JP2009138180A - Polycarbonate resin composition - Google Patents

Abstract

Disclosed is a polycarbonate resin composition that improves the compatibility between polycarbonate and polylactic acid, has a good appearance without pearly luster, and has improved appearance and fluidity without impairing impact resistance.
A block copolymer having a polyester structural unit (II) obtained by esterifying a polycarbonate (A), a polylactic acid (B), a polyhydroxycarboxylic acid structural unit (I), and a dicarboxylic acid and a diol. A polycarbonate resin composition comprising a polymer (C).
[Selection figure] None

Description

  The present invention relates to a polycarbonate resin composition modified with polylactic acid, and more specifically, a polycarbonate resin composition excellent in fluidity and impact resistance in which poor compatibility between polyhydroxycarboxylic acid and polycarbonate is improved with a specific polyester resin. It is about things.

  Polycarbonate resins are widely used in all fields as excellent engineering plastics. Also, a polycarbonate / polylactic acid alloy having good fluidity using plant-derived polylactic acid is known from the viewpoint of reducing environmental burden. However, the simple polycarbonate / polylactic acid alloy has poor compatibility due to low compatibility between polycarbonate and polylactic acid, and further, since the heat resistance, thermal stability, impact resistance, etc. are insufficient, it is improved. is needed.

  The resin composition composed of polycarbonate and polylactic acid has a feature that the appearance is pearly luster (see, for example, Patent Document 1), but when applied to a colored molded product such as a casing when it has pearly luster, There was a problem in that stable coloring could not be performed and color unevenness was caused. In addition, a resin composition in which polycarbonate and polylactic acid are reacted and compatibilized with a radical initiator to improve heat resistance is known (see, for example, Patent Document 2), but not an aromatic polycarbonate but an aliphatic polyester carbonate. Therefore, heat resistance and impact resistance were insufficient as compared with general-purpose aromatic polycarbonate systems.

  Although a technique of adding an aromatic vinyl / conjugated diene block copolymer as a third component has also been reported (for example, see Patent Document 3), although the impact resistance is improved, the appearance defect cannot be sufficiently improved. There was a problem. Although improvement by addition of a compound having a functional group that reacts with active hydrogen has been reported (for example, see Patent Document 4), sufficient effects have not been obtained. Although attempts have been made to refine the polylactic acid domain using a block copolymer of caprolactone and polylactic acid (see, for example, Patent Document 5), there has been a problem that appearance defects cannot be sufficiently improved.

JP-A-7-109413 JP 2002-371172 A JP 2007-131895 A JP 2006-241209 A JP 2007-138131 A

  The problem to be solved by the present invention is to improve the compatibility between polycarbonate and polylactic acid, to have a good appearance without pearly luster, and to improve the appearance and fluidity without impairing the impact resistance. It is to provide a resin composition.

  As a result of extensive research, the present inventor has found that the above-described problems of the present invention can be solved by using a block copolymer having a polyhydroxycarboxylic acid structural unit and a specific polyester structural unit. Was completed.

  That is, the present invention has a polyester structural unit (II) obtained by esterifying a polycarbonate (A), a polylactic acid (B), a polyhydroxycarboxylic acid structural unit (I), and a dicarboxylic acid and a diol. A polycarbonate resin composition comprising a block copolymer (C) and a resin molded product using the resin composition are provided. Moreover, this invention provides the manufacturing method of the said block copolymer (C).

  According to the present invention, there is provided a polycarbonate resin composition having improved compatibility between polycarbonate and polylactic acid, having a good appearance without pearly luster, and improved fluidity without impairing impact resistance. be able to. Therefore, the polycarbonate resin composition obtained by the present invention can be suitably used for various molded products such as OA equipment parts and power tool parts.

  The polycarbonate (A) used in the present invention is obtained by, for example, a method of interfacial polycondensation of divalent phenol and carbonyl halide, a method of melt polymerization (transesterification method) of divalent phenol and carbonic acid diester, or the like. What was manufactured can be used.

  Examples of the divalent phenol include hydroquinone, resorcin, catechol, 4,4′-dihydroxydiphenyl, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane [ Bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4′-hydroxyphenyl) butane, bis (4-hydroxyphenyl) cycloalkane, bis (4 -Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, 4,4'-dihydroxydiphenyl ether, and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use a bis (hydroxyphenyl) alkane-based compound such as bisphenol A that is widely available as a main raw material, and a bis (hydroxyphenyl) alkane-based compound such as bisphenol A is used as a main raw material. A molded product obtained by molding the polycarbonate resin composition is excellent in impact resistance.

  As the carbonyl halide, for example, carbonyl chloride generally referred to as phosgene, carbonyl bromide, and a mixture thereof can be used.

  Examples of the carbonic acid diester include diphenyl carbonate, bis (methylphenyl) carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and mixtures thereof. .

  The method of interfacial polycondensation of the divalent phenol and the carbonyl halide is, for example, generally referred to as a phosgene method, specifically, a sodium hydroxide aqueous solution in which the divalent phenol is dispersed, and a halogen carbonyl. The solution is mixed with a methylene chloride solution in which the solution is dissolved and stirred to cause interfacial polycondensation.

  The divalent phenol and carbonic acid diester are melt-polymerized (transesterification method) by, for example, heating and melting the divalent phenol and carbonic acid diester and proceeding the transesterification reaction by dephenol reaction to polycondensation. It is a method to make it.

  As the method for producing the polycarbonate (A), among the various production methods described above, the method of interfacial polycondensation of the divalent phenol and the carbonyl halide is the content of low molecular weight by-products such as phenols. It is preferable because it is small. Further, the polycarbonate (A) obtained by this method can exhibit high impact resistance after molding.

  The polycarbonate (A) is a weight average molecular weight (the weight average molecular weight described below is a value in terms of styrene measured by a gel permeation chromatography method (hereinafter referred to as “GPC method”)). ) Is preferably 15,000 to 60,000 because it is excellent in the balance of mechanical strength, impact resistance, and composition fluidity of the molded article obtained, and 25,000 to 45 It is preferable to use those having a weight average molecular weight in the range of 1,000, since further excellent mechanical properties and composition fluidity can be obtained.

  For adjusting the molecular weight of such polycarbonate, phenol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol and the like are used.

  Examples of the polylactic acid (B) used in the present invention include L-polylactic acid, D-polylactic acid, D, L-polylactic acid, stereocomplex polylactic acid composed of a mixture of L-polylactic acid and D-polylactic acid, and These mixtures can be preferably used.

  The D, L-polylactic acid is a copolymer of L-lactic acid or L-lactide and D-lactic acid or D-lactide, and particularly the proportion of structural units derived from L-lactic acid or L-lactide or D -It is preferable to use what the ratio of the structural unit derived from lactic acid or D-lactide is 90 mass% or more, and it is more preferable to use what is 95 mass% or more. By using such D, L-polylactic acid, a polylactic acid resin composition excellent in heat resistance and molding processability can be obtained.

  The ratio of the L-form and D-form (optical isomer ratio) constituting the D, L-polylactic acid is determined by performing high performance liquid chromatography equipped with an optical isomer separation column on lactic acid obtained by hydrolyzing it. It can be determined by separating the L-lactic acid and D-lactic acid and then quantifying them. Examples of the hydrolysis method include a method in which D, L-polylactic acid and a sodium hydroxide / methanol mixed solution are mixed using a water bath soaker set at 65 ° C., for example. In quantification using high performance liquid chromatography, it is preferable to use one that has been previously neutralized with a diluted hydrochloric acid solution or the like.

  The polylactic acid has a molecular weight in the range of 50,000 to 400,000 in terms of standard polystyrene in terms of standard polystyrene by the GPC method from the viewpoint of maintaining good moldability and mechanical properties. It is preferable to use those having a mass average molecular weight in the range of 100,000 to 400,000.

  The GPC method uses, for example, a gel permeation chromatography measuring apparatus (“HLC-8220” manufactured by Tosoh Corporation), and includes two TSK gel SuperHZM-M and two TSK gel SuperHZ-2000 columns. And TSK SuperH-H as a guard column and tetrahydrofuran as a developing solvent.

