WO2011071162A1 - ポリカーボネート樹脂組成物並びにこれを成形して得られる成形体、フィルム、プレート及び射出成形品 - Google Patents
ポリカーボネート樹脂組成物並びにこれを成形して得られる成形体、フィルム、プレート及び射出成形品 Download PDFInfo
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- WO2011071162A1 WO2011071162A1 PCT/JP2010/072282 JP2010072282W WO2011071162A1 WO 2011071162 A1 WO2011071162 A1 WO 2011071162A1 JP 2010072282 W JP2010072282 W JP 2010072282W WO 2011071162 A1 WO2011071162 A1 WO 2011071162A1
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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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
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- 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, transparency, hue, heat resistance, thermal stability, moldability, and mechanical strength, and a molded body, film, plate and injection molded product thereof.
- Polyvinyl chloride resin which has been known as a resin that has a good balance of physical properties such as transparency and mechanical properties, can be widely controlled by plasticizers and various compounding agents depending on the application. Has been used for various purposes. However, in recent years, from the viewpoint of environmental problems and the like, the conversion from polyvinyl chloride resin to other resins has been actively studied.
- One of the promising candidates for a substitute resin for polyvinyl chloride resin is a polycarbonate resin excellent in transparency, heat resistance, and impact resistance, and is used in various applications.
- 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.
- 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. .
- the releasability is poor at the time of melt molding and it is difficult to use it for a transparent material or an optical material.
- the polycarbonate resin has a high melt viscosity and low fluidity, and therefore has a drawback that it is inferior in moldability when molding a sheet, film, molded product or the like.
- polycarbonate resins when used in optical applications, polycarbonate resins have a high photoelastic coefficient and are liable to cause a phase difference due to stress.
- 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, and thus 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 (for example, Patent Document 8).
- Patent Document 9 discloses a resin composition in which a polycarbonate resin and a polyester resin such as polybutylene terephthalate and polyethylene terephthalate are mixed
- Patent Document 10 discloses a transesterification rate of the polycarbonate resin and the polyester resin.
- Patent Documents 11 and 12 disclose resin compositions made of a polycarbonate resin and an amorphous polyester resin.
- 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 secondary processed product obtained from the conventional resin composition as disclosed in Patent Document 9 still does not satisfy sufficient transparency. This is presumably because the transesterification reaction between the polycarbonate resin and the polyester resin does not proceed sufficiently. Further, the resin composition disclosed in Patent Document 10 has problems such as difficulty in controlling the transesterification reaction and the need to use a polycarbonate resin having a functional group at the terminal.
- Patent Document 11 and Patent Document 12 are excellent in transparency, heat resistance, and impact resistance, the photoelastic coefficient is increased by mixing an amorphous polyester resin. There was a problem that it would be even higher.
- An object of the present invention is to provide a polycarbonate resin composition excellent in weather resistance, transparency, hue, heat resistance, thermal stability, moldability, and mechanical strength, and a molded product thereof, by solving the above-mentioned conventional problems. There is to do.
- the present inventors have the following polycarbonate resin composition not only has excellent light resistance, but also excellent transparency, hue, heat resistance, thermal stability, It has been found that it has moldability and mechanical strength, and has reached the present invention. That is, the gist of the present invention resides in the following [1] to [20].
- the polycarbonate resin composition whose ratio of the structural unit derived from is 45 mol% or more.
- the polycarbonate resin composition (X) has a single glass transition temperature, and the glass transition temperature is equal to or higher than the glass transition temperature of the aliphatic polycarbonate resin (A), and the glass of the aromatic polycarbonate resin (B).
- the ratio of the structural unit derived from the dihydroxy compound (b) of the aliphatic hydrocarbon to the structural unit derived from all the dihydroxy compounds in the aliphatic polycarbonate resin (A) is 45 mol% or more and 80 mol% or less,
- the polycarbonate resin (A) used in the present invention is not particularly limited in its production method.
- the dihydroxy compound (a) having a portion represented by the following formula (1) in a general form and a part of the structure, and an aliphatic group It can be obtained by polycondensation by a transesterification reaction using a dihydroxy compound containing a hydrocarbon dihydroxy compound (b) and a carbonic acid diester as raw materials.
- the polycarbonate resin (A) used in the present invention is a structural unit derived from a dihydroxy compound (a) having a moiety represented by the following formula (1) and a structural unit derived from an aliphatic hydrocarbon dihydroxy compound (b). Including.
- the site represented by the formula (1) is a part of —CH 2 —O—H 2 is excluded.
- the polycarbonate resin composition of the present invention comprises at least a structural unit derived from a dihydroxy compound having a site represented by the formula (1) and a structural unit derived from an aliphatic hydrocarbon dihydroxy compound (b). It may contain (A) and may be a polycarbonate copolymer further containing a structural unit derived from another dihydroxy compound other than the structural unit derived from the dihydroxy compound. Moreover, in this invention, polycarbonate resin (A) may be used individually by 1 type, and may mix and use 2 or more types.
- the polycarbonate resin (A) is also understood as the aromatic polycarbonate resin (B) described later.
- one type of polycarbonate does not serve as both the polycarbonate resin (A) and the aromatic polycarbonate resin (B), and the polycarbonate resin (A) is derived from the aromatic dihydroxy compound.
- the polycarbonate resin composition of the present invention contains at least one selected from the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in addition to the polycarbonate resin (A). Includes polycarbonate.
- dihydroxy compound examples of the dihydroxy compound used in the polycarbonate resin (A) according to the present invention include a dihydroxy compound (a) having a portion represented by the formula (1) in a part of the structure, and an aliphatic hydrocarbon dihydroxy compound (b). If it contains, it will not specifically limit.
- dihydroxy compound (a) having a site represented by the formula (1) in a part of the structure include oxyalkylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene 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-butyl Phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphen ) Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9
- oxyalkylene glycols such as diethylene glycol and triethylene glycol and compounds having a cyclic ether structure are preferable.
- anhydrous sugar alcohols typified by dihydroxy compounds represented by the following formula (2)
- a compound having a cyclic ether structure represented by the following formula (3) is preferred.
- R 1 to R 4 are each independently an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.
- dihydroxy compound represented by the above formula (2) examples include isosorbide, isomannide and isoidet which are in a stereoisomeric relationship, and these may be used alone or in combination of two or more. May be.
- 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).
- various kinds that are abundant and easily available as plant-derived resources are used.
- 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 aliphatic hydrocarbon dihydroxy compound (b) is a compound having an aliphatic hydrocarbon skeleton and two hydroxy groups, and if the aliphatic hydrocarbon skeleton is a hydrocarbon skeleton having no unsaturated bond, branching is performed. It may have a cyclic structure. In the case of a compound having a cyclic structure hydrocarbon skeleton and two hydroxy groups, the hydroxy group may be directly bonded to the cyclic structure or may be bonded to the cyclic structure via a saturated hydrocarbon group. .
- the cyclic structure may be monocyclic or polycyclic.
- linear aliphatic hydrocarbon dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-heptanediol, and 1,6-hexanediol, neopentyl
- dihydroxy compounds of linear branched aliphatic hydrocarbons such as glycol and hexylene glycol
- dihydroxy compounds of alicyclic hydrocarbons such as 1,2-cyclohexanediol and 1,4-cyclohexanedimethanol.
- Examples of the alicyclic hydrocarbon dihydroxy compound include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol; Cyclohexenediols such as 4-cyclohexene-1,2-diol, cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 4 -Cyclohexene dimethanol such as cyclohexene-1,2-diol, norbornane dimethanol such as 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1 , - adamantan
- alicyclic hydrocarbon dihydroxy compounds are preferred, more preferably those having cyclohexane in their structure, and in particular, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1, 4-Cyclohexanedimethanol is preferred.
- the lower limit of the proportion of structural units derived from the aliphatic hydrocarbon dihydroxy compound (b) to the structural units derived from all dihydroxy compounds in the polycarbonate resin (A) is 45 mol% or more, usually 50 mol% or more.
- the amount is preferably 52 mol% or more, more preferably 55 mol% or more, and particularly preferably 60 mol% or more.
- the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, more preferably 75 mol% or less, and particularly preferably 70 mol% or less.
- the polycarbonate resin (A) used in the present invention comprises a structural unit derived from the dihydroxy compound (a) having a portion represented by the formula (1) in a part of the structure, and an aliphatic hydrocarbon dihydroxy compound (b).
- the structural unit derived from As long as the structural unit derived from is contained, the structural unit derived from other dihydroxy compounds other than those dihydroxy compounds may be included.
- these other dihydroxy compounds it is possible to obtain the effects of improving the flexibility and moldability of the polycarbonate resin (A), but the content ratio of the structural units derived from the other dihydroxy compounds If the amount is too large, mechanical properties and heat resistance may be reduced.
- the amount of structural units derived from other dihydroxy compounds relative to all structural units derived from dihydroxy compounds is preferably 40 moles relative to all structural units derived from dihydroxy compounds. % Or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, and particularly preferably 10 mol% or less.
- a polycarbonate resin having a structure different from that of the aromatic polycarbonate resin (B) is used as the polycarbonate resin (A).
- 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane 2, 2-bis (4-hydroxy-3,5-diethylphenyl) propane
- 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane 2,2-bis (4-hydroxy-3, 5-Dibromophenyl) propane
- 2,2-bis (4-hydroxyphenyl) pentane 2,4'-dihydroxy-diphenylmethane
- bis (4-hydroxyphenyl) methane bis (4-hydroxy-5-nitrophenyl) methane
- 1,1-bis (4-hydroxyphenyl) ethane 1,1-bis (4-hydroxyphenyl) ethane
- 3,3-bis (4-hydroxyphenyl) pentane -Bis (4-hydroxyphenyl) cyclohexane
- bis (4-hydroxyphenyl) sulfone 2,4'-dihydroxydiphenylsulfone
- dihydroxy compound examples include an aliphatic dihydroxy compound described in International Publication No. 2004/111106 and an alicyclic dihydroxy compound described in International Publication No. 2007/148604.
