time of filtration with a filter becomes too high, and may cause deterioration of the polycarbonate resin. Therefore, it is preferably less than 160 ° C, more preferably less than 145 ° C, Preferably it is less than 140 degreeC, Most preferably, it is less than 130 degreeC.
- the glass transition temperature of the present invention means that the temperature is raised from room temperature to a temperature sufficiently exceeding the glass transition temperature at a heating rate of 20 ° C./min in a nitrogen stream, and after maintaining the temperature for 3 minutes, it is 20 ° C. to 30 ° C. Obtained by heating at a rate of 20 ° C./min to a temperature well above the glass transition temperature (obtained by the second temperature increase). This refers to the extrapolated glass transition start temperature obtained from DSC data.
- the concentration of the terminal group represented by the following structural formula (9) of the polycarbonate resin constituting the polycarbonate resin pellet obtained in the present invention is preferably 20 ⁇ eq / g or more, more preferably 40 ⁇ eq / g or more, particularly preferably. It is 50 ⁇ eq / g or more.
- the concentration of the end group is too low, coloring tends to increase during filtration. If it is too high, gas tends to be generated at the time of filtration, and there is a possibility of causing problems such as running out of gas in the strand. Therefore, it is preferably 200 ⁇ eq / g or less, more preferably 150 ⁇ eq / g or less, particularly preferably. 100 ⁇ eq / g or less.
- Examples of the method for controlling the concentration of the terminal group represented by the structural formula (9) include a method for controlling the molar ratio of the dihydroxy compound containing the dihydroxy compound of the present invention and the diester carbonate, or a transesterification reaction.
- polymerization temperature of time, the temperature of a reflux condenser, etc. according to the easiness of volatilization of a monomer is mentioned.
- the use of a reactor having a reflux condenser at the initial stage of polymerization is effective for stabilizing the terminal group concentration.
- the polycarbonate resin of 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 (7), Alternatively, it is inevitable that aromatic monohydroxy compounds such as substituted phenols are by-produced and remain in the polycarbonate resin.
- the content of the compound in the polycarbonate resin obtained by cooling and solidifying is determined by extrusion with a vacuum vent. It is preferable that the content is less than 0.1% by mass, more preferably less than 0.05% by mass, and particularly preferably less than 0.03% by mass. However, it is difficult to remove these compounds completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 0.0001% by mass.
- aromatic monohydroxy compounds may naturally have a substituent depending on the raw material to be used, and may have, for example, an alkyl group having 5 or less carbon atoms.
- diphenyl carbonate is used as the carbonic acid diester, the aromatic monohydroxy compound is phenol.
- the polycarbonate resin pellet obtained by the method of 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. Also, before performing various moldings, if necessary, the resin is heat stabilizer, neutralizer, UV absorber, mold release agent, colorant, antistatic agent, lubricant, lubricant, plasticizer, compatibilizing Additives such as additives or flame retardants can also be mixed with a tumbler, super mixer, floater, V-type blender, nauter mixer, Banbury mixer or extruder.
- the foreign matter having a thickness of 25 ⁇ m or more contained in a 30 ⁇ m ⁇ 5 ⁇ m-thick film formed from the resin is preferably 1000 / m 2.
- Polycarbonate resin pellets obtained by the method of the present invention are, for example, aromatic polycarbonate, aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic resin, amorphous polyolefin, synthetic resin such as ABS or AS, polylactic acid or It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as polybutylene succinate or rubber.
- polycarbonate resin pellets that are excellent in thermal stability, hue, and mechanical strength and have few foreign substances.
- the barrel set temperature of a 20 mm diameter single screw extruder equipped with a T die is 210 ° C, 220 ° C, 230 ° C, 230 ° C, 220 ° C from the pellet supply side, and polycarbonate resin pellets are melt extruded.
- a film having a thickness of 35 ⁇ m ⁇ 5 ⁇ m was formed using a cooling roll, and the number of foreign matters of 25 ⁇ m or more per 1 m 2 was measured using an optical control system (Film Quality Testing System (model FSA100)).
- Example 1 (First stage reaction) In a polymerization reactor equipped with a heat medium jacket and a stirring blade using oil as a heat medium, a distillation pipe connected to a vacuum pump and a condenser, the molar ratio of ISB / TCDDM / DPC is 70/30/100.
- the cesium carbonate in the aqueous solution was charged to 2.5 ⁇ 10 ⁇ 6 mol (converted to cesium metal atoms) per 1 mol of all dihydroxy compounds, and then sufficiently substituted with nitrogen (oxygen concentration 0.0005 vol% to 0.001 vol%).