  The polylactic acid can be produced, for example, by a condensation polymerization method of lactic acid or a ring-opening polymerization method of lactide which is a cyclic dimer of lactic acid. The polycondensation reaction of lactic acid is a method in which a carboxyl group and a hydroxyl group of lactic acid are esterified. For example, L-lactic acid, D-lactic acid or a mixture thereof is azeotropically dehydrated in the presence of a high-boiling solvent under reduced pressure. A method is mentioned. The ring-opening polymerization method using the lactide is a method in which the ring-opened lactides are esterified with each other. For example, L-lactide or D-lactide is opened in the presence of a polymerization regulator and a polymerization catalyst. The method of letting it be mentioned. Furthermore, D, L-lactide, which is a dimer of L-lactic acid and D-lactic acid, may be used in combination within the scope of achieving the object of the present invention.

  Further, according to the present invention, at least one hydroxycarboxylic acid selected from the group consisting of polyglycolic acid having strength and toughness, polycaprolactone having flexibility, polyhydroxybutyrate having high plantiness, and polyhydroxyvalylate. An acid-derived polymer can also be preferably used. For example, examples of the hydroxycarboxylic acid-derived polymer include a polymer of polyglycolic acid and polylactic acid, and a polymer of polyglycolic acid and polycaprolactone. Here, the plant degree refers to mass% (volume% may be specified) of plant-derived raw materials in products, commodities, and plastics. For example, if the plant degree is 100%, it means that the plastic is produced only from plant-derived materials.

  The block copolymer (C) used in the present invention has a polyhydroxycarboxylic acid structural unit (I) and a polyester structural unit (II) obtained by esterifying a dicarboxylic acid and a diol.

  More specifically, when the polyhydroxycarboxylic acid structural unit (I) is X and the polyester structural unit (II) obtained by esterification reaction of dicarboxylic acid and diol is Y, a block copolymer (C The form of) varies depending on the charge ratio and molecular weight of the raw materials used when producing the block copolymer (C), but an XY block copolymer, an XYX block copolymer, a random block copolymer, and these And the like. Moreover, as long as the characteristic of a block copolymer (C) is not impaired, these may contain polyhydroxycarboxylic acid, polyester, etc. as a non-copolymerization thing.

  Further, the block copolymer (C) used in the present invention comprises a carbodiimide in addition to the above-mentioned polyhydroxycarboxylic acid structural unit (I) and a polyester structural unit (II) obtained by esterification reaction of a dicarboxylic acid and a diol. It has structural unit (III). Those having a carbodiimide structural unit (III) are effective in preventing performance deterioration due to hydrolysis of ester bonds.

  That is, in the present invention, by adding a copolymer comprising a polyhydroxycarboxylic acid structural unit (I) and a polyester structural unit (II) to the polycarbonate (A), the intended impact properties and fluidity can be improved. The same effect can be obtained by using a copolymer having a carbodiimide structural unit (III) introduced in addition to the polyhydroxycarboxylic acid structural unit (I) and the polyester structural unit (II).

  By introducing the carbodiimide structural unit (III) into the block copolymer (C), it is expected that the hydrolysis resistance is improved as compared with the case where the carbodiimide compound is simply added. Here, a carbodiimide compound is present in the vicinity of the block copolymer (C) in order to improve the hydrolyzability of the block copolymer (C), which is considered to be inferior in hydrolysis resistance compared to polycarbonate. However, when a carbodiimide compound is simply added, the carbodiimide compound cannot be surely present in the vicinity of the block copolymer (C). Therefore, by introducing the carbodiimide structural unit (III) into the block copolymer (C) in advance, it is possible to construct a form similar to the state in which a carbodiimide compound is present in the vicinity of the block copolymer (C). it can.

  More specifically, the polyhydroxycarboxylic acid structural unit (I) is X, the polyester structural unit (II) obtained by esterifying the dicarboxylic acid and the diol is Y, and the carbodiimide structural unit (III) is Z. The form of the block copolymer (C) at this time varies depending on the charge ratio and molecular weight of the raw materials used in producing the block copolymer (C), but the XY block copolymer formed by the former two A structure in which a polymer, an XYX type block copolymer, a random block copolymer is chain-extended with Z, or a structure in which Y is chain-extended with Z and X is block or randomly copolymerized, and These mixtures etc. are mentioned. Moreover, as long as the characteristic of a block copolymer (C) is not impaired, these may contain polyhydroxycarboxylic acid, polyester, etc. as a non-copolymerization thing.

  The blending ratio of the polycarbonate (A) and the polylactic acid (B) in the polycarbonate resin composition of the present invention is not particularly limited, but aims to reduce the environmental burden of the polycarbonate (A) derived from petroleum. In that case, it is desirable to use as much polylactic acid derived from plants as possible. Further, in order to satisfy the registration standard of “Biomass Plastic” of Japan Bioplastics Association (JBPA), it is desirable to contain 25% by mass or more of polylactic acid in the polycarbonate resin composition.

  The blending ratio of the polylactic acid (B) and the block copolymer (C) is in the range of 99/1 to 50/50 based on the mass of the polylactic acid (B) / the block copolymer (C). The range of 95/5 to 50/50 is more preferable. If it is this range, the compatibility of polycarbonate (A) and polylactic acid (B) will improve, and polylactic acid (B) will disperse | distribute favorably in polycarbonate (A).

  The block copolymer (C) has a mass ratio [(I) / (II)] of the polyester structural unit (I) and the polyhydroxycarboxylic acid structural unit (II) in the range of 95/5 to 10/90. It is preferable that it is in the range of 85/15 to 20/80, more preferably in the range of 75/25 to 30/70. When there are many polyhydroxycarboxylic acid structural units (II), pelletization of the obtained block copolymer becomes easy and workability | operativity becomes favorable.

  The block copolymer (C) preferably has a weight average molecular weight in the range of 5,000 to 400,000 in the GPC method from the viewpoint of the effect as a compatibilizing agent. Is more preferably in the range of 15,000, and particularly preferably in the range of 15,000 to 300,000.

  Ratio (I) + (II) / (III) of the total amount of the polyhydroxycarboxylic acid structural unit (I) and the polyester structural unit (II) and the carbodiimide structural unit (III) in the block copolymer (C) ) Is preferably in the range of 95/5 to 99.9 / 0.1 on a mass basis. If it is this range, block copolymerization of block copolymer (C) can accelerate | stimulate chain | strand extension reaction, and durability of the polycarbonate resin composition of this invention by hydrolysis of block copolymer (C) Can be suppressed.

  The polyester (II ′) that forms the polyester structural unit (II) of the block copolymer (C) is a polyester that can be produced by reacting a diol, a dicarboxylic acid, and a hydroxycarboxylic acid.

  The polyester (II ′) may be crystalline or non-crystalline, but in order to obtain a film or sheet excellent in transparency and moldability, non-crystalline polyester is used. Is preferred. Here, “crystalline polyester” and “non-crystalline polyester” as used in the present invention are defined by the presence or absence of a melting point. Specifically, “amorphous polyester” refers to a polyester having a heat of fusion of 0 kJ / kg. The melting point is about 10 mg of a film piece of polyester (II ′) which has been conditioned in a standard state, according to JIS-K7122, using a differential scanning calorimeter “DSC 220C” manufactured by TA Instruments. And can be obtained by performing measurement from −100 ° C. to 210 ° C. at a nitrogen gas flow rate of 50 ml / min and a heating rate of 10 ° C./min. The polyester (II ′) having no endothermic peak within the measurement temperature range can be referred to as an amorphous polyester.

  Moreover, as said polyester (II '), what has an acid value of 10 or less is preferable, it is more preferable that it is 8 or less, and it is especially preferable that it is the range of 0.1-5. When polyester having an acid value within this range is used, a block excellent in molding processability that can suppress unreacted substances by improving the conversion rate of the reaction when producing the block copolymer (C) and is difficult to gel. A copolymer (C) can be obtained.

  In addition, when the polyester (II ′) is a so-called random copolymer in which a structural unit derived from a diol and a structural unit derived from a dicarboxylic acid are randomly arranged, a by-product is generated. This is preferable because it can be suppressed and the polyester (II ′) can have a high molecular weight.