- structural units derived from the above aliphatic dihydroxy compounds selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. It is preferable to include a structural unit derived from at least one compound.
- the six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond.
- the heat resistance of the obtained polycarbonate can be increased.
- the number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, more preferably 30 or less.
- Examples of the alicyclic dihydroxy compound containing the 5-membered ring structure or 6-membered ring structure include those described in the above-mentioned International Publication No. 2007/148604, such as tricyclodecane dimethanol, adamantanediol and pentacyclo. Pentadecanedimethanol can be preferably exemplified, and these may be used alone or in combination of two or more.
- the glass transition temperature of the aliphatic 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 85 ° C. or higher and 105 ° C. or lower. Is more preferable.
- the reduced viscosity which is an index of the molecular weight of the aliphatic polycarbonate resin (A) was prepared by using methylene chloride as a solvent and adjusting the polycarbonate concentration to 0.60 g / dl precisely at a temperature of 20.0 ° C. ⁇ 0.1 ° C. Usually, it is 0.20 dl / g or more and 1.0 dl / g or less, preferably 0.3 dl / g or more and 0.8 dl / g or less. If the reduced viscosity of the aliphatic polycarbonate resin (A) is too low, the mechanical strength when molded into a lens or the like tends to decrease. On the other hand, if the reduced viscosity of the aliphatic polycarbonate resin (A) is excessively high, fluidity during molding is lowered, cycle characteristics are lowered, and distortion of the molded product tends to increase.
- 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 Inorganic 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 formula (4) 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.
- the carbonic acid diester represented by the formula (4) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, preferably diphenyl carbonate.
- Substituted diphenyl carbonate particularly preferably 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.
- 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 formula (4) 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 that can be used in the production of the polycarbonate resin (A) used in the present invention (hereinafter sometimes simply referred to as a catalyst or a polymerization catalyst) has an effect on the light transmittance at a wavelength of 350 nm and the yellow index value. Can give.
- 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, and a basic ammonium of Group 1 or 2 (hereinafter, 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.
- Group 1 metal compounds and / or Group 2 metal compounds are 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, and more preferably lithium and a long-period periodic table per mole of all dihydroxy compounds used in the polymerization.
- the amount of metal is preferably 1 mol per 1 mol of all the dihydroxy compounds.
- 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 by using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester represented by the above formula (4), phenol and substituted phenol are secondary substances. It is unavoidable that it remains in the polycarbonate resin (A), but phenol and substituted phenol also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance. May cause odor at times.
- 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, from the viewpoint of light resistance and odor reduction.
- the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight.
- 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 includes a dihydroxy compound (a) having a site represented by the formula (1) according to the present invention and a dihydroxy compound containing at least an aliphatic hydrocarbon dihydroxy compound (b), although it is obtained by polycondensation with the carbonic acid diester of the formula (4) by a transesterification reaction, it is preferable that the dihydroxy compound and the carbonic acid diester as raw materials are uniformly mixed 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. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often resulting in problems such as solidification. If the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated, resulting in a deterioration of the hue of the polycarbonate resin thus obtained, which may adversely affect light resistance.
- the operation of mixing the dihydroxy compound containing the dihydroxy compound used in the present invention, which is a raw material of the polycarbonate resin (A) used in the present invention, and the carbonic acid diester represented by the above formula (4) is performed at an oxygen concentration of 10 vol% or less, It is preferable to carry out in an atmosphere of 0.0001 vol% to 10 vol%, especially 0.0001 vol% to 5 vol%, especially 0.0001 vol% to 1 vol% from the viewpoint of preventing hue deterioration.
- the carbonic acid diester represented by the formula (4) is 0.90 to 1 with respect to the dihydroxy compound including the dihydroxy compound used in the present invention used in the reaction. It is preferably used at a molar ratio of .20, more preferably 0.95 to 1.10. When this molar ratio is decreased, the terminal hydroxyl group of the produced polycarbonate resin is increased, the thermal stability of the polymer is deteriorated, coloring occurs during molding, the rate of transesterification reaction is reduced, and the desired high molecular weight. The body may not be obtained.
- rate of transesterification may fall or manufacture of polycarbonate resin (A) of the desired molecular weight may become difficult.
- 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 molar ratio of the carbonic acid diester represented by the formula (4) is increased with respect to the dihydroxy compound including the dihydroxy compound used in the present invention, the amount of residual carbonic acid diester in the obtained polycarbonate resin (A) is increased.
- they may absorb 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 an unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight.
- 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, continuous, or a combination of batch and continuous.
- Appropriate selection of the internal temperature and pressure in the reaction system is important from the viewpoints of hue and light resistance.
- 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.
- 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 0.20 dl / g or more, preferably 0.30 dL / g or more. Yes, 0.35 dL / g or more is more preferable, and the upper limit of the reduced viscosity is 1.20 dL / g or less, more preferably 1.00 dL / g or less, and even more preferably 0.80 dL / g or less. If the reduced viscosity of the polycarbonate resin (A) is too low, the mechanical strength of the molded product may be small. If it is too large, the fluidity at the time of molding tends to decrease and the productivity and moldability tend to decrease. .
- 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 formula (5) in the polycarbonate resin (A) used in the present invention is usually 20 ⁇ eq / g, preferably 40 ⁇ eq / g, particularly preferably 50 ⁇ eq / g.
- the upper limit is usually 160 ⁇ eq / g, preferably 140 ⁇ eq / g, particularly preferably 100 ⁇ eq / g.
- the concentration of the end group represented by the following formula (5) is too high, even if the hue at the time of polymerization or at the time of molding is good, the hue after UV exposure may be deteriorated. Stability may be reduced.
- the concentration of the terminal group represented by the following formula (5) 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 formula (4) is controlled.
- the method and the like of controlling the type and amount of the catalyst during the transesterification reaction, the polymerization pressure and the polymerization temperature are exemplified.
- 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 by C / (C + D).
- C / (C + D) is preferably 0.1 or less, more preferably 0.05 or less, particularly preferably 0.02 or less, and preferably 0.01 or less.
- C / (C + D) can be quantified by 1 H-NMR.
- 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 has any conventionally known one as long as it has an aromatic ring in the structure. May also be used, and may include a structural unit derived from a dihydroxy compound having a site represented by the formula (1).
- the polycarbonate resin has the largest number of structural units derived from the dihydroxy compound having an aromatic ring, and more preferably aromatic to all the structural units derived from the dihydroxy compound.
- a polycarbonate resin having a structure derived from a dihydroxy compound having a ring of 50 mol% or more, more preferably 70 mol% or more, particularly preferably 90 mol% or more is used.
- 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 formula (1).
- the aromatic polycarbonate resin (B) used in the present invention may be a homopolymer or a copolymer. Moreover, the aromatic polycarbonate resin (B) may have a branched structure. More specifically, it is a polycarbonate resin having a repeating structure represented by the following formula (6).
- Ar 1 and Ar 2 each independently represent an arylene group which may have a substituent
- X represents a single bond or a divalent group.
- the arylene group which may have a substituent is not particularly limited as long as it is an arylene group, but is preferably an arylene group having 3 or less aromatic rings, more preferably A phenylene group.
- the substituent that Ar 1 and Ar 2 may independently have include an alkyl group having 1 to 10 carbon atoms which may have a substituent, and a carbon number which may have a substituent.
- Examples thereof include an alkoxy group having 1 to 10 carbon atoms, a halogen group, a halogenated alkyl group having 1 to 10 carbon atoms, and an aromatic group having 6 to 20 carbon atoms which may have a substituent.
- substituents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aromatic group having 6 to 20 carbon atoms is preferable, and more preferable.
- an alkylene group having a chain structure having 1 to 6 carbon atoms which may have a substituent an alkylidene group having a chain structure having 1 to 6 carbon atoms which may have a substituent
- a C3-C6 cyclic structure alkylene group which may have a substituent a C3-C6 cyclic structure alkylidene group which may have a substituent, -O-, -S-, —CO— or —SO 2 —
- an aryl group is preferable, and a phenyl group is particularly preferable.
- 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 Bisphenol compounds having an alkylidene group having 6 or less carbon atoms such as -bis- (4-hydroxyphenyl) cyclohexane are 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 diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, and dibutyl carbonate. And dialkyl carbonates such as dicyclohexyl carbonate. 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 100,000 or less, preferably 10,000 or more and 50,000, from the balance of mechanical properties and moldability. In the following, those of 15,000 to 35,000 are more preferably used.
- the reduced viscosity of the aromatic polycarbonate resin (B) was measured at a temperature of 20.0 ° C.
- methylene chloride as a solvent and adjusting the polycarbonate concentration to 0.60 g / dl, Usually, it is 0.23 dl / g or more and 0.80 dl / g or less, preferably 0.27 dl / g or more and 0.72 dl / g or less, more preferably 0.40 dl / g or more and 0.61 dl / g or less, more preferably The thing of 0.50 dl / g or more is used.
- the glass transition temperature of the aromatic polycarbonate resin (B) used in the present invention is preferably 110 to 180 ° C.
- the aromatic polycarbonate resin (B) may be used alone or in combination of two or more.
- the polycarbonate resin composition (X) of the present invention comprises a structural unit derived from a dihydroxy compound (a) having a site represented by the following formula (1) in a part of the structure and an aliphatic hydrocarbon dihydroxy compound (b). It is the polycarbonate resin composition (X) containing the polycarbonate resin (A) containing the structural unit derived from and the aromatic polycarbonate resin (B). However, the case where the site represented by the following formula (1) is a part of —CH 2 —O—H is excluded.
- the structural unit derived from the dihydroxy compound (a) having a site represented by the formula (1) in a part of the structure and the dihydroxy compound (b) of an aliphatic hydrocarbon A polycarbonate resin containing a structural unit derived from the above, wherein the structural unit derived from the dihydroxy compound (b) of the aliphatic hydrocarbon is 50 mol% or more with respect to the structural unit derived from the entire dihydroxy compound (A ) And the aromatic polycarbonate resin (B) at the same time, and the content ratio of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) is not particularly limited.