- the DPC used was purified by distillation to have a chloride ion concentration of 10 ppb or less.
- a heated heat medium is circulated through the heat medium jacket of the reactor, and stirring is started when the reaction liquid (that is, the internal temperature) reaches 100 ° C., and the contents are kept while maintaining the internal temperature at 100 ° C. Thaw and homogenize.
- the temperature rise is started, the internal temperature is set to 220 ° C. in 40 minutes, the pressure reduction is started when the internal temperature reaches 220 ° C., and 13.3 kPa (absolute pressure, the same applies hereinafter) in 90 minutes.
- the temperature of the oil introduced into the heat medium jacket (heat medium jacket inlet temperature) is appropriately adjusted so that the vapor of phenol generated by the reaction starts to distill and the internal temperature is controlled to be constant at 220 ° C. It was adjusted.
- the temperature of the heat medium oil was set at 242 ° C., and other time periods were set at less than 242 ° C.
- the polycarbonate oligomer obtained in the first stage was transferred to a polymerization reactor equipped with a heat medium jacket using oil as a heat medium, a stirring blade, and a distillation pipe connected to a vacuum pump under a nitrogen atmosphere.
- a condenser using hot water (inlet temperature 45 ° C.) as a refrigerant and a cold trap using dry ice as a refrigerant were installed downstream of the condenser.
- the resulting pellet had a reduced viscosity of 0.362, a terminal phenyl group concentration of 66 ⁇ eq / g, a terminal double bond of 7.5 ⁇ eq / g, a YI of 25.4, a phenol content of 965 ppm, a DPC content of 19 ppm, The amount of foreign matter of 25 ⁇ m or more was 3035 / m 2 .
- a leaf disk filter [manufactured by Nippon Seisen Co., Ltd.] [materials made of stainless steel (with an outer diameter of 112 mm, an inner diameter of 38 mm, and a filtration accuracy of 99%] in a containment container having an internal volume of 0.91 (L) downstream thereof.
- a filter unit equipped with four SUS304, SUS316)] was arranged. Prior to use, the filter was roasted at 310 ° C.
- the inlet side and outlet side of the filter unit were set to be horizontal, and a die for forming a strand was attached to the outlet side of the filter unit.
- the kneading disk length (kneading element ratio) in the length of the elements constituting the entire screw of the extruder was 13.9%.
- Sensors for measuring the resin temperature are installed in the outlet channel of the extruder, the inlet channel of the filter unit, and the outlet channel of the filter unit.
- the barrel temperature of the extruder is set to 220 from the pellet supply side. C, 230 ° C, 230 ° C, 235 ° C, 240 ° C, 240 ° C, 240 ° C, 240 ° C, 240 ° C.
- the polycarbonate resin pellets obtained above were supplied to this at 10 kg / h, and at the same time, the screw rotation of the extruder was set to 100 rpm, and devolatilization was performed from the vent port using a vacuum pump. At this time, the pressure in the vent portion was 300 Pa or less in absolute pressure.
- the temperature of the polycarbonate resin discharged from the die through the filter unit was measured using a thermometer, and it was 257 ° C.
- the discharged polycarbonate resin was cooled with water in the form of a strand, solidified, and then rotated with a rotary cutter. Pelletized.
- the reduced viscosity of the pellets was 0.332, YI was 59.6, the phenol content was 427 ppm, and the DPC content was 25 ppm. Further, the pellet was dried at 110 ° C. for 12 hours using a clean oven, a film was formed by the method described above, and the amount of foreign matter was measured. These results are shown in Table 1.
- the above kneading element ratio is a value calculated from the following formula.
- Kneading element ratio (%) (total length of kneading disc / total length of screw) x 100
- Example 2 The same procedure as in Example 1 was performed except that the amount of resin supplied to the extruder was 15 kg / h and the screw rotation speed was 130 rpm.
- the temperature of the polycarbonate resin discharged from the die was 264 ° C., the reduced viscosity was 0.334, the YI of the pellet was 63.2, the phenol content was 476 ppm, and the DPC content was 27 ppm.
- Example 3 The same procedure as in Example 1 was performed except that the amount of resin supplied to the extruder was 20 kg / h and the screw rotation speed was 150 rpm.
- the temperature of the polycarbonate resin discharged from the die was 269 ° C., the reduced viscosity was 0.328, the YI of the pellet was 65.6, the phenol content was 482 ppm, and the DPC content was 29 ppm.