  The polyester (II ′) preferably has a weight average molecular weight of 5,000 to 200,000, more preferably 5,000 to 200,000, and more preferably 5,000 to 200,000. It is particularly preferred. The block copolymer (C) having a polyester structural unit (II) derived from the polyester (II ′) having a weight average molecular weight within this range has a good appearance when mixed with polycarbonate, and has impact resistance and fluidity. Can be improved.

  Although it does not specifically limit as diol used when manufacturing said polyester (II '), For example, it is preferable to use aliphatic diol, aromatic diol, and alicyclic diol.

  Specific examples of the aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanedimeta , Neopentyl glycol, 3,3-diethyl-1,3-propanediol, 3,3-dibutyl-1,3-propanediol, 2-methyl-2,4-pentanediol, n-butoxyethylene glycol, Dimer acid diol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, xylylene glycol, phenylethylene glycol and the like can be used.

  As the aromatic diol, an ethylene oxide adduct or propylene oxide adduct of bisphenol A can also be used. Examples of the alicyclic diol include cyclohexanedimethanol and hydrogenated bisphenol A.

Although said diol can also be used independently, 2 or more types can also be used together. For example, the combined use of 1,2-propanediol and polyethylene glycol, the combined use of ethylene glycol and 1,4-butanediol, and the like can be mentioned.
above

  Examples of the dicarboxylic acid used in producing the polyester (II ′) include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, Examples thereof include aliphatic dicarboxylic acids such as dimer acid, unsaturated aliphatic dicarboxylic acids such as fumaric acid, succinic anhydride, adipic anhydride, phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. These can be used alone or in combination of two or more.

  As the dicarboxylic acid, the performance of the resulting block copolymer (C), specifically, excellent impact resistance and fluidity can be imparted to the polycarbonate, so adipic acid, sebacic acid or their anhydrides It is preferable to use these esterified products.

  Moreover, it is possible to use a hydroxycarboxylic acid as long as the effects of the present invention are not impaired when the polyester (II ′) is produced. The hydroxycarboxylic acid is not particularly limited as long as it is a compound having a hydroxyl group and a carboxyl group in one molecule. For example, lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, Examples include 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, and p-hydroxybenzoic acid. These can be used alone or in combination of two or more. When a hydroxycarboxylic acid having an optical isomer is used, any of D-form, L-form, and racemate can be used. The hydroxycarboxylic acid may be solid or liquid, and may be used as an aqueous solution.

  As the hydroxycarboxylic acid, use of lactic acid or glycolic acid is easy to obtain, the reaction control when producing the polyester (II ′) is easy, a dimer or a 3 amount of polyester. It is preferable because generation of by-products such as body can be greatly suppressed. Moreover, it is easy to adjust the molecular weight of the obtained polyester to a relatively high molecular weight by using the hydroxycarboxylic acid.

  The production method of the polyester (II ′) is not particularly limited. For example, the diol, dicarboxylic acid, anhydride or esterified product thereof, and the hydroxycarboxylic acid may be used as necessary using an esterification catalyst. Thus, it can be produced by esterification by a known and usual esterification reaction. At that time, in order to suppress coloring of the polyester (II ′), an antioxidant such as a phosphite compound, the total of the diol, the dicarboxylic acid, its anhydride or its esterified product, and the hydroxycarboxylic acid It is preferable to use in the range of 10 to 2000 ppm with respect to the amount.

  The hydroxycarboxylic acid may be an esterification reaction by mixing diol, dicarboxylic acid, anhydride or esterified product thereof, and hydroxycarboxylic acid, but the diol and dicarboxylic acid, anhydride thereof or the diol may be mixed. After reacting in advance with the esterified product, hydroxycarboxylic acid may be mixed and esterified.

  The combination of the diol and the dicarboxylic acid is not particularly limited, but a combination of a diol having 3 to 8 carbon atoms and a dicarboxylic acid having 4 to 12 carbon atoms is preferable.

  As the esterification catalyst, it is preferable to use a catalyst composed of at least one metal selected from the group consisting of Groups 2, 3, and 4 of the periodic table, or a metal compound thereof. Examples of the metal include metals such as Ti, Sn, Zn, Al, Zr, Mg, Hf, and Ge. Examples of the metal compound include titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, tin octoate, 2-ethylhexanetin, acetylacetonate zinc, zirconium tetrachloride, and zirconium tetrachloride tetrahydrofuran complex. Examples include hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, and tetraethoxygermanium.

  The amount of the esterification catalyst used is usually an amount that can control the reaction and obtain good quality, and is generally 10 to 1000 ppm based on the total amount of diol, dicarboxylic acid and hydroxycarboxylic acid. The range is preferable, the range of 20 to 800 ppm is more preferable, and the range of 30 to 500 ppm is particularly preferable from the viewpoint of reducing the coloration of the polyester (II ′).

  The esterification catalyst may be added when the raw materials such as diol and dicarboxylic acid are charged, or may be added before the reaction system is depressurized.

  Further, the esterification catalyst can be deactivated by a publicly known method after the production of the polyester (II ′) to suppress side reactions during melt-mixing with the polylactic acid or lactone described later. It is preferable because it is possible. As a method for deactivating the esterification catalyst, for example, there is a method using a chelating agent.

  As the chelating agent, a known and commonly used organic chelating agent or inorganic chelating agent can be used. Examples of organic chelating agents include amino acids, phenols, hydroxycarboxylic acids, diketones, amines, oximes, phenanthrolines, pyridine compounds, dithio compounds, diazo compounds, thiols, porphyrins, and nitrogen as a coordinating atom. Examples thereof include phenols having atoms and carboxylic acids. Examples of the inorganic chelating agent include phosphorus compounds such as phosphoric acid, phosphoric acid ester, phosphorous acid, and phosphorous acid ester.

  Further, before and after the addition of the deactivator for the esterification catalyst, the polyester (II ′) is reacted with an acid anhydride, a polyvalent isocyanate, a peroxide, etc. to make the chemical structure of the polyester (B) branched. It can also be set as the high molecular weight polyester (B). Further, the compound (III ′) having at least one carbodiimide group described later may be reacted at this stage.

  The temperature for producing the polyester (II ′) is preferably in the range of 150 to 260 ° C., and more preferably in the range of 180 to 230 ° C. The polymerization time for producing the polyester (II ′) is preferably 2 hours or more, and more preferably in the range of 4 to 60 hours. The degree of reduced pressure when producing the polyester (II ′) is preferably 1.33 kPa or less, and more preferably 0.26 kPa or less.

  The polyhydroxycarboxylic acid (I ′) constituting the polyhydroxycarboxylic acid structural unit (I) may be any one that consists of a repeating unit of an aliphatic carboxylic acid having a hydroxyl group in the molecule, such as polylactic acid, Examples include polycaprolactone, polyglycolic acid, polyhydroxybutyrate, polyhydroxyvalylate, polylactic acid / glycolic acid copolymer, polyhydroxybutyrate / valerate copolymer, and the like. These can be used alone or in combination of two or more.

  As the polyhydroxycarboxylic acid (I ′), polylactic acid is preferably used as a main component in order to impart moldability. That is, the content of polylactic acid contained in the polyhydroxycarboxylic acid (I ′) is preferably 50% by mass or more, more preferably 60% by mass or more, and most preferably 100% by mass. . The block copolymer (C) using 50% by mass or more of polylactic acid as the polyhydroxycarboxylic acid (I ′) can impart excellent fluidity and impact resistance to the polycarbonate resin composition.

  In addition, the polyhydroxycarboxylic acid (I ′) is an L-form, D-form, or a mixture of L-form and D-form when the repeating unit has an asymmetric carbon atom such as polylactic acid (the mixing ratio is particularly Any of racemates can be used. In the present invention, “polylactic acid” means poly (L-lactic acid) whose structural unit is L-lactic acid, poly (D-lactic acid) whose structural unit is D-lactic acid, structural units that are L-lactic acid and D-lactic acid. Poly (DL-lactic acid) or a mixture thereof.