- the weight ratio of the resin (A) to the aromatic polycarbonate resin (B) is 1:99 to 99: 1. More preferably from 5:95 95: A 5, particularly preferably contains at 10:90 90:10.
- the polycarbonate resin is arbitrarily positioned as the polycarbonate resin (A) or the aromatic polycarbonate resin (B), and the ratio Should be in the above range.
- at least one polycarbonate resin selected from the polycarbonate resin (A) and the aromatic polycarbonate resin (B) is used with respect to 100 parts by weight of the polycarbonate resin composition (X).
- the total amount of the polycarbonate resin component used in the polycarbonate resin composition (X) of the present invention is a polycarbonate resin selected from the polycarbonate resin (A) and the aromatic polycarbonate resin (B). It is particularly preferable in terms of obtaining.
- the proportion of the structural unit derived from the aliphatic hydrocarbon dihydroxy compound (b) in the polycarbonate resin (A) is smaller than that of the present invention, the total light transmittance of the polycarbonate resin composition (X) is small. Therefore, the initial yellow index (YI) value tends to increase. On the other hand, if the proportion of the polycarbonate resin (A) in the polycarbonate resin composition (X) is too small, the yellow index (YI) value after the sunshine weather meter irradiation test described later tends to increase.
- the polycarbonate resin composition (X) in the present invention preferably has a single glass transition temperature from the viewpoint of maintaining transparency of the polycarbonate resin composition and a molded product formed by molding the polycarbonate resin.
- the polycarbonate resin composition (X) has a single glass transition temperature means that the polycarbonate resin composition (X) has a strain of 0.1%, a frequency of 10 Hz, and a heating rate of 3 ° C./min.
- Tan ⁇ loss tangent measured by dynamic viscoelastic temperature dispersion measurement (dynamic viscoelasticity measurement of JIS K7198A method (1991)
- loss tangent (tan ⁇ ) Means that there is one local maximum.
- the single glass transition temperature of the polycarbonate resin composition (X) means that the main dispersion of the loss elastic modulus (E ′′) measured in the dynamic viscoelasticity measurement for the polycarbonate resin composition (X). It can also be said that there is one peak, in other words, one maximum value of the loss elastic modulus (E ′′).
- a single glass transition temperature can be confirmed by differential scanning calorimetry. Specifically, in accordance with JIS K7121 (1987), when the glass transition temperature is measured using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min, the inflection point indicating the glass transition temperature is It can be said that only one appears.
- a single glass transition temperature of a polymer blend composition means that the resin to be mixed is in a compatible state on the nanometer order (molecular level). Can be acknowledged.
- the glass transition temperature of the polycarbonate resin composition (X) is represented by a temperature indicating the peak value of the main dispersion of loss tangent (tan ⁇ ) measured by the above-described dynamic viscoelastic temperature dispersion measurement,
- the glass transition temperature is preferably in the range of not less than the glass transition temperature of the aliphatic polycarbonate resin (A) and not more than the glass transition temperature of the aromatic polycarbonate resin (B).
- the proportion of the aliphatic polycarbonate resin (A) in the mixture (X) comprising the aliphatic polycarbonate resin (A) and the aromatic polycarbonate resin (B) is in the range of 1% by mass to 99% by mass. Although it can mix arbitrarily, especially regarding a lower limit, it is preferable that it is 50 mass% or more, it is more preferable that it is 55 mass% or more, and it is especially preferable that it is 60 mass% or more.
- By making the ratio of the aliphatic polycarbonate resin (A) 50% by mass or more and 99% by mass or less it not only has excellent heat resistance, impact resistance and fluidity but also excellent weather resistance. An excellent resin composition can be provided for the intended use.
- the aliphatic polycarbonate resin (A) and the aromatic polycarbonate resin (B) constituting the resin composition of the present invention are excellent in compatibility
- the aliphatic polycarbonate resin (A) and the aromatic polycarbonate resin (B ) Is a single glass transition temperature which is the peak value of the main dispersion of loss tangent (tan ⁇ ) measured by dynamic viscoelastic temperature dispersion measurement, and the glass transition temperature is Resin composition not only having a glass transition temperature of the aliphatic polycarbonate resin (A) but not higher than the glass transition temperature of the aromatic polycarbonate resin (B), which is excellent not only in heat resistance and impact resistance but also in transparency. It is a thing.
- the glass transition temperature of the polycarbonate resin composition (X) in the present invention is preferably 75 ° C. or higher and 130 ° C. or lower, more preferably 80 ° C. or higher and 125 ° C. or lower, 85 ° C. or higher, 120 ° C. or lower. More preferably, it is not higher than ° C.
- a resin composition having excellent heat resistance can be provided.
- 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 blending amount of the resin other than the polycarbonate resin is a ratio of 1 part by weight or more and 30 parts by weight or less with respect to 100% by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferably blended at a ratio of 3 parts by weight or more and 20 parts by weight or less, more preferably 5 parts by weight or more and 10 parts by weight or less.
- 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 blending amount of the heat stabilizer is 0.0001 parts by weight or more and 1 part by weight or less with respect to 100% 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, more preferably 0.0005 parts by weight or more and 0.5 parts by weight or less, and more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. preferable.
- 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 blending amount of the antioxidant is 0.0001 parts 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. It is preferable to mix, more preferably 0.0005 parts by weight or more and 0.5 parts by weight or less, and more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. preferable.
- 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 0.0001 parts 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. It is preferable to mix, more preferably 0.0005 parts by weight or more and 0.5 parts by weight or less, and more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. preferable. 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, ethylene glycol distearate 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 release agent is preferably 0.0001 parts by weight or more, more preferably 0.01 parts by weight 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.
- 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; regardless of the polymerization method, the polycarbonate resin in the middle of kneading the polycarbonate resin with another compounding agent is melted.
- a polycarbonate resin in a solid state such as pellets or powder using an extruder or the like.
- 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.
- an epoxy compound can be further blended in the polycarbonate resin composition (X).
- the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexyl Carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3 ', 4'-epoxy
- the compounding amount of the epoxy compound is preferably 0.0001% by mass or more and 5% by mass or less with respect to 100% by mass of the resin composition constituting the molded article of the present invention. It is more preferable to mix
- additives such as plasticizers, pigments, dyes, fillers and the like can be further added to the polycarbonate resin composition of the present invention.
- the polycarbonate resin composition Charpy notched impact strength which is measured in accordance with ISO 179 (2000 years) is preferably 10 kJ / m 2 or more, more preferably 12 kJ / m 2 or more. If the notched Charpy impact strength is too small, the injection-molded product tends to break easily at the stress concentration point. In consideration of the difficulty of realization, the upper limit is 200 kJ / m 2 .
- the polycarbonate resin composition (X) described above is molded to obtain a molded article of polycarbonate resin.
- the molding method of the molded product of the polycarbonate resin is not particularly limited, but the polycarbonate resin (A), the aromatic polycarbonate resin (B) and, if necessary, other raw materials such as other resins and additives are directly mixed, and an extruder Alternatively, it is put into an injection molding machine and molded, or the raw material is melt-mixed using a twin screw extruder, extruded into a strand shape to produce pellets, and then the pellets are put into an extruder or injection molding machine.
- a method of charging and molding can be mentioned. In any method, it is necessary to consider a decrease in molecular weight due to hydrolysis of the polycarbonate resin, and the latter is preferably selected for uniform mixing. Therefore, the latter manufacturing method will be described below.
- the melt extrusion temperature is preferably 200 ° C. or higher and 260 ° C. or lower, more preferably 210 ° C. or higher and 250 ° C. or lower, and further preferably 220 ° C. or higher and 240 ° C.
- a film, a plate, or an injection molded product can be molded by the following method.
- a method for forming a film and a plate in addition to a roll stretching, a tenter stretching method, a tubular method, and an inflation method, a general T die casting method, a pressing method, or the like can be employed as a film or plate forming method.
- film is a thin flat product whose thickness is extremely small compared to the length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll.
- JIS K6900 (1994) in general, a “sheet” is a thin product that is thin by definition as defined in JIS, and whose thickness is small instead of length and width.
- sheet is included and the term “sheet” is used. In some cases, “film” is included.
- the molding method of the injection molded body is not particularly limited, and for example, an injection molding method such as a general injection molding method for a thermoplastic resin, a gas assist molding method, and an injection compression molding method can be employed.
- an injection molding method such as a general injection molding method for a thermoplastic resin, a gas assist molding method, and an injection compression molding method can be employed.
- an in-mold molding method, a gas press molding method, a two-color molding method, a sandwich molding method, or the like can be employed in accordance with other purposes.
- the polycarbonate resin composition of the present invention is preferably transparent depending on the properties required for its application. Specifically, the transparency can be evaluated by, for example, the total light transmittance of the molded article, and a material having a high total light transmittance is preferable.
- the total light transmittance is measured using a molded body (thickness 3 mm) molded from the polycarbonate resin composition of the present invention, and is preferably 60% or more, more preferably 70% or more, and particularly preferably 80. What has the total light transmittance of% or more is preferable.
- the total light transmittance measured based on JIS K7361-1 (1997) at a thickness of 1 mm of the molded body is preferably 80% or more, more preferably 83% or more, and 85% or more. More preferably it is.
- haze measured based on JIS K7105 (1981) is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less. When the total light transmittance and the haze are within such ranges, it can be widely used in various applications that require transparency.
- the total light transmittance measured based on JIS K7361-1 (1997) when the resin composition is molded to a thickness of 0.2 mm is preferably 80% or more, and more preferably 83% or more. More preferably, it is more preferably 85% or more.