- Example 4 The same operation as in Example 1 was performed except that a leaf disk filter having a filtration accuracy of 99% of 40 ⁇ m was used.
- the YI of the pellet was 55.3, which was better than that of Example 1, but the amount of foreign matter slightly increased to 1710 / m 2 .
- Example 5 In the raw material preparation tank sufficiently substituted with nitrogen (oxygen concentration 0.0005 vol% to 0.001 vol%), the raw material prepared so that the ISB / CHDM / DPC molar ratio is 50/50/100 is used as the heat medium.
- the raw material preparation tank sufficiently substituted with nitrogen (oxygen concentration 0.0005 vol% to 0.001 vol%), the raw material prepared so that the ISB / CHDM / DPC molar ratio is 50/50/100 is used as the heat medium.
- a raw material supply pipe From the connected catalyst supply pipe, calcium acetate monohydrate in an aqueous solution was continuously supplied so as to be 1.25 ⁇ 10 ⁇ 6 mol (calcium metal atom equivalent) per 1 mol of all dihydroxy compounds.
- the upstream raw material filtration filter opening is 10 ⁇ m, downstream The mesh opening was 1 ⁇ m.
- the distillation pipe is provided with a reflux condenser using oil (inlet temperature 130 ° C.) as a refrigerant, and phenol and the like that are not condensed in the reflux condenser.
- a condenser using warm water (inlet temperature 45 ° C.) as a refrigerant was disposed.
- the internal temperature is controlled to be constant at 185 ° C.
- the pressure is 25 kPa
- the residence time is 1.5 hours, and the reaction solution is continuously extracted from the bottom of the reaction tank.
- the second polymerization reactor includes a heat medium jacket, a heat medium internal coil, a stirring blade, a distillation pipe connected to a vacuum pump, and a distillation pipe having a reflux condenser and a condenser.
- the inner temperature was 213 ° C.
- the pressure was 14 kPa
- the residence time was controlled to be constant at 1 hour, and the reaction solution was continuously withdrawn from the bottom of the reaction vessel and supplied to the third polymerization reactor.
- the third polymerization reactor is controlled so as to be constant at an internal temperature of 229 ° C., a pressure of 6 kPa, and a residence time of 1 hour.
- the polycondensation reaction proceeds while distilling off the by-produced phenol, and the reaction solution is transferred to the reaction vessel. It was continuously extracted from the bottom and supplied to a horizontal stirring reactor (fourth polymerization reactor) having two horizontal rotating shafts and mutually discontinuous stirring blades mounted substantially perpendicular to the horizontal shaft.
- the fourth polymerization reactor was controlled so that the internal temperature near the inlet was 228 ° C., the internal temperature near the outlet was 240 ° C., the pressure was 0.07 kPa, and the residence time was 2 hours, and the polycondensation reaction was further advanced. .
- the extruder 0.1% of water was supplied to the polycarbonate resin to be treated, and the vent port was connected to a vacuum pump to remove volatile components contained in the polycarbonate resin.
- the barrel temperature of the extruder was set to 245 ° C. for the 4 blocks upstream, 225 ° C. for the 6 blocks downstream, and the screw rotation speed was 250 rotations.
- the polycarbonate resin processed by the extruder was supplied to a filter unit having a resin inlet at the bottom and an outlet at the top through a gear pump installed at the outlet.
- Table 2 shows the temperature of the resin sampled before the filter unit and various measured values.
- a leaf disk filter manufactured by Nippon Pole Co., Ltd. having a mesh size of 7 ⁇ m was mounted inside the filter unit to remove foreign substances in the polycarbonate resin.
- the filter Prior to use, the filter was roasted at 310 ° C. for 40 hours in a water vapor atmosphere and then at 420 ° C. for 52 hours in an air atmosphere, cooled to room temperature, and then immersed in a 30 wt% nitric acid aqueous solution for 30 minutes. Then, an oxide film was formed, washed and dried.
- the filter unit was equipped with a heater composed of a plurality of blocks, and each temperature was set to 230 to 240 ° C.
- a die On the outlet side of the filter unit, a die was installed through a polymer pipe equipped with a heater composed of a plurality of blocks. The set temperature of the polymer pipe heater was set to 220 to 230 ° C, and the heater of the dice was set to 220 ° C.
- the filter outlet resin temperature and the die outlet resin temperature were measured in the same manner as in Example 1.
- the polycarbonate resin was extracted in the form of a strand in a room maintained at a class 10000 cleanness from the die, solidified in a water tank, and pelletized with a rotary cutter.