  When the polyhydroxycarboxylic acid (I ′) is polylactic acid, in order to form a stereocomplex with the polylactic acid (B), when the structural unit of the polylactic acid (B) is L-lactic acid, When the hydroxycarboxylic acid (I ′) is poly (D-lactic acid) and the structural unit of the polylactic acid (B) is D-lactic acid, the polyhydroxycarboxylic acid (I ′) is poly (L-lactic acid). Thus, a stereocomplex is formed, and the polycarbonate resin composition of the present invention has a high melting point, which is preferable since heat resistance, mechanical properties, and the like are improved.

  The molecular weight of the polyhydroxycarboxylic acid structural unit (I) used in the present invention is not particularly limited as long as it does not impair the effects of the present invention. However, from the viewpoint that the resulting block copolymer (C) can impart excellent properties such as melt moldability and impact resistance to the polycarbonate, the weight average molecular weight by the GPC method is 5,000 to 400, Is preferably in the range of 10,000 to 400,000, more preferably in the range of 10,000 to 300,000, and most preferably in the range of 15,000 to 250,000.

  The block copolymer (C) has a strain of 1 to 60% using a rotary rheometer at a frequency of 1 Hz and a temperature within the range of the melting point of the molding resin to the melting point + 50 ° C. When changed, the storage elastic modulus G ′ (M%) of the strain M% (1 <M ≦ 60) is in the range of 90 to 100% of the storage elastic modulus G ′ (1%) of the strain 1%. It is preferable to use it.

  Although it does not specifically limit as said rotation type rheometer, For example, the Ares viscoelasticity measuring apparatus by a TA instrument company can be used.

  The measurement conditions are preferably frequency: 1 Hz, temperature: melting point of the block copolymer (C) to the melting point + 50 ° C., but if the viscosity after the melting point of the molding resin is low, the melting point to the melting point of the copolymer. A range of + 30 ° C. is more preferable. Further, the parallel plate is not particularly limited as long as it is within the range of 25 mmφ and the gap (distance between the parallel plates): 0.5 to 2.0 mm, but 0.5 to 1.0 mm is particularly preferable. Further, a cone plate can be preferably used in addition to the parallel plate.

  Under the above conditions, a curve indicating the relationship with the storage elastic modulus (G ′) when the strain is changed is measured. In the block copolymer (C), when the strain is changed from 1 to 60%, the storage elastic modulus G ′ (M%) of strain M% (1 <M ≦ 60) is 1%. It is preferably within the range of 90 to 100% of '(1%), and particularly preferably within the range of 95 to 100%.

  As a manufacturing method of the said block copolymer (C), the following methods 1-3 are mentioned, for example.

(Method 1)
A production method in which the polyester (II ′) and the polyhydroxycarboxylic acid (I ′) are esterified in the presence of an esterification catalyst under reduced pressure conditions.

(Method 2)
A production method in which the polyester (II ′) and lactone are reacted in the presence of a ring-opening polymerization catalyst.

(Method 3)
A production method in which the polyester (II ′) and the polyhydroxycarboxylic acid (I ′) are subjected to an azeotropic dehydration polycondensation reaction under reduced pressure conditions in the presence of a high-boiling solvent using an esterification catalyst.

  In Method 1, for example, the block copolymer (C) is obtained by polycondensation reaction of the diol, the dicarboxylic acid, an anhydride thereof, or an esterified product thereof, and, if necessary, a hydroxycarboxylic acid. The reaction product obtained by esterifying the polyester (II ′) and the polyhydroxycarboxylic acid (I ′) in the presence of an esterification catalyst under reduced pressure conditions, using a rotary rheometer, has a frequency of 1 Hz, When the strain was changed from 1% to 60% under the measurement conditions within the range of the melting point of the reactant to the melting point + 50 ° C., the storage elastic modulus G ′ (M%) of the strain M% (1 <M ≦ 60) ) Can be produced by continuing the esterification reaction until it reaches 90 to 100% of the storage elastic modulus G ′ (1%) with a strain of 1%.

  The reaction temperature in Method 1 is preferably in the range of 170 to 220 ° C, and more preferably in the range of 180 to 210 ° C. By reacting at a temperature in this range, it is possible to suppress a decrease in the molecular weight of the resulting block copolymer (C).

  In addition, the degree of reduced pressure in Method 1 is preferably as the vacuum is higher because the polymerization reaction proceeds more rapidly. Specifically, it is preferably 2 kPa or less, more preferably 1 kPa or less, and particularly preferably 0.5 kPa or less.

  As the kind of the esterification catalyst, the same esterification catalyst as that exemplified as the one that can be used for producing the polyester (II ′) can be used.

  Moreover, since the presence of moisture lowers the molecular weight of the resulting block copolymer (C), it is particularly preferable to use the polyester (II ′) that has been sufficiently dried before the reaction.

  The amount of the esterification catalyst used is preferably in the range of 50 to 500 ppm, more preferably in the range of 50 to 300 ppm, and more preferably 50 to 200 ppm with respect to the total amount of polyester (II ′) and polyhydroxycarboxylic acid (I ′). The range of is particularly preferable. If the amount of the catalyst used is within this range, the polymer chain of the polyhydroxycarboxylic acid (I ′) generated during the reaction is prevented from being cut, so that the molecular weight reduction of the block copolymer (C) is suppressed and a good hue is achieved. Can be obtained.

  As a method for producing the block copolymer (C) by reacting the polyester (II ′) and lactone in Method 2 in the presence of a ring-opening polymerization catalyst, for example, in a reaction kettle set to a predetermined temperature, The polyester (II ′) and the lactone are dispersed and homogenized in a suitable good solvent, and then a ring-opening polymerization catalyst is added and reacted.

  The lactone is preferably a 5-membered ring or a 6-membered ring lactone. Examples of such a lactone include propiolactone, butyrolactone, valerolactone, and caprolactone. These can be used alone or in combination of two or more.

  As the reaction temperature, it is sufficient that the reaction proceeds substantially. From the viewpoint of preventing coloring and thermal decomposition of the resulting block copolymer (C), the reaction temperature is preferably in the range of 150 to 220 ° C. It is more preferable that the temperature is in the range of ° C, and it is particularly preferable that the temperature is in the range of 170 to 200 ° C.

  Moreover, in the method 2, it is preferable to carry out in the atmosphere of inert gas, such as nitrogen and argon. Furthermore, since water in the reaction system generally lowers the molecular weight of the block copolymer (C) obtained, it is preferable to use the polyester (II ′) that has been sufficiently dried before the reaction.

  Examples of the ring-opening polymerization catalyst include alkoxides such as Sn, Ti, Zr, Zn, Ge, Co, Fe, Al, Mn, and Hf. Among these, tin powder, tin octanoate, tin 2-ethylhexylate, dibutyltin dilaurate, tetraisopropyl titanate, tetrabutoxy titanium, titanium oxyacetylacetonate, iron (III) acetylacetonate, iron (III) ethoxide, aluminum Isopropoxide and aluminum acetylacetonate are preferred because they have a high activity for the reaction.

  As a high boiling point solvent to be used in the method 3 in which the polyester (II ′) and the polyhydroxycarboxylic acid (I ′) are subjected to an azeotropic dehydration polycondensation reaction under high pressure in the presence of a high boiling point solvent and a transesterification catalyst. Examples include xylene, anisole, diphenyl ether and the like. The degree of vacuum is preferably in the range of 1,000 to 3,000 Pa because the high boiling point solvent refluxes the reaction system. In addition, when making it react under reduced pressure, it is preferable to use the apparatus in which the said high boiling point solvent recirculate | refluxs.

  Also in Method 3, since the presence of moisture lowers the molecular weight of the resulting block copolymer (C), in particular, the polyester (II ′) should be sufficiently dried before the reaction. Is preferred.

  Examples of the method for producing the block copolymer (C) include the above-described methods 1 to 3. Among these, methods 1 and 2 that do not require removal of the solvent are preferable.

  The block copolymer (C) may have a high molecular weight by branching the chemical structure by using, for example, a polyol, an acid anhydride, a polyvalent isocyanate, an epoxy compound, or a peroxide. .

  The block copolymer (C) is obtained by extracting and removing the esterification catalyst or ring-opening polymerization catalyst used in the production by using an appropriate solvent after the production, or by using a chelating agent. In addition, the storage stability can be further improved by inactivating the ring-opening polymerization catalyst.