- haze measured based on JIS K7105 (1981) is preferably 3% or less, more preferably 2% or less, still more preferably 1.8% or less, and 1.5%. It is particularly preferred that When the total light transmittance and the haze are within such ranges, it can be widely used in various applications that require transparency.
- the polycarbonate resin composition of the present invention has high weather resistance.
- This weather resistance can be evaluated by, for example, irradiation treatment using a sunshine carbon arc. More specifically, as will be described later, with a specific device, using a specific filter or the like, mainly light having a wavelength of 300 nm or more and 1100 nm or less, a black panel temperature of 63 ° C., a relative humidity of 50%, and rainfall per hour. Evaluation can be performed by irradiating a sample for 500 hours with a discharge voltage of 50 V and a discharge current of 60 A using a sunshine carbon arc in an environment where the spray time is 12 minutes.
- the total light transmittance after subjecting the molded body (thickness 3 mm) molded from the polycarbonate resin composition of the present invention to irradiation treatment for 500 hours using the sunshine carbon arc is preferably 85% or more,
- the upper limit is 99% or less, and the difference in yellow index (YI) values before and after the irradiation treatment is preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less.
- the photoelastic coefficient at a light wavelength of 600 nm is 7 ⁇ 10 ⁇ 11 Pa ⁇ 1 or less, and it is 6.5 ⁇ 10 ⁇ 11 Pa ⁇ 1 or less. More preferably, it is 6 ⁇ 10 ⁇ 11 Pa ⁇ 1 or less. If the photoelastic coefficient is within such a range, a phase difference due to stress hardly occurs, and it can be widely used for optical applications such as various lenses.
- the resin composition of the present invention preferably has a total light transmittance of 60% or more of an injection molded product measured with a D65 light source using a haze meter based on JIS K7105 (1981).
- the film, plate, or injection-molded product obtained from the resin composition of the present invention is excellent in mechanical properties such as transparency, impact resistance, breaking strength and elongation, and has excellent heat resistance and fluidity. . Therefore, the use of the resin composition of the present invention is not particularly limited. For example, for building materials, interior parts, transparent sheets, sheets for resin-coated metal plates, molding (vacuum / pressure molding, hot press molding, etc.) It can be used for injection molding products such as sheets, coloring plates, transparent plates, shrink films, shrink labels, shrink tubes, automobile interior materials, home appliance housings, various parts, and OA equipment parts.
- the molded article of the present invention has a low photoelastic coefficient and is excellent in transparency, heat resistance, and impact resistance. Therefore, the use of the molded article of the present invention is not particularly limited. It can be used for various lenses such as a pickup lens for optical disks, light guide plates for liquid crystal displays, various optical films and sheets, optical disks, condenser films and the like. Moreover, since the polycarbonate resin molded product 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.
- PC3 Novalex M7027BF manufactured by Mitsubishi Engineering Plastics, Reduced viscosity 0.56 dl / g
- PC4 Mitsubishi Engineering Plastics Novalex 7022J, Reduced viscosity 0.47 dl / g
- Example 1-1 After dry blending PC1 and PC3 at a mass 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, and solidified by cooling 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.
- TEX30HSS-32 twin screw extruder manufactured by Nippon Steel
- Example 1-2 Samples were prepared and evaluated in the same manner as in Example 1-1 except that PC1 and PC3 were mixed at a mixing mass ratio of 60:40. The results are shown in Table 1.
- Example 1-3 Samples were prepared and evaluated in the same manner as in Example 1-1, except that PC1 and PC3 were mixed at a mixing mass ratio of 40:60. The results are shown in Table 1.
- Example 1-1 Samples were prepared and evaluated in the same manner as in Example 1-1 except that PC2 and PC4 were mixed at a mixing mass ratio of 60:40. The results are shown in Table 1.
- Example 1-2 Samples were prepared and evaluated in the same manner as in Example 1-1 except that PC2 and PC3 were mixed at a mixing mass ratio of 60:40. The results are shown in Table 1.
- the concentration of the polycarbonate resin sample is (Use a 0.6 g / dl solution.)
- PC4 Structural unit derived from isosorbide / Structural unit derived from 1,4-cyclohexaned
- Example 2-1 After PC1 and PC6 were dry blended at a mass ratio of 90:10, they were compounded at 240 ° C. using a 40 mm ⁇ small unidirectional twin screw extruder manufactured by Mitsubishi Heavy Industries, and formed into a pellet shape. Samples for various evaluations were produced by injection molding of the obtained pellets using an injection molding machine IS50E (screw diameter 25 mm) manufactured by Toshiba Machine. The main molding conditions are as follows.
- Example 2-2 Samples were prepared and evaluated in the same manner as in Example 2-1, except that PC1 and PC6 were mixed at a mixing mass ratio of 60:40. The results are shown in Table 2.
- Example 2-3 Samples were prepared and evaluated in the same manner as in Example 2-1, except that PC1 and PC6 were mixed at a mixing mass ratio of 30:70. The results are shown in Table 2.
- Example 2-4 Samples were prepared and evaluated in the same manner as in Example 2-1, except that PC2 and PC6 were mixed at a mixing mass ratio of 60:40. The results are shown in Table 2.
- Example 2-5 Samples were prepared and evaluated in the same manner as in Example 2-1, except that PC3 and PC6 were mixed at a mixing mass ratio of 60:40. The results are shown in Table 2.
- Example 2-1 Samples were prepared and evaluated in the same manner as in Example 2-1, except that the fatty polycarbonate resin (A) was not used, only PC6 was used, and the mold temperature was 100 ° C. The results are shown in Table 2.
- Example 2-2 Samples were prepared and evaluated in the same manner as in Example 2-1, except that PC4 and PC6 were mixed at a mixing mass ratio of 60:40. The results are shown in Table 2.
- Example 2-3 Samples were prepared and evaluated in the same manner as in Example 2-1, except that PC5 and PC6 were mixed at a mixing mass ratio of 60:40. The results are shown in Table 2.
- the molded product of the present invention had a low photoelastic coefficient and excellent transparency, heat resistance, and impact resistance as long as it was within the specified range of the present invention.
- each of the comparative examples has a high photoelastic coefficient.
- Comparative Examples 2-2 and 2-3 are inferior to Examples in terms of transparency and Comparative Examples 2-2 to 2-4 in terms of impact resistance. It was. From this, it can be seen that the molded article of the present invention has a low photoelastic coefficient and is excellent in transparency, heat resistance and impact resistance.
- Examples 3-1 to 3-5 Comparative Examples 3-1 to 3-3>
- the various measured values and evaluation about the raw material and test piece which are displayed in this specification were performed as follows.
- the flow direction from the extruder of the film is called the vertical direction
- the orthogonal direction is called the horizontal direction.
- the concentration of the polycarbonate resin sample is (Use a 0.6 g / dl solution.)
- Tensile elastic modulus Based on JIS K7127 (1999), a test piece having a length of 400 mm, a width of 10 mm, and a thickness of 0.2 mm was prepared so that the transverse direction was the measurement direction, and a universal material testing machine MODEL205 manufactured by Intesco. The tensile modulus was measured under the conditions of a temperature of 23 ° C. and a tensile speed of 5 mm / min. The tensile modulus was 2.0 GPa or more.
- Impact resistance (breaking energy) Using a hydroshot high-speed impact tester (“HTM-1 type” manufactured by Shimadzu Corporation), a sheet cut into a size of 100 mm in the vertical direction and 100 mm in the horizontal direction is used as a sample, fixed with a clamp, and the sheet at a temperature of 23 ° C.
- the impact energy (kgf ⁇ mm) at the time of breaking the sample was measured by applying an impact by dropping a strike center having a diameter of 1/2 inch in the center at a dropping speed of 3 m / sec. Those having a fracture energy of 100 kgf ⁇ mm or more were regarded as acceptable.
- TMA softening temperature Using a sample for evaluation of 5 mm in length ⁇ 5 mm in width (thickness varies depending on each test piece), the softening temperature was measured by TMA based on JIS K7196 (1991). Measure the TMA curve at a temperature of 23 ° C, a relative humidity of 50%, an indenter pressure of 0.5N, and a heating rate of 5 ° C / min. The softening temperature was calculated from this value, which was defined as the needle penetration temperature at the intersection with the extension of the tangential line where the penetration speed reached the maximum to the low temperature side. The TMA softening temperature passed 70 ° C. or higher.
- a glass transition temperature is single, and all light transmittance, haze, tensile fracture strength / elongation, tensile elastic modulus, impact resistance, heat resistance, and fluidity are all acceptable.
- ⁇ The glass transition temperature is single, and the total light transmittance, haze, tensile fracture strength / elongation, tensile elastic modulus, impact resistance, heat resistance, and fluidity all pass, but the fluidity is slightly Inferior (those over 10,000).
- ⁇ Glass transition temperature is single, the total light transmittance, haze, tensile fracture strength / elongation, impact resistance, heat resistance, and fluidity are acceptable, but the tensile elastic modulus is inferior, but there is no practical problem. Things.
- X The glass transition temperature is not single, or one or more of the total light transmittance, haze, tensile fracture strength / elongation, tensile elastic modulus, impact resistance, heat resistance, and fluidity is rejected. Levels that have practical problems.
- PC4 Structural unit derived from isosorbide / Structural unit derived from 1,4-cyclohexaned
- Example 3-1 PC1 and PC6 were dry blended at a mixing mass ratio of 90:10, kneaded at 220 ° C. using a 40 mm ⁇ co-directional twin screw extruder, extruded from a T-die, and then cast into a casting roll of about 80 ° C. The sheet was rapidly cooled to prepare a sheet having a thickness of 0.2 mm. The obtained sheet was evaluated for glass transition temperature, tensile fracture strength / elongation, tensile elastic modulus, impact resistance, heat resistance, and fluidity. The results are shown in Table 3.
- Example 3-2 PC1 and PC6 were mixed at a mixing mass ratio of 60:40, and a sheet was prepared and evaluated in the same manner as in Example 3-1, except that the casting roll temperature was 100 ° C. The results are shown in Table 3.