- the analytical values are shown in Table 2.
- Example 6 The internal temperature of the first polymerization reactor is 194 ° C., the pressure is 27 kPa, the internal temperature of the second polymerization reactor is 190 ° C., the pressure is 19 kPa, the internal temperature of the third polymerization reactor is 213 ° C., the pressure is 7.5 kPa, The same procedure as in Example 1 was performed except that the inner temperature near the inlet of the fourth polymerization reactor was 214 ° C., the inner temperature near the outlet was 228 ° C., the pressure was 0.7 kPa, and the die heater was set to 230 ° C. It was.
- Example 7 The internal temperature of the first polymerization reactor is 190 ° C., the pressure is 25 kPa, the internal temperature of the second polymerization reactor is 196 ° C., the pressure is 17.7 kPa, the internal temperature of the third polymerization reactor is 215 ° C., and the pressure is 6. 9 kPa, the internal temperature near the inlet of the fourth polymerization reactor is 218 ° C., the internal temperature near the outlet is 232 ° C., the pressure is 0.9 kPa, the barrel temperature of the extruder is set to 240 ° C. for the upstream 4 blocks, and the downstream The same procedure as in Example 1 was conducted except that the above 6 blocks were changed to 185 ° C.
- Example 8 In the raw material preparation tank, the molar ratio of ISB / CHDM / DPC is adjusted to 70/30/100, the internal temperature of the first polymerization reactor is 188 ° C., the pressure is 24.2 kPa, and the second polymerization reactor The internal temperature was 194 ° C., the pressure was 19.9 kPa, the internal temperature of the third polymerization reactor was 214 ° C., the pressure was 9.9 kPa, the internal temperature near the inlet of the fourth polymerization reactor was 218 ° C., and the internal temperature near the outlet Was 232 ° C., the pressure was 0.1 kPa, the barrel temperature of the extruder was set in the same manner as in Example 1 except that the upstream 4 blocks were 240 ° C. and the downstream 6 blocks were 195 ° C.
- Example 9 The same operation as in Example 6 was performed except that the aperture of the filter was changed to 22 ⁇ m. The pressure loss in the polymer filter was reduced, the decrease in molecular weight and the increase in double bond ends tended to be suppressed, and the pellet color tone was improved, but the amount of foreign matter increased.
- Example 10 The same operation as in Example 9 was performed except that the total length of the kneading disk of the extruder was 12% of the total length of the screw.
- the internal temperature of the third polymerization reactor is 240 ° C.
- the pressure is 4 kPa
- the internal temperature near the inlet of the fourth polymerization reactor is 240 ° C.
- the internal temperature near the outlet is 252 ° C.
- the pressure is 0.02 kPa
- the barrel temperature of the extruder The upstream 4 blocks are 250 ° C
- the downstream 6 blocks are 260 ° C
- the screw speed is 280rpm
- the filter unit heater set temperature is 270 to 280 ° C
- the polymer pipe heater set temperature is 270 to 280 ° C.
- the same procedure as in Example 1 was performed except that the die heater was set at 280 ° C.
- the pressure loss in the polymer filter tended to be suppressed, the temperature of the polycarbonate resin discharged from the die was 285 ° C., and it was markedly colored. Further, gas was generated from the die, the strands were disturbed, and pellets could not be obtained.
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JP2017165892A (ja) * | 2016-03-17 | 2017-09-21 | 三菱ケミカル株式会社 | 透明樹脂フィルム |
JP2018036535A (ja) * | 2016-08-31 | 2018-03-08 | 三菱ケミカル株式会社 | 厚み位相差(Rth)が負の値を有するフィルムの製造方法 |
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KR102013975B1 (ko) * | 2012-04-18 | 2019-08-23 | 데이진 가부시키가이샤 | 코폴리카보네이트 |
JP6006653B2 (ja) * | 2013-02-04 | 2016-10-12 | 出光興産株式会社 | ポリカーボネート樹脂用押出造粒装置およびポリカーボネート樹脂押出造粒方法 |
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KR102404309B1 (ko) * | 2016-03-30 | 2022-05-31 | 미츠비시 가스 가가쿠 가부시키가이샤 | 방향족 폴리카보네이트 수지 조성물 및 방향족 폴리카보네이트 수지의 제조 방법 |
CN111993616A (zh) * | 2020-08-10 | 2020-11-27 | 广西长科新材料有限公司 | 一种高效br和sbr橡胶的溶解设备 |
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