  In Method 1, since the esterification reaction is carried out without changing the original molecular weights of the raw material polyhydroxycarboxylic acid (I ′) and polyester (II ′), the polymerization catalyst used at the time of production of each raw material Is preferably deactivated.

  Moreover, the following method is mentioned as a specific manufacturing method of the said block copolymer (C).

  The raw material polyhydroxycarboxylic acid (I ′) and polyester (II ′) are supplied to the reactor and melted at 150 to 230 ° C. in an inert gas atmosphere. If it is the temperature of this range, polyhydroxycarboxylic acid (I ') will become easy to melt | dissolve and a raw material will become difficult to thermally decompose. In addition, it is preferable that the polyhydroxycarboxylic acid (I ′) is sufficiently dried in advance, so that the viscosity is not reduced due to hydrolysis at the time of melting, and the block copolymer is not colored, resulting in an excellent molten mixture. .

  Further, the reactor is preferably a vertical or horizontal tank reactor corresponding to a high vacuum and batch or continuous. The blade used for the reactor is not particularly limited, but may be appropriately selected according to the viscosity or molecular weight of the block copolymer to be produced. Examples of the shape of the wing include a paddle type, an anchor type, a helical type, a large wing, and the like as a wing of a vertical reactor, and examples of a wing of a horizontal reactor include a lattice type, a glasses type, and a rib. Examples include molds. Further, when the polyester (II ') is produced in one reactor and then the block copolymer is produced, a blade having excellent surface renewability corresponding to a low viscosity to high viscosity region is preferred.

  The method for melting the polyhydroxycarboxylic acid (I ′) and the polyester (II ′) is not particularly limited, but it is preferably performed in an inert gas atmosphere. For example, both of them may be simultaneously supplied to the reactor under an inert gas atmosphere such as nitrogen or argon. When the polyester (II ′) is in a liquid state, the polyester (II ′) is charged into the reactor in advance, Polyhydroxycarboxylic acid (I ′) may be added to the reactor, or polyhydroxycarboxylic acid (I ′) and polyester (II ′) may be melted using an extruder or the like and then added to the reactor. .

  Here, the esterification reaction referred to in the present invention is a reaction of obtaining an ester by dehydration of an acid and an alcohol, and causing an alcohol, an acid or another ester to act on the ester to cause an exchange of an acid group or an alkyl group, The transesterification reaction etc. which produce | generate another kind of ester are included.

  In the block copolymer (C) obtained by the above production method, if the remaining monomer is removed by a conventionally known method, the storage stability of the obtained block copolymer can be further improved. Examples of a method for removing the remaining monomer include a method for removing the remaining monomer by decompression after the catalyst deactivation treatment.

  As a method for removing the esterification catalyst, for example, a method of immersing the block copolymer in a methanol / hydrochloric acid aqueous solution, an acetone / hydrochloric acid aqueous solution, or a mixed solvent thereof as a solvent and extracting the esterification catalyst into the solvent. And a method in which the block copolymer is melted and charged into the solvent and washed while the block copolymer is precipitated. By such a method, a trace amount of residual monomer, oligomer, etc. can be simultaneously removed by washing.

  The compound (III ′) used for introducing the carbodiimide structural unit (III) into the structure of the block copolymer (C) is a compound having at least one carbodiimide group. Moreover, it is preferable that the said compound (III ') has functional groups, such as an isocyanate group and an epoxy group, as a functional group which reacts with the hydroxyl group or carboxyl group which the said polyester (II') has.

  As the compound (III ′), polycarbodiimide is preferable. The polycarbodiimide preferably has a functional group such as an isocyanate group or an epoxy group as a functional group that reacts with the hydroxyl group or carboxyl group of the polyester (II ′), but has two or more carbodiimide groups. If it is polycarbodiimide, since a part of carbodiimide group reacts with the hydroxyl group or carboxyl group of the said polyester (II '), it does not necessarily need to have functional groups, such as an isocyanate group and an epoxy group. In this case, even if the carbodiimide group of the polycarbodiimide reacts with the hydroxyl group or carboxyl group of the polyester (II ′), other carbodiimide groups remain. As a result, in the structure of the block copolymer (C), A carbodiimide structural unit (III) can be introduced.

  The polycarbodiimide is synthesized, for example, by using an organophosphorus compound or an organometallic compound as a catalyst and subjecting various polyisocyanates to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of about 70 ° C. or higher. What can be done. In these compounds, isocyanate groups may remain.

  Examples of the polycarbodiimide include poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (diisopropylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimide), and the like. And aromatic polycarbodiimides such as poly (4,4′-dicyclohexylmethanecarbodiimide) and the like, and aliphatic polycarbodiimides such as poly (diisopropylcarbodiimide) and the like. These can be used alone or in combination of two or more. Among these, aromatic polycarbodiimide or alicyclic polycarbodiimide is preferable because good hydrolysis resistance can be obtained.

  Examples of the method for introducing the carbodiimide structural unit (III) into the structure of the block copolymer (C) include the following methods AD.

(Method A)
Prior to block copolymerization with the polyhydroxycarboxylic acid (I ′), the polyester (II ′) and the compound (III ′) are reacted, and the polyester (II ′) is subjected to chain extension to form a carbodiimide structural unit (III ), Followed by block copolymerization with polyhydroxycarboxylic acid (I ′).

(Method B)
The molten mixture of the polyhydroxycarboxylic acid (I ′) and the polyester (II ′) is subjected to block copolymerization by esterification under reduced pressure conditions in the presence of an esterification catalyst, and then the compound (III ′). ), And the carbodiimide structural unit (III) is introduced by chain extension.

(Method C)
Using a lactone as the monomer instead of the polyhydroxycarboxylic acid (I ′) to form a polyhydroxycarboxylic acid (I ′) segment by a ring-opening reaction from the end of the polyester (II ′), A method of reacting compound (III ′) and introducing carbodiimide structural unit (III) by chain extension.

(Method D)
A method of reacting the polyhydroxycarboxylic acid (I ′) with the polyester (II ′) in the presence of the compound (III ′).

  Moreover, when introducing the carbodiimide structural unit (III) into the structure of the block copolymer (C), two or more of the above methods A to D may be combined.

  In the polycarbonate resin composition of the present invention, monocarbodiimide may be blended for the purpose of improving hydrolysis resistance. Examples of the monocarbodiimide include diphenylcarbodiimide, bis (2,6-dimethylphenyl) carbodiimide, bis (2,6-diethylphenyl) carbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, and bis (2,6- Di-t-butylphenyl) carbodiimide, bis (o-methylphenyl) carbodiimide, bis (p-methylphenyl) carbodiimide, bis (2,4,6-trimethylphenyl) carbodiimide, 2,4,6-triisopropylphenyl) Aromatic monocarbodiimides such as carbodiimide and bis (2,4,6-triisobutylphenyl) carbodiimide; Alicyclic monocarbodiimides such as di-cyclohexylcarbodiimide; Di-isopropylcarbodiimide and di-octadecylcarbodi And aliphatic mono carbodiimides such as bromide and the like.

  Aromatic monocarbodiimide is preferred for the purpose of obtaining good hydrolysis resistance and lowering the carboxyl group terminal concentration of each polymer blended in the polycarbonate resin composition, and bis (2,6-diisopropylphenyl) carbodiimide, bis (2 , 6-Dimethylphenyl) carbodiimide is more preferred. These monocarbodiimides can be used alone or in combination of two or more.

  If necessary, the polycarbonate resin composition of the present invention can be blended with additives, other synthetic resins, elastomers, and the like as long as the object of the present invention is not impaired.

  Examples of the additive include hindered phenol-based, phosphorus-based (phosphite-based, phosphate-based, etc.), amine-based antioxidants; benzotriazole-based, benzophenone-based UV absorbers, etc .; hindered amine Light stabilizers such as aliphatic carboxylic acid ester, paraffin, silicone oil, polyethylene wax and other internal lubricants, mold release agents, flame retardants, flame retardant aids, antistatic agents, colorants, various organic fillers , Inorganic fillers, antiblocking agents, various coupling agents, surfactants, colorants, foaming agents, natural materials, and the like.