- Example 3-3 PC1 and PC6 were mixed at a mixing mass ratio of 20:80, and a sheet was prepared and evaluated in the same manner as in Example 3-1, except that the casting roll temperature was 130 ° C. The results are shown in Table 3.
- Example 3-4 PC2 and PC6 were mixed at a mixing mass ratio of 60:40, and a sheet was prepared and evaluated in the same manner as in Example 3-1, except that the casting roll temperature was 120 ° C. The results are shown in Table 3.
- Example 3-5 PC4 and PC6 were mixed at a mixing mass ratio of 60:40, and a sheet was prepared and evaluated in the same manner as in Example 3-1, except that the casting roll temperature was 110 ° C. The results are shown in Table 3.
- Example 3-2 A sheet was prepared and evaluated in the same manner as in Example 3-1, except that no aliphatic polycarbonate resin was used and only PC6 was used and the casting roll temperature was 130 ° C. The results are shown in Table 3.
- the resin composition of the present invention was excellent in transparency, heat resistance, impact resistance, and fluidity within the specified range of the present invention.
- the fluidity was superior to that of Example 3-3 and the rigidity was superior to that of Example 3-5.
- Comparative Example 3-1 and Comparative Example 3-3 were inferior to Examples in terms of transparency and impact resistance
- Comparative Example 3-2 was inferior to Examples in terms of fluidity. This shows that the resin composition of the present invention is a resin composition excellent in transparency, heat resistance, impact resistance, and fluidity.
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Abstract
Description
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。ポリカーボネート樹脂は、溶融粘度が高く、流動性が低いため、シート、フィルム、成形品等を成形する際に、成形性に劣るという欠点があった。また、特に光学用途へ使用する際、ポリカーボネート樹脂は光弾性係数が高く、応力により位相差が生じやすいため、限られた用途のみの使用に留まっているのが現状である。
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]~[20]に存する。
[1]
構造の一部に下記式(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肪族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(X)であって、該ポリカーボネート樹脂(A)中の全ジヒドロキシ化合物に由来する構成単位に対する脂肪族炭化水素のジヒドロキシ化合物(b)に由来する構成単位の割合が45モル%以上であるポリカーボネート樹脂組成物。
[2]
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、全光線透過率が85%以上であり、かつ該照射処理前後におけるイエローインデックス(YI)値の差が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]
前記ポリカーボネート樹脂組成物(X)が単一のガラス転移温度を有し、かつ、該ガラス転移温度が前記脂肪族ポリカーボネート樹脂(A)のガラス転移温度以上、前記芳香族ポリカーボネート樹脂(B)のガラス転移温度以下の範囲にある、[1]または[2]に記載のポリカーボネート樹脂組成物。
[4]
前記脂肪族ポリカーボネート樹脂(A)のガラス転移温度が、75℃以上、105℃以下である[1]から「3」のいずれか1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組成物(X)のガラス転移温度が、75℃以上、130℃以下である[1]から[4]のいずれか1に記載のポリカーボネート樹脂組成物。
[6]
JIS K7105(1981年)に基づきヘーズメーターを使用してD65光源にて測定した射出成形品の全光線透過率が60%以上である、[1]から[5]のいずれか1に記載のポリカーボネート樹脂組成物。
[7]
厚み1mmにおけるJIS K7361-1(1997年)に基づき測定した全光線透過率が80%以上であり、かつ、JIS K7105(1981年)に基づき測定したヘーズが5%以下である[1]から[6]のいずれか1に記載のポリカーボネート樹脂組成物。
[8]
ISO179(2000年)に準拠して測定されたノッチ付シャルピー衝撃強度が10kJ/m2以上である、[1]から[7]いずれか1に記載のポリカーボネート樹脂組成物。
[9]
前記脂肪族ポリカーボネート樹脂(A)中の全ジヒドロキシ化合物に由来する構成単位に対する前記脂肪族炭化水素のジヒドロキシ化合物(b)に由来する構成単位の割合が45モル%以上、80モル%以下であり、
前記ポリカーボネート樹脂組成物(X)中に占める脂肪族ポリカーボネート樹脂(A)の割合が1質量%以上、99質量%以下である、[1]から[8]のいずれか1に記載のポリカーボネート樹脂組成物。
[10]
前記ジヒドロキシ化合物(a)が、下記式(2)で表されるジヒドロキシ化合物である、[1]から[9]のいずれか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、[1]から[10]のいずれか1に記載のポリカーボネート樹脂組成物。
[12]
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[11]のいずれか1に記載のポリカーボネート樹脂組成物。
[13]
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[12]のいずれか1に記載のポリカーボネート樹脂組成物。
[14]
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[13]のいずれか1に記載のポリカーボネート樹脂組成物。
[15]
[1]から[14]のいずれか1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体。
[16]
600nmの光波長における光弾性係数が7×10-11Pa-1以下である、[15]に記載の成形体。
[17]
[1]から[14]のいずれか1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フィルム。
[18]
厚み0.2mmに成形したときのJIS K7361-1(1997年)に基づき測定した全光線透過率が80%以上であり、かつ、JIS K7105(1981年)に基づき測定したヘーズが3%以下である、[17]に記載のフィルム。
[19]
[1]から[14]のいずれか1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プレート。
[20]
[1]から[14]のいずれか1に記載のポリカーボネート樹脂組成物を射出成形して得られる射出成形品。
ここで、“質量%”、“質量ppm”及び“質量部”は、それぞれ“重量%”、“重量ppm”及び“重量部”と同義である。また、単に“ppm”と記載した場合は、“重量ppm”のことを示す。
本発明で用いるポリカーボネート樹脂(A)は、その製造方法に特に制限は無いが、通状、構造の一部に下記式(1)で表される部位を有するジヒドロキシ化合物(a)と、脂肪族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)は下記式(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肪族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。但し、式(1)で表される部位が -CH2-O-H の一部である場合を除く。
本発明に係るポリカーボネート樹脂(A)で用いるジヒドロキシ化合物としては、構造の一部に前記式(1)で表される部位を有するジヒドロキシ化合物(a)と、脂肪族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、下記式(2)で表されるジヒドロキシ化合物および下記式(3)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など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、耐熱性の観点からは、下記式(2)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、下記式(3)で表される環状エーテル構造を有する化合物が好ましい。
更に、ポリカーボネート樹脂(A)中に占める脂肪族炭化水素のジヒドロキシ化合物(b)の割合が所定量以上であると、耐候性、色相及び機械的強度に優れたポリカーボネート樹脂組成物を得ることが可能となる。ポリカーボネート樹脂(A)中に占める、全ジヒドロキシ化合物に由来する構成単位に対する、脂肪族炭化水素のジヒドロキシ化合物(b)に由来する構成単位の割合は、下限が45モル%以上、通常50モル%以上、好ましくは52モル%以上、更に好ましくは55モル%以上、特に好ましくは60モル%以上である。45モル%以上とすることによって芳香族ポリカーボネート樹脂(B)との相溶性が良好となり、混合物(X)及び成形体の透明性、機械特性を十分に向上し、光弾性係数を低下させることができる。一方、上限は、好ましくは90モル%以下、更に好ましくは80モル%以下、より好ましくは75モル%以下、特に好ましくは70モル%以下である。上限を上記範囲とすることで脂肪族ポリカーボネート樹脂(A)に起因する大幅な耐熱性低下、軟質化を防止でき、幅広い用途で使用が可能となる。
上記脂肪族ポリカーボネート樹脂(A)の分子量の指標である還元粘度は、溶媒として塩化メチレンを用い、ポリカーボネート濃度を0.60g/dlに精密に調整し、温度20.0℃±0.1℃で測定され、通常、0.20dl/g以上1.0dl/g以下で、好ましくは0.3dl/g以上0.8dl/g以下の範囲内である。
脂肪族ポリカーボネート樹脂(A)の還元粘度が過度に低いと、レンズ等に成形した際の機械的強度が低下する傾向がある。また、脂肪族ポリカーボネート樹脂(A)の還元粘度が過度に高いと、成形する際の流動性が低下し、サイクル特性を低下させ、成形品の歪みが大きくなり易い傾向がある。
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、下記式(4)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。
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式(4)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/又は2族金属化合物が使用される。
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、本発明に係る式(1)で表される部位を有するジヒドロキシ化合物(a)および脂肪族炭化水素のジヒドロキシ化合物(b)を少なくとも含むジヒドロキシ化合物と、前記式(4)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。
このモル比率が小さくなると、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て、ポリマーの熱安定性が悪化し、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可能性がある。
更には、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に対して、前記式(4)で表される炭酸ジエステルのモル比率が増大すると、得られるポリカーボネート樹脂(A)中の残存炭酸ジエステル量が増加し、これらが紫外線を吸収してポリカーボネート樹脂の耐光性を悪化させる場合があり、好ましくない。 本発明で用いるポリカーボネート樹脂(A)に残存する炭酸ジエステルの濃度は、好ましくは200重量ppm以下、更に好ましくは100重量ppm以下、特に好ましくは60重量ppm以下、中でも30重量ppm以下が好適である。現実的にポリカーボネート樹脂(A)は未反応の炭酸ジエステルを含むことがあり、濃度の下限値は通常1重量ppmである。
重合初期においては、相対的に低温、低真空でプレポリマーを得、重合後期においては相対的に高温、高真空で所定の値まで分子量を上昇させることが好ましいが、各分子量段階でのジャケット温度と内温、反応系内の圧力を適切に選択することが色相や耐光性の観点から重要である。例えば、重合反応が所定の値に到達する前に温度、圧力のどちらか一方でも早く変化させすぎると、未反応のモノマーが留出し、ジヒドロキシ化合物と炭酸ジエステルのモル比を狂わせ、重合速度の低下を招いたり、所定の分子量や末端基を持つポリマーが得られなかったりして結果的に本願発明の目的を達成することができない可能性がある。
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)の還元粘度が低すぎると成形品の機械的強度が小さい可能性があり、大きすぎると、成形する際の流動性が低下し、生産性や成形性を低下させる傾向がある。
下記式(5)で表される末端基の濃度を制御するには、原料である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式(4)で表される炭酸ジエステルのモル比率を制御する他、エステル交換反応時の触媒の種類や量、重合圧力や重合温度を制御する方法等が挙げられる。
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、構造中に芳香族環を有するものであれば、従前知られる如何なるものも使用することが可能であり、前記式(1)で表される部位を有するジヒドロキシ化合物に由来する構成単位を含むものであっても構わない。好ましくは、ジヒドロキシ化合物に由来する全構成単位中、芳香族環を有するジヒドロキシ化合物に由来する構成単位が最も多いポリカーボネート樹脂であって、より好ましくはジヒドロキシ化合物に由来する全構成単位に対して芳香族環を有するジヒドロキシ化合物に由来する構造が50モル%以上、更に好ましくは70モル%以上、特に好ましくは90モル%以上のポリカーボネート樹脂が用いられる。ただし、前記式(1)で表される部位を有するジヒドロキシ化合物に由来する構成単位を含むものである場合、ポリカーボネート樹脂(A)とは異なる構造のポリカーボネート樹脂が使用される。
より具体的には、下記式(6)で表される繰返し構造を有するポリカーボネート樹脂である。
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)プロパンなどの、アルキリデン基によりフェノール類が連結されたビスフェノール化合物があげられる。
本発明のポリカーボネート樹脂組成物(X)は、構造の一部に下記式(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肪族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(X)である。但し、下記式(1)で表される部位が-CH2-O-Hの一部である場合を除く。
また、上記動的粘弾性測定のほか、示差走査熱量測定などによってもガラス転移温度が単一であることを確認することができる。具体的には、JIS K7121(1987年)に準じて、加熱速度10℃/分で示差走査熱量計(DSC)を用いてガラス転移温度を測定した際に、ガラス転移温度を示す変曲点が1つだけ現れるものであるということもできる。
<ポリカーボネート樹脂以外の樹脂>
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、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。
さらに、本発明の成形体の耐加水分解性をさらに向上するため、ポリカーボネート樹脂組成物(X)にはさらにエポキシ系化合物を配合することができる。エポキシ系化合物の具体例としては、エポキシ化大豆油、エポキシ化アマニ油、フェニルグリシジルエーテル、アリルグリシジルエーテル、t-ブチルフェニルグリシジルエーテル、3,4-エポキシシクロヘキシルメチル-3',4'-エポキシシクロヘキシルカルボキシレート、3,4-エポキシ-6-メチルシクロヘキシルメチル-3',4'-エポキシ-6'-メチルシクロヘキシルカルボキシレート、2,3-エポキシシクロヘキシルメチル-3',4'-エポキシシクロヘキシルカルボキシレート、4-(3,4-エポキシ-5-メチルシクロヘキシル) ブチル-3',4'-エポキシシクロヘキシルカルボキシレート、3,4-エポキシシクロヘキシルエチレンオキシド、シクロヘキシルメチルー3,4-エポキシシクロヘキシルカルボキシレート、3,4-エポキシ-6-メチルシクロヘキシルメチル-6'-メチルシロヘキシルカルボキシレート、ビスフェノールAジグリシジルエーテル、テトラブロモビスフェノールAグリシジルエーテル、フタル酸のジグリシジルエステル、ヘキサヒドロフタル酸のジグリシジルエステル、ビス-エポキシジシクロペンタジエニルエーテル、ビス-エポキシエチレングリコール、ビス-エポキシシクロヘキシルアジペート、ブタジエンジエポキシド、テトラフェニルエチレンエポキシド、オクチルエポキシタレート、エポキシ化ポリブタジエン、3,4-ジメチル-1,2-エポキシシクロヘキサン、3,5-ジメチル-1,2-エポキシシクロヘキサン、3-メチル-5-t-ブチル-1,2-エポキシシクロヘキサン、オクタデシル-2,2-ジメチル-3,4-エポキシシクロヘキシルカルボキシレート、N-ブチル-2,2-ジメチル-3,4-エポキシシクロヘキシルカルボキシレート、シクロヘキシル-2-メチル-3,4-エポキシシクロヘキシルカルボキシレート、N-ブチル-2-イソプロピル-3,4-エポキシ-5-メチルシクロヘキシルカルボキシレート、オクタデシル-3,4-エポキシシクロヘキシルカルボキシレート、2-エチルヘキシル-3',4'-エポキシシクロヘキシルカルボキシレート、4,6-ジメチル-2,3-エポキシシクロヘキシル-3',4'-エポキシシクロヘキシルカルボキシレート、4,5-エポキシ無水テトラヒドロフタル酸、3-t-ブチル-4,5-エポキシ無水テトラヒドロフタル酸、ジエチル-4,5-エポキシ-シス-1,2-シクロヘキシルジカルボキシレート、ジ-N-ブチル-3-tブチル-4,5-エポキシ-シス-1,2-シクロヘキシルジカルボキシレートなどが挙げられる。ビスフェノールAジグリシジルエーテルが相溶性などの点から好ましい。前記エポキシ系化合物の配合量としては、本発明の成形体を構成する樹脂組成物100質量%に対して、0.0001質量%以上、5質量%以下の割合で配合することが好ましく、0.001質量%以上、1質量%以下の割合で配合することがより好ましく、0.005質量%以上、0.5質量%以下の割合で配合することがさらに好ましい。かかる範囲でエポキシ系化合物を配合することにより、成形体表面へのエポキシ系化合物のブリード、各種成形品の機械特性低下を生じることなく、成形体の耐加水分解性を向上することができる。
本発明における、ポリカーボネート樹脂組成物は、ISO179(2000年)に準拠して測定されたノッチ付シャルピー衝撃強度が、好ましくは10kJ/m2以上、更に好ましくは12kJ/m2以上である。ノッチ付シャルピー衝撃強度が小さすぎると、射出成形品が応力集中箇所で容易に破断する傾向がある。また、実現の困難性を考慮すると上限は200kJ/m2である。
本発明の成形品では、上述したポリカーボネート樹脂組成物(X)を成形して、ポリカーボネート樹脂の成形品が得られる。ポリカーボネート樹脂の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。いずれの方法においても、ポリカーボネート樹脂の加水分解による分子量の低下を考慮する必要があり、均一に混合させるためには後者を選択するのが好ましい。そこで、以下後者の製造方法について説明する。
本発明のポリカーボネート樹脂組成物は、その用途で要求される特性によっては、透明であることが好ましい。この透明であることは、具体的には例えば、成形された成形体の全光線透過率により評価することが可能であって、全光線透過率が高いものが好ましい。全光線透過率は、本発明のポリカーボネート樹脂組成物から成形された成形体(厚さ3mm)を用いて測定し、60%以上であることが好ましく、より好ましくは70%以上、特に好ましくは80%以上の全光線透過率を有するものが好ましい。
本発明のポリカーボネート樹脂組成物は、高い耐候性を有するものであるが、この耐候性は、例えばサンシャインカーボンアークを用いた照射処理により評価することができる。より具体的には、後述するが、特定の装置で、特定のフィルターなどを用い、主として300nm以上、1100nm以下の波長の光を、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、試料に500時間照射することで評価することが可能である。
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。
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、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。
(3)引張試験
ISO527(1993年)に準拠し、引張試験を行い、破壊呼びひずみを測定した。
(4)荷重たわみ温度
ISO75(2004年)に準拠し、荷重1.80MPaでの荷重たわみ温度を測定した。
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/1,4-シクロヘキサンジメタノールに由来する構成単位=70/30モル%、還元粘度 0.51dl/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M7027BF、
還元粘度 0.56dl/g
PC4:
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、
還元粘度 0.47dl/g
PC1、及び、PC3を質量比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)および物性測定用ISO試験片を成形した。
得られたサンプルについて、全光線透過率、引張試験および荷重たわみ温度の測定を行なった。結果を表1に示す。
PC1、及び、PC3を混合質量比60:40の割合で混合した以外は実施例1-1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を混合質量比40:60の割合で混合した以外は実施例1-1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、PC4を混合質量比60:40の割合で混合した以外は実施例1-1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を混合質量比60:40の割合で混合した以外は実施例1-1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のみを、窒素雰囲気下、70℃で6時間乾燥した後に、成形した以外は実施例1-1と同様の評価を行なった。結果を表1に示す。
PC2のみを、窒素雰囲気下、80℃で6時間乾燥した後に、成形した以外は実施例1-1と同様の評価を行なった。結果を表1に示す。