  Examples of the other synthetic resins include synthetic resins such as polyethylene, polypropylene, polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and polymethyl methacrylate. Examples of the elastomer include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, and acrylic elastomer.

  It is preferable to add an inorganic filler to the polycarbonate resin composition of the present invention because mechanical strength, dimensional stability and the like are improved. Moreover, you may mix | blend an inorganic filler with the polycarbonate resin composition of this invention for the purpose of an increase.

  Examples of the inorganic filler include zinc sulfate, potassium hydrogen sulfate, aluminum sulfate, antimony sulfate, sulfate ester, potassium sulfate, cobalt sulfate, sodium hydrogen sulfate, iron sulfate, copper sulfate, sodium sulfate, nickel sulfate, and barium sulfate. Metal sulfate compounds such as magnesium sulfate and ammonium sulfate; Titanium compounds such as titanium oxide; Carbonate compounds such as potassium carbonate; Metal hydroxide compounds such as aluminum hydroxide and magnesium hydroxide; Silica compounds such as synthetic silica and natural silica Calcium aluminate, dihydrate gypsum, zinc borate, barium metaborate, borax; nitrate compounds such as sodium nitrate, molybdenum compounds, zirconium compounds, antimony compounds and modified products thereof; complex of silicon dioxide and aluminum oxide Such as fine particles It is below.

  Other inorganic fillers include, for example, potassium titanate whiskers, mineral fibers (rock wool, etc.), glass fibers, carbon fibers, metal fibers (stainless fibers, etc.), aluminum borate whiskers, silicon nitride whiskers, boron fibers. , Tetrapotted zinc oxide whisker, talc, clay, kaolin clay, natural mica, synthetic mica, pearl mica, aluminum foil, alumina, glass flakes, glass beads, glass balloon, carbon black, graphite, calcium carbonate, calcium sulfate, silica Examples include calcium acid, titanium oxide, zinc oxide, silica, asbestos, and quartz powder.

  Even if these inorganic fillers are untreated, they may be subjected to chemical or physical surface treatment in advance. Examples of the surface treatment agent used for the surface treatment include silane coupling agent systems, higher fatty acid systems, fatty acid metal salt systems, unsaturated organic acid systems, organic titanate systems, resin acid systems, and polyethylene glycol systems.

  Examples of the flame retardant include boric acid flame retardant compounds, phosphorus flame retardant compounds, nitrogen flame retardant compounds, halogen flame retardant compounds, organic flame retardant compounds, colloid flame retardant compounds, and the like.

  The above-mentioned components may be blended and kneaded by ordinary methods, for example, ribbon blender, drum tumbler, Henschel mixer, Banbury mixer, single screw extruder, twin screw extruder, conida, multiaxial It can carry out by the method using a screw extruder etc. The heating temperature for kneading is usually in the range of 240 to 320 ° C.

  The polycarbonate resin composition of the present invention can be produced by various extrusion molding methods (cold runner method, hot runner method molding method, as well as injection compression molding, injection press molding, gas assist injection molding, foam molding (by supercritical fluid injection). Injection molding methods such as insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding) It can also be used in the form of a molded sheet, film or the like. In addition, an inflation method, a calendar method, a casting method, or the like can be used for forming a sheet or a film. Furthermore, it can be formed as a heat-shrinkable tube by applying a specific stretching operation. Further, the polycarbonate resin composition of the present invention can be made into a hollow molded product by rotational molding or blow molding.

  The polycarbonate resin composition of the present invention is an exterior material for office automation equipment and home appliances, such as a personal computer, a notebook computer, a game machine, a display device (CRT, liquid crystal, plasma, projector, organic EL, etc.), mouse, printer, Exterior materials such as copiers, scanners and fax machines (including these multifunction devices), keyboard keys, switch moldings, personal digital assistants (so-called PDAs), mobile phones, mobile books (dictionaries, etc.), mobile TVs, recording Media (CD, MD, DVD, next-generation high-density disk, hard disk, etc.) drive, recording medium (IC card, smart media, memory stick, etc.) reader, optical camera, digital camera, parabolic antenna, electric tool, VTR, Iron, hair dryer, rice cooker, microwave, Hibiki equipment, lighting equipment, refrigerators, air conditioners, air purifiers, it is possible to use negative ion generator, and a resin product formed like a typewriter. Also, trays, cups, dishes, shampoo bottles, OA housings, cosmetic bottles, beverage bottles, oil containers, injection molded products (golf tees, cotton swab cores, candy sticks, brushes, toothbrushes, helmets, syringes, dishes, Cups, combs, razor handles, tape cassettes and cases, disposable spoons and forks, stationery such as ballpoint pens, etc.).

  In addition, binding tape (bonding band), prepaid card, balloons, pantyhose, hair cap, sponge, cellophane tape, umbrella, feather, plastic gloves, hair cap, rope, tube, foam tray, foam cushioning material, cushioning material, packaging It can be used in various fields such as wood and cigarette filters.

  Furthermore, it can also be used for vehicle parts such as various containers, sundries, lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, car audio visual parts, auto mobile computer parts, etc. it can.

  The resin molded product obtained by molding the polycarbonate resin composition of the present invention can be imparted with other functions by surface modification. Surface modification here means a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. The method used for normal resin molded products can be applied. The resin composition of the present invention can provide a good product with one coat even if the coating composition has a low hue due to its good hue.

  In the polycarbonate resin composition of the present invention, the reason why the block copolymer (C) is also effective as a compatibilizer for a polymer alloy of polycarbonate and polylactic acid is not clear, but the block copolymer (C) Because it is a block copolymer having both a polylactic acid structure with good compatibility with polylactic acid and a polyester structure with a relatively high affinity with polycarbonate, it has a unique morphology that satisfies impact resistance and fluidity. Guessed.

  Hereinafter, the present invention will be described in more detail with specific examples.

<< Production Example 1 >> Production Example of Polyester (II'-1) A reactor is charged with 1 molar equivalent of sebacic acid and 1.4 molar equivalent of 1,2-propanediol, and from 150 ° C to 230 ° C under a nitrogen stream, The temperature was raised by 10 ° C. per hour, and stirring was carried out while distilling off the produced water to carry out an esterification reaction. Then, after reacting at 230 ° C. for 2 hours, 100 ppm of titanium tetraisopropoxide as a polymerization catalyst was added to the total amount of sebacic acid and 1,2-propanediol, and reacted at a reduced pressure of 200 Pa for 15 hours. After completion of the reaction, by adding 110 ppm of 2-ethylhexanoic acid phosphate as a polymerization catalyst deactivator with respect to the total amount of sebacic acid and 1,2-propanediol, and stirring at 333 Pa and 220 ° C. for 1 hour. A polyester (II′-1) having a number average molecular weight of 35,000 and a weight average molecular weight of 63,000 was obtained.

<< Production Example 2 >> Production Example of Polyester (II'-2) A reactor is charged with 1 molar equivalent of sebacic acid and 1.4 molar equivalent of 1,2-propanediol, and from 150 ° C to 230 ° C under a nitrogen stream, The temperature was raised by 10 ° C. per hour, and stirring was carried out while distilling off the produced water to carry out an esterification reaction. Then, after reacting at 230 ° C. for 2 hours, 100 ppm of titanium tetraisopropoxide as a polymerization catalyst was added to the total amount of sebacic acid and 1,2-propanediol, and reacted at a reduced pressure of 200 Pa for 8 hours. After completion of the reaction, by adding 110 ppm of 2-ethylhexanoic acid phosphate as a polymerization catalyst deactivator with respect to the total amount of sebacic acid and 1,2-propanediol, and stirring at 333 Pa and 220 ° C. for 1 hour. A polyester (II′-1) having a number average molecular weight of 17,000 and a weight average molecular weight of 31,000 was obtained.

<< Production Example 3 >> Production Example of Block Copolymer (C-1) A reactor was charged with 50 g of the polyester (II′-1) obtained in Production Example 1, and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-1) and the polylactic acid (I′-1) were uniformly melt-mixed, the mixture was further melt-mixed for 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added in an amount of 500 ppm with respect to the total amount of the reaction product, and a block copolymer having a number average molecular weight of 58,000 and a weight average molecular weight of 125,000. The union (C-1) was obtained.