なお、本明細書中に表示される原料及び試験片についての種々の測定値及び評価は次のようにして行った。ここで、フィルムの押出機からの流れ方向を縦方向、その直交方向を横方向と呼ぶ。
ウベローデ粘度計を使用し、ポリカーボネート樹脂試料の塩化メチレン溶液(0.6g/dl)を調製し、20℃におけるηspを測定し、以下の式(I)及び(II)より粘度平均分子量(Mv)を求めた。
ηsp/C=[η]×(1+0.28ηsp) (I)
[η]=1.23×10-4×(Mv)0.83 (II)
(式(I)中、ηspはポリカーボネート樹脂試料の塩化メチレン中20℃で測定した比粘度であり、Cはこの塩化メチレン溶液の濃度である。塩化メチレン溶液としては、ポリカーボネート樹脂試料の濃度が0.6g/dlの溶液を使用する。)
中央理化社製DT-504型自動粘度計にてウベローデ型粘度計を用い、溶媒として、塩化メチレンを用い、温度20.0℃±0.1℃でポリカーボネート樹脂試料の還元粘度を測定した。濃度は0.60g/dlになるように、精密に調整した後に測定した。
溶媒の通過時間t0、溶液の通過時間tから、下記式:
ηrel=t/t0
より相対粘度ηrelを求め、 相対粘度ηrelから、下記式:
ηsp=(η-η0)/η0=ηrel-1
より比粘度ηspを求めた。
比粘度ηspを濃度c(g/dl)で割って、下記式:
ηred=ηsp/c
より還元粘度(換算粘度)ηredを求めた。
この数値が高いほど分子量が大きい。
粘弾性スペクトロメーターDVA-200(アイティー計測制御株式会社製)を用い、歪み0.1%、周波数10Hz、昇温速度3℃/分にて動的粘弾性の温度分散測定(JIS K7198A法(1991年)の動的粘弾性測定)を行った。そして損失正接(tanδ)の主分散のピークを示す温度をガラス転移温度とした。
王子計測機器社製KOBRA-WRを用いて、幅15mm×長さ60mm×厚み0.2mmのサンプルを遅相軸側が引張方向となるようにセットし、引張荷重を50gfずつ増加したときの位相差の変化を測定し、結果を直線近似して傾きを算出した。続いて、下記式を用いて光弾性係数を算出した。
「光弾性係数」=「傾き」×1.5×10-8/9.8(Pa-1)
光弾性係数は7×10-11Pa―1以下を合格とした。
JIS K7105(1981年)に基づいて、全光線透過率および拡散透過率を測定し、ヘーズを以下の式で算出した。厚み1mmでの全光線透過率が80%以上、ヘーズが5%以下であるものを合格とした。
[ヘーズ]=[拡散透過率]/[全光線透過率]×100
JIS K-7110(1999年)に基づいて、2号A試験片(ノッチ付き、長さ64mm×幅12.7mm×厚さ4mm)を作製し、東洋精機製作所製JISL-Dを用いて23℃におけるアイゾット衝撃強度の測定を行った。アイゾット衝撃強度は15kJ/m2以上であるものを合格とした。
JIS K-7191A(2007年)法に基づいて、長さ80mm×幅10mm×厚さ4mmの試験片を作製し、東洋精器社製S-3Mを用いて荷重たわみ温度の測定を行った。測定は、フラットワイズ方向、試験片に加える曲げ応力0.45MPaの条件で行った。荷重たわみ温度が70℃以上であるものを合格とした。
PC1:
イソソルビドに由来する構造単位/1,4-シクロヘキサンジメタノールに由来する構造単位=30/70モル%、
ガラス転移温度=80℃、還元粘度 0.69dl/g
PC2:
イソソルビドに由来する構造単位/1,4-シクロヘキサンジメタノールに由来する構造単位=40/60モル%、
ガラス転移温度=90℃、還元粘度 0.69dl/g
PC3:
イソソルビドに由来する構造単位/1,4-シクロヘキサンジメタノールに由来する構造単位=50/50モル%、
ガラス転移温度=101℃、還元粘度 0.57dl/g
PC4:
イソソルビドに由来する構造単位/1,4-シクロヘキサンジメタノールに由来する構造単位=60/40モル%、
ガラス転移温度=110℃、還元粘度 0.51dl/g
PC5:
イソソルビドに由来する構造単位/トリシクロデカンジメタノールに由来する構造単位=50/50モル%
ガラス転移温度=110℃、還元粘度 0.60dl/g
PC6:三菱エンジニアリングプラスチックス社製ユーピロンS3000
ガラス転移温度=150℃、還元粘度 0.49dl/g、粘度平均分子量=20,000
PC1、及び、PC6を質量比90:10の割合でドライブレンドした後、三菱重工製40mmφ小型同方向二軸押出機を用いて240℃でコンパウンドし、ペレット形状にした。得られたペレットを東芝機械製射出成形機 IS50E(スクリュー径25mm)を用い、各種評価用のサンプルを射出成形にて作製した。主な成形条件は以下の通りである。
1)温度条件:シリンダー温度(240℃) 金型温度(6℃)
2)射出条件:射出圧力(115MPa) 保持圧力(55MPa)
3)計量条件:スクリュー回転数(65rpm) 背圧(15MPa)
得られたサンプルについて、ガラス転移温度、光弾性係数、全光線透過率、ヘーズ、アイゾット衝撃強度、荷重たわみ温度の測定を行なった結果を表1に示す。
PC1、及び、PC6を混合質量比60:40の割合で混合した以外は実施例2-1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2に示す。
PC1、及び、PC6を混合質量比30:70の割合で混合した以外は実施例2-1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2に示す。
PC2、及び、PC6を混合質量比60:40の割合で混合した以外は実施例2-1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2に示す。
PC3、及び、PC6を混合質量比60:40の割合で混合した以外は実施例2-1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2に示す。
脂肪ポリカーボネート樹脂(A)を使用せずに、PC6のみを用い、金型温度を100℃とした以外は実施例2-1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2に示す。
PC4、及び、PC6を混合質量比60:40の割合で混合した以外は実施例2-1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2に示す。
PC5、及び、PC6を混合質量比60:40の割合で混合した以外は実施例2-1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2に示す。
脂肪族ポリカーボネート樹脂(A)の代わりに、イーストマンケミカル社製PCTG24635(ポリ(1,4-シクロヘキシレンジメチレンテレフタレート)グリコール)を用い、PCTG24635、及び、PC6を混合質量比60:40の割合で混合した以外は実施例2-1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2に示す。
なお、本明細書中に表示される原料及び試験片についての種々の測定値及び評価は次の様にして行った。ここで、フィルムの押出機からの流れ方向を縦方向、その直交方向を横方向と呼ぶ。
ウベローデ粘度計を使用し、ポリカーボネート樹脂試料の塩化メチレン溶液(0.6g/dl)を調製し、20℃におけるηspを測定し、以下の式(I)及び(II)より粘度平均分子量(Mv)を求めた。
ηsp/C=[η]×(1+0.28ηsp) (I)
[η]=1.23×10-4×(Mv)0.83 (II)
(式(I)中、ηspはポリカーボネート樹脂試料の塩化メチレン中20℃で測定した比粘度であり、Cはこの塩化メチレン溶液の濃度である。塩化メチレン溶液としては、ポリカーボネート樹脂試料の濃度が0.6g/dlの溶液を使用する。)
中央理化社製DT-504型自動粘度計にてウベローデ型粘度計を用い、溶媒として、塩化メチレンを用い、温度20.0℃±0.1℃でポリカーボネート樹脂試料の還元粘度を測定した。濃度は0.60g/dlになるように、精密に調整した後に測定した。
溶媒の通過時間t0、溶液の通過時間tから、下記式:
ηrel=t/t0
より相対粘度ηrelを求め、 相対粘度ηrelから、下記式:
ηsp=(η-η0)/η0=ηrel-1
より比粘度ηspを求めた。
比粘度ηspを濃度c(g/dl)で割って、下記式:
ηred=ηsp/c
より還元粘度(換算粘度)ηredを求めた。
この数値が高いほど分子量が大きい。
示差走査熱量計(メトラー社製「DSC822」)を用いて、試料約10mgを10℃/minの昇温速度で加熱して測定し、JIS K7121(1987)に準拠して、低温側のベースラインを高温側に延長した直線と、ガラス転移の階段状変化部分の曲線の勾配が最大になるような点で引いた折線との交点の温度である、補外ガラス転移開始温度Tigを求めた。
JIS K7105(1981年)に基づいて、全光線透過率および拡散透過率を測定し、ヘーズを以下の式で算出した。厚み0.2mmでの全光線透過率が80%以上、ヘーズが3%以下であるものを合格とした。
[ヘーズ]=[拡散透過率]/[全光線透過率]×100
JIS K7127(1999年)に基づき、横方向が測定方向となるように長さ120mm、幅10mm、厚み0.2mmの試験片を作製し、インテスコ社製万能材料試験機MODEL205を用いて、温度23℃ 、試験速度200mm/分の条件で引張り破壊強度・伸度の測定を行なった。引張破壊強度が50MPa以上、引張破壊伸度が100%以上のものを合格とした。
JIS K7127(1999年)に基づき、横方向が測定方向となるように長さ400mm、幅10mm、厚み0.2mmの試験片を作製し、インテスコ社製万能材料試験機MODEL205を用いて、温度23℃、引張速度5mm/minの条件で引張弾性率の測定を行った。引張弾性率は2.0GPa以上を合格とした。
ハイドロショット高速衝撃試験器(島津製作所社製「HTM-1型」)を用いて、縦方向100mm×横方向100mmの大きさに切り出したシートを試料とし、クランプで固定し、温度23℃でシート中央に直径が1/2インチの撃芯を落下速度3m/秒で落として衝撃を与え、試料が破壊するときの破壊エネルギー(kgf・mm)を測定した。破壊エネルギーが100kgf・mm以上のものを合格とした。
長さ5mm×幅5mm(厚みはそれぞれの試験片により異なる)の評価用サンプルを用いて、JIS K7196(1991年)に基づき、TMAによる軟化温度の測定を行った。温度23℃、相対湿度50%、圧子への圧力0.5N、昇温速度5℃/分にてTMA曲線を測定し、圧子が侵入を始めるよりも低温側に認められる直線部分を高温側に延長し、侵入速度が最大となる部分の接線の低温側への延長との交点を針侵入温度とし、この値から軟化温度を算出した。TMA軟化温度は70℃以上を合格とした。
島津製作所社製「高化式フローテスターCFT-500C型」を用いて、内径1mm、長さ2mmのノズルを用いて、温度200℃、せん断速度100sec-1とした時の溶融粘度を測定した。200℃、100sec-1における粘度が1,000Pa・s以上、20,000Pa・s以下であるものを合格とした。
各評価項目を総合して、各実施例及び比較例について以下の4基準をもって判定した。
◎:ガラス転移温度が単一であり、全光線透過率、ヘーズ、引張破壊強度・伸度、引張弾性率、耐衝撃性、耐熱性、流動性の全てが合格となるもの。
○:ガラス転移温度が単一であり、全光線透過率、ヘーズ、引張破壊強度・伸度、引張弾性率、耐衝撃性、耐熱性、流動性の全てが合格となるものの、流動性が若干劣るもの(10,000以上であるもの)。
△:ガラス転移温度が単一であり、全光線透過率、ヘーズ、引張破壊強度・伸度、耐衝撃性、耐熱性、流動性が合格となり、引張弾性率が劣るものの実用的に問題ないレベルのもの。
×:ガラス転移温度が単一でない、または、全光線透過率、ヘーズ、引張破壊強度・伸度、引張弾性率、耐衝撃性、耐熱性、流動性の内、1項目以上が不合格となり、実用的に問題があるレベルのもの。
PC1:
イソソルビドに由来する構造単位/1,4-シクロヘキサンジメタノールに由来する構造単位=30/70モル%、
ガラス転移温度=80℃、還元粘度 0.69dl/g
PC2:
イソソルビドに由来する構造単位/1,4-シクロヘキサンジメタノールに由来する構造単位=50/50モル%、
ガラス転移温度=101℃、還元粘度 0.57dl/g
PC3:
イソソルビドに由来する構造単位/1,4-シクロヘキサンジメタノールに由来する構造単位=60/40モル%、
ガラス転移温度=110℃、還元粘度 0.51dl/g
PC4:
イソソルビドに由来する構造単位/1,4-シクロヘキサンジメタノールに由来する構造単位=10/90モル%、
ガラス転移温度=50℃、還元粘度 0.51dl/g
PC5:
イソソルビドに由来する構造単位/トリシクロデカンジメタノールに由来する構造単位=50/50モル%、
ガラス転移温度=110℃、還元粘度 0.60dl/g
PC6:
三菱エンジニアリングプラスチックス社製ユーピロンS3000、