<< Production Example 4 >> Production Example of Block Copolymer (C-2) A reactor was charged with 50 g of the polyester (II′-1) obtained in Production Example 1 and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-1) and the polylactic acid (I′-1) were uniformly melt-mixed, a polycarbodiimide having an isocyanate group (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Ltd.) 0.25 g was added and melt mixed for another 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator of the esterification catalyst, 2-ethylhexanoic acid phosphate is added at 500 ppm with respect to the total amount of the reaction product, and the block copolymer having a number average molecular weight of 83,000 and a weight average molecular weight of 152,000. The union (C-2) was obtained.

<< Production Example 5 >> Production Example of Block Copolymer (C-3) A reactor was charged with 50 g of the polyester (II′-2) obtained in Production Example 2 and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (C-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melt mixed. did. After visually confirming that the polyester (II′-2) and the polylactic acid (C-1) were uniformly melt-mixed, a polycarbodiimide having an isocyanate group (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Inc.) 0 .25 g was added and melt mixed for another 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added in an amount of 500 ppm based on the total amount of the reaction product, and a block copolymer having a number average molecular weight of 62,000 and a weight average molecular weight of 135,000. The union (C-3) was obtained.

Production Example 6 Production Example of Block Copolymer (C-4) Manufacture except that polycarbodiimide having an isocyanate group (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Ltd.) was changed from 0.25 g to 0.5 g. The reaction was conducted in the same manner as in Example 4 to obtain a block copolymer (C-4) having a number average molecular weight of 79,000 and a weight average molecular weight of 158,000.

<< Production Example 7 >> Production Example of Polyester (II'-3) A reactor is charged with 1 molar equivalent of adipic acid and 1.1 molar equivalent of 1,4-butanediol, and from 150 ° C to 230 ° C under a nitrogen stream, The temperature was raised by 10 ° C. per hour, and stirring was carried out while distilling off the produced water to carry out an esterification reaction. Then, after reacting at 230 ° C. for 2 hours, 100 ppm of titanium tetraisopropoxide as a polymerization catalyst was added to the total amount of adipic acid and 1,4-butanediol, and reacted at a reduced pressure of 200 Pa for 15 hours. After completion of the reaction, by adding 110 ppm of 2-ethylhexanoic acid phosphate as a deactivator for the polymerization catalyst with respect to the total amount of adipic acid and 1,4-butanediol, and stirring at 333 Pa, 220 ° C. for 1 hour. A polyester (II′-3) having a number average molecular weight of 29,000 and a weight average molecular weight of 43,000 was obtained.

<< Production Example 8 >> Production Example of Polyester (II'-4) A reactor was charged with 1 molar equivalent of adipic acid and 1.1 molar equivalent of 1,4-butanediol, and from 150 ° C to 230 ° C under a nitrogen stream, The temperature was raised by 10 ° C. per hour, and stirring was carried out while distilling off the produced water to carry out an esterification reaction. Then, after reacting at 230 ° C. for 2 hours, 100 ppm of titanium tetraisopropoxide as a polymerization catalyst was added to the total amount of adipic acid and 1,4-butanediol, and reacted at a reduced pressure of 200 Pa for 8 hours. After completion of the reaction, by adding 110 ppm of 2-ethylhexanoic acid phosphate as a deactivator for the polymerization catalyst with respect to the total amount of adipic acid and 1,4-butanediol, and stirring at 333 Pa, 220 ° C. for 1 hour. A polyester (II′-4) having a number average molecular weight of 21,000 and a weight average molecular weight of 31,000 was obtained.

<< Production Example 9 >> Production Example of Polyester (II'-5) A reactor is charged with 1 molar equivalent of adipic acid and 1.1 molar equivalent of 2-methyl-1,2-propanediol, and from 150 ° C under a nitrogen stream. The temperature was raised to 230 ° C. by 10 ° C. per hour, and the mixture was stirred while distilling off the generated water to conduct an esterification reaction. Then, after reacting at 230 ° C. for 2 hours, 100 ppm of titanium tetraisopropoxide as a polymerization catalyst was added to the total amount of adipic acid and 2-methyl-1,2-propanediol, and the reaction was performed at a reduced pressure of 200 Pa for 15 hours. I let you. After completion of the reaction, 110 ppm of 2-ethylhexanoic acid phosphate as a deactivator for the polymerization catalyst was added to the total amount of adipic acid and 2-methyl-1,2-propanediol, and 333 Pa at 220 ° C. for 1 hour. By stirring, a polyester (II′-5) having a number average molecular weight of 28,000 and a weight average molecular weight of 43,000 was obtained.

<< Production Example 10 >> Production Example of Polyester (II'-6) A reactor was charged with 1 molar equivalent of adipic acid and 1.1 molar equivalent of 2-methyl-1,2-propanediol, and from 150 ° C under a nitrogen stream. The temperature was raised to 230 ° C. by 10 ° C. per hour, and the mixture was stirred while distilling off the generated water to conduct an esterification reaction. Then, after reacting at 230 ° C. for 2 hours, titanium tetraisopropoxide as a polymerization catalyst was added at 100 ppm with respect to the total amount of adipic acid and 2-methyl-1,2-propanediol, and the reaction was performed at a reduced pressure of 200 Pa for 8 hours. I let you. After completion of the reaction, 110 ppm of 2-ethylhexanoic acid phosphate as a deactivator for the polymerization catalyst was added to the total amount of adipic acid and 2-methyl-1,2-propanediol, and 333 Pa at 220 ° C. for 1 hour. By stirring, a polyester (II′-6) having a number average molecular weight of 22,000 and a weight average molecular weight of 32,000 was obtained.

<< Production Example 11 >> Production Example of Polyester (II'-7) A reactor is charged with 1 molar equivalent of adipic acid and 1.4 molar equivalent of 1,3-propanediol, and from 150 ° C to 230 ° C under a nitrogen stream, The temperature was raised by 10 ° C. per hour, and stirring was carried out while distilling off the produced water to carry out an esterification reaction. Then, after reacting at 230 ° C. for 2 hours, 100 ppm of titanium tetraisopropoxide as a polymerization catalyst was added to the total amount of adipic acid and 1,3-propanediol, and reacted at a reduced pressure of 200 Pa for 15 hours. After completion of the reaction, by adding 110 ppm of 2-ethylhexanoic acid phosphate as a polymerization catalyst deactivator with respect to the total amount of adipic acid and 1,3-propanediol, and stirring at 333 Pa, 220 ° C. for 1 hour. A polyester (II′-5) having a number average molecular weight of 30,000 and a weight average molecular weight of 45,000 was obtained.

<< Production Example 12 >> Production Example of Block Copolymer (C-5) A reactor was charged with 50 g of the polyester (II′-3) obtained in Production Example 7, and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-3) and the polylactic acid (I′-1) were uniformly melt-mixed, the mixture was further melt-mixed for 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added at 500 ppm with respect to the total amount of the reaction product, and a block copolymer having a number average molecular weight of 44,000 and a weight average molecular weight of 70,000. The union (C-5) was obtained.

<< Production Example 13 >> Production Example of Block Copolymer (C-6) A reactor was charged with 50 g of the polyester (II′-3) obtained in Production Example 7, and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-3) and the polylactic acid (I′-1) were uniformly melt-mixed, a polycarbodiimide having an isocyanate group (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Ltd.) 0.25 g was added and melt mixed for another 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added in an amount of 500 ppm based on the total amount of the reaction product, and a block copolymer having a number average molecular weight of 80,000 and a weight average molecular weight of 148,000 The union (C-6) was obtained.

<< Production Example 14 >> Production Example of Block Copolymer (C-7) A reactor was charged with 50 g of the polyester (II'-4) obtained in Production Example 8, and heated in a nitrogen atmosphere at a jacket temperature of 200 ° C. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-4) and the polylactic acid (I′-1) were uniformly melt-mixed, the mixture was further melt-mixed for 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added in an amount of 500 ppm based on the total amount of the reaction product, and a block copolymer having a number average molecular weight of 33,000 and a weight average molecular weight of 50,000. The union (C-7) was obtained.

<< Production Example 15 >> Production Example of Block Copolymer (C-8) A reactor was charged with 50 g of the polyester (II′-4) obtained in Production Example 8, and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-4) and the polylactic acid (I′-1) were uniformly melt-mixed, a polycarbodiimide having an isocyanate group (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Ltd.) 0.25 g was added and melt mixed for another 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added in an amount of 500 ppm based on the total amount of the reaction product, and a block copolymer having a number average molecular weight of 62,000 and a weight average molecular weight of 128,000. The union (C-8) was obtained.

<< Production Example 16 >> Production Example of Block Copolymer (C-9) A reactor was charged with 50 g of the polyester (II′-5) obtained in Production Example 9, and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-5) and the polylactic acid (I′-1) were uniformly melt-mixed, the mixture was further melt-mixed for 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added in an amount of 500 ppm based on the total amount of the reaction product, and a block copolymer having a number average molecular weight of 42,000 and a weight average molecular weight of 69,000. The union (C-9) was obtained.

<< Production Example 17 >> Production Example of Block Copolymer (C-10) A reactor was charged with 50 g of the polyester (II′-5) obtained in Production Example 9 and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-5) and the polylactic acid (I′-1) were uniformly melt-mixed, a polycarbodiimide having an isocyanate group (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Ltd.) 0.25 g was added and melt mixed for another 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added in an amount of 500 ppm based on the total amount of the reaction product, and a block copolymer having a number average molecular weight of 72,000 and a weight average molecular weight of 150,000. The union (C-10) was obtained.

<< Production Example 18 >> Production Example of Block Copolymer (C-11) 30 g of the polyester (II′-6) obtained in Production Example 10 was charged into a reactor and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 70 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-6) and the polylactic acid (I′-1) were uniformly melt-mixed, the mixture was further melt-mixed for 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added at 500 ppm with respect to the total amount of the reaction product, and a block copolymer having a number average molecular weight of 44,000 and a weight average molecular weight of 67,000. The union (C-11) was obtained.

<< Production Example 19 >> Production Example of Block Copolymer (C-12) A reactor was charged with 30 g of the polyester (II′-6) obtained in Production Example 10 and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 70 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-6) and the polylactic acid (I′-1) were uniformly melt-mixed, a polycarbodiimide having an isocyanate group (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Ltd.) 0.25 g was added and melt mixed for another 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added at 500 ppm with respect to the total amount of the reaction product, and a block copolymer having a number average molecular weight of 81,000 and a weight average molecular weight of 158,000. The union (C-12) was obtained.

<< Production Example 20 >> Production Example of Block Copolymer (C-13) A reactor was charged with 50 g of the polyester (II′-7) obtained in Production Example 11, and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-7) and the polylactic acid (I′-1) were uniformly melt-mixed, the mixture was further melt-mixed for 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added at 500 ppm with respect to the total amount of the reaction product, and a block copolymer having a number average molecular weight of 39,000 and a weight average molecular weight of 63,000. The union (C-13) was obtained.

<< Production Example 21 >> Production Example of Block Copolymer (C-14) A reactor was charged with 50 g of the polyester (II′-7) obtained in Production Example 11, and heated at a jacket temperature of 200 ° C. in a nitrogen atmosphere. . Thereafter, 50 g of polylactic acid (I′-1) [number average molecular weight 92,000, weight average molecular weight 170,000, L isomer: D isomer = 98.5: 1.5 (molar ratio)] was added and melted. Mixed. After visually confirming that the polyester (II′-7) and the polylactic acid (I′-1) were uniformly melt-mixed, a polycarbodiimide having an isocyanate group (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Ltd.) 0.25 g was added and melt mixed for another 2 hours. Next, 200 ppm of titanium tetrabutoxide as an esterification catalyst was added to the total amount of the molten mixture, and reacted at a reduced pressure of 80 Pa for 4 hours. After completion of the reaction, as a deactivator for the esterification catalyst, 2-ethylhexanoic acid phosphate is added at 500 ppm with respect to the total amount of the reaction product, and a block copolymer having a number average molecular weight of 77,000 and a weight average molecular weight of 148,000. The union (C-14) was obtained.

<< Production Example 22 >> Production Example of Block Copolymer (C-15) 100 g of L-lactide (Pureac) and 150 g of polycaprolactone ("Placcel H1P" manufactured by Daicel Chemical Industries, Ltd .: molecular weight 10,000) are stirred. In a reaction vessel equipped with an apparatus, the mixture was uniformly dissolved at 150 ° C. in a nitrogen atmosphere, and then 45 mg of tin octylate was added, followed by polymerization reaction for 1 hour. After the completion of the polymerization reaction, the reaction product is dissolved in chloroform, precipitated with stirring in methanol, the monomer is completely removed, and the polylactic acid and polylactic acid having a number average molecular weight of 13,000 and a weight average molecular weight of 21,000 are obtained. A block copolymer (C-15) with caprolactone was obtained.

  The number average molecular weights (Mn) of the polyesters (II′-1) to (II′-7) and the block copolymers (C-1) to (C-15) obtained in Production Examples 1 to 22 above. And the measuring method of a weight average molecular weight (Mw) is as follows.

[Method of measuring number average molecular weight (Mn) and weight average molecular weight (Mw)]
Using a gel permeation chromatography measuring device (“HLC-8220” manufactured by Tosoh Corporation), two TSK gel SuperHZM-M, two TSK gel SuperHZ-2000, and TSK SuperH as guard columns are used as columns. Using -H, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by comparison with standard polystyrene.

  A polycarbonate resin composition was prepared as follows using the block copolymers (C-1) to (C-15) obtained in Production Examples 3 to 6 and 12 to 22.

Example 1
7.5 kg of polycarbonate (aromatic polycarbonate (general-purpose low viscosity type)) with a melt flow rate (hereinafter referred to as “MFR”) at a temperature of 280 ° C. and a load of 21.18 N of 16 g / 10 min., Polylactic acid (Mitsui Chemicals, Inc.) 2.5 kg of company “Lacia H-400”), 0.5 kg of block copolymer (C-1) obtained in Production Example 3, 5 g of stabilizer (“Ultranox 641” manufactured by GE Chemicals) and antioxidant After dry blending 5 g of the agent ("Irganox 1010" manufactured by Ciba Specialty Chemicals Co., Ltd.), they were used with a Laboplast mill twin screw extruder (manufactured by Toyo Seiki Seisakusyo Co., Ltd.) having a rotation speed of 20 rpm and a temperature of 260 ° C. The mixture was melt mixed and extruded to obtain pellets of a polycarbonate resin composition.

(Example 2)
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 1 except that the blending amount of the block copolymer (C-1) was changed from 0.5 kg to 1.0 kg.

(Example 3)
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 1 except that the blending amount of the block copolymer (C-1) was changed from 0.5 kg to 1.5 kg.

Example 4
A pellet of polycarbonate resin composition was obtained in the same manner as in Example 2 except that 50 g of polycarbodiimide having an isocyanate group (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Ltd.) was added.

(Example 5)
A pellet of polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-2) obtained in Production Example 4 was used instead of the block copolymer (C-1). It was.

(Example 6)
A pellet of polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-3) obtained in Production Example 5 was used instead of the block copolymer (C-1). It was.

(Example 7)
A pellet of polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-4) obtained in Production Example 6 was used instead of the block copolymer (C-1). It was.

(Example 8)
A pellet of polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-5) obtained in Production Example 12 was used instead of the block copolymer (C-1). It was.

Example 9
A pellet of polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-6) obtained in Production Example 13 was used instead of the block copolymer (C-1). It was.

(Example 10)
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-7) obtained in Production Example 14 was used instead of the block copolymer (C-1). It was.

(Example 11)
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-8) obtained in Production Example 15 was used instead of the block copolymer (C-1). It was.

Example 12
A pellet of polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-9) obtained in Production Example 16 was used instead of the block copolymer (C-1). It was.

(Example 13)
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-10) obtained in Production Example 17 was used instead of the block copolymer (C-1). It was.

(Example 14)
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-11) obtained in Production Example 18 was used instead of