ガラス転移温度=150℃、還元粘度 0.49dl/g、粘度平均分子量=20,000
PC1、及び、PC6を混合質量比90:10の割合でドライブレンドした後、40mmφ同方向二軸押出機を用いて220℃で混練した後、Tダイより押出し、次いで約80℃のキャスティングロールにて急冷し、厚み0.2mmのシートを作製した。得られたシートについて、ガラス転移温度、引張破壊強度・伸度、引張弾性率、耐衝撃性、耐熱性、流動性の評価を行った。結果を表3に示す。
PC1、及び、PC6を混合質量比60:40の割合で混合し、キャスティングロール温度を100℃とした以外は実施例3-1と同様の方法でシートの作製、評価を行った。結果を表3に示す。
PC1、及び、PC6を混合質量比20:80の割合で混合し、キャスティングロール温度を130℃とした以外は実施例3-1と同様の方法でシートの作製、評価を行った。結果を表3に示す。
PC2、及び、PC6を混合質量比60:40の割合で混合し、キャスティングロール温度を120℃とした以外は実施例3-1と同様の方法でシートの作製、評価を行った。結果を表3に示す。
PC3、及び、PC6を混合質量比60:40の割合で混合し、キャスティングロール温度を120℃とした以外は実施例3-1と同様の方法でシートの作製、評価を行った。結果を表3に示す。
PC4、及び、PC6を混合質量比60:40の割合で混合し、キャスティングロール温度を110℃とした以外は実施例3-1と同様の方法でシートの作製、評価を行った。結果を表3に示す。
脂肪族ポリカーボネート樹脂を使用せずに、PC6のみを用い、キャスティングロール温度を130℃とした以外は実施例3-1と同様の方法で、シートの作製、評価を行った。結果を表3に示す。
PC5、及び、PC6を混合質量比60:40の割合で混合し、キャスティングロール温度を100℃とした以外は実施例3-1と同様の方法でシートの作製、評価を行った。結果を表3に示す。
Claims (20)
- 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、全光線透過率が85%以上であり、かつ該照射処理前後におけるイエローインデックス(YI)値の差が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組成物(X)が単一のガラス転移温度を有し、かつ、該ガラス転移温度が前記脂肪族ポリカーボネート樹脂(A)のガラス転移温度以上、前記芳香族ポリカーボネート樹脂(B)のガラス転移温度以下の範囲にある、請求項1または請求項2に記載のポリカーボネート樹脂組成物。
- 前記脂肪族ポリカーボネート樹脂(A)のガラス転移温度が、75℃以上、105℃以下である請求項1から請求項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組成物(X)のガラス転移温度が、75℃以上、130℃以下である請求項1から請求項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。
- JIS K7105(1981年)に基づきヘーズメーターを使用してD65光源にて測定した射出成形品の全光線透過率が60%以上である、請求項1から請求項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。
- 厚み1mmにおけるJIS K7361-1(1997年)に基づき測定した全光線透過率が80%以上であり、かつ、JIS K7105(1981年)に基づき測定したヘーズが5%以下である請求項1から請求項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。
- ISO179(2000年)に準拠して測定されたノッチ付シャルピー衝撃強度が10kJ/m2以上である、請求項1から請求項7いずれか1項に記載のポリカーボネート樹脂組成物。
- 前記脂肪族ポリカーボネート樹脂(A)中の全ジヒドロキシ化合物に由来する構成単位に対する前記脂肪族炭化水素のジヒドロキシ化合物(b)に由来する構成単位の割合が45モル%以上、80モル%以下であり、
前記ポリカーボネート樹脂組成物(X)中に占める脂肪族ポリカーボネート樹脂(A)の割合が1質量%以上、99質量%以下である、請求項1から請求項8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、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から請求項10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から請求項11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から請求項12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から請求項13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から請求項14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体。
- 600nmの光波長における光弾性係数が7×10-11Pa-1以下である、請求項15に記載の成形体。
- 請求項1から請求項14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フィルム。
- 厚み0.2mmに成形したときのJIS K7361-1(1997年)に基づき測定した全光線透過率が80%以上であり、かつ、JIS K7105(1981年)に基づき測定したヘーズが3%以下である、請求項17に記載のフィルム。
- 請求項1から請求項14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プレート。
- 請求項1から請求項14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射出成形して得られる射出成形品。
Priority Applications (4)
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|---|---|---|---|
| EP10836081.9A EP2511339B1 (en) | 2009-12-10 | 2010-12-10 | Polycarbonate resin composition and molded body, film, plate and injection-molded article obtained by molding same |
| KR1020127013405A KR101814832B1 (ko) | 2009-12-10 | 2010-12-10 | 폴리카보네이트 수지 조성물 그리고 이것을 성형하여 얻어지는 성형체, 필름, 플레이트 및 사출 성형품 |
| CN201080055922.2A CN102656231B (zh) | 2009-12-10 | 2010-12-10 | 聚碳酸酯树脂组合物以及将其成型而得到的成型体、膜、板和注射成型品 |
| US13/489,983 US8481625B2 (en) | 2009-12-10 | 2012-06-06 | Polycarbonate resin composition, and molded object, film, plate, and injection-molded article obtained by molding the same |
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| JP2009280865A JP5716274B2 (ja) | 2009-12-10 | 2009-12-10 | 樹脂組成物並びにこれを成形してなるフィルム、プレート及び射出成形品 |
| JP2009-280865 | 2009-12-10 | ||
| JP2009-288107 | 2009-12-18 | ||
| JP2009288107A JP2011127037A (ja) | 2009-12-18 | 2009-12-18 | 低光弾性成形体 |
| JP2010-185058 | 2010-08-20 | ||
| JP2010185058A JP6151471B2 (ja) | 2010-08-20 | 2010-08-20 | ポリカーボネート樹脂組成物及び成形品 |
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| US13/489,983 Continuation US8481625B2 (en) | 2009-12-10 | 2012-06-06 | Polycarbonate resin composition, and molded object, film, plate, and injection-molded article obtained by molding the same |
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| US (1) | US8481625B2 (ja) |
| EP (1) | EP2511339B1 (ja) |
| KR (1) | KR101814832B1 (ja) |
| CN (1) | CN102656231B (ja) |
| TW (1) | TWI492986B (ja) |
| WO (1) | WO2011071162A1 (ja) |
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| JP2013049847A (ja) * | 2011-08-03 | 2013-03-14 | Mitsubishi Chemicals Corp | 自動車内装品 |
| CN103842464A (zh) * | 2011-08-18 | 2014-06-04 | Sk新技术株式会社 | 热熔性组合物 |
| JP2017014502A (ja) * | 2015-06-30 | 2017-01-19 | 三菱化学株式会社 | ポリカーボネート樹脂組成物、その製造方法、成形体 |
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|---|---|---|---|---|
| JP2013049846A (ja) * | 2011-08-03 | 2013-03-14 | Mitsubishi Chemicals Corp | 遮音部材 |
| JP2013049847A (ja) * | 2011-08-03 | 2013-03-14 | Mitsubishi Chemicals Corp | 自動車内装品 |
| CN103842464A (zh) * | 2011-08-18 | 2014-06-04 | Sk新技术株式会社 | 热熔性组合物 |
| JP2017014502A (ja) * | 2015-06-30 | 2017-01-19 | 三菱化学株式会社 | ポリカーボネート樹脂組成物、その製造方法、成形体 |
| KR20180022712A (ko) | 2015-06-30 | 2018-03-06 | 미쯔비시 케미컬 주식회사 | 폴리카보네이트 수지 조성물, 그 제조 방법, 성형체 |
| US10526446B2 (en) | 2015-06-30 | 2020-01-07 | Mitsubishi Chemical Corporation | Polycarbonate resin composition, method for producing same, and molded object |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2511339B1 (en) | 2017-06-07 |
| KR20120117756A (ko) | 2012-10-24 |
| KR101814832B1 (ko) | 2018-01-30 |
| TW201130912A (en) | 2011-09-16 |
| US20120245266A1 (en) | 2012-09-27 |
| CN102656231B (zh) | 2014-04-30 |
| CN102656231A (zh) | 2012-09-05 |
| EP2511339A4 (en) | 2015-07-08 |
| TWI492986B (zh) | 2015-07-21 |
| US8481625B2 (en) | 2013-07-09 |
| EP2511339A1 (en) | 2012-10-17 |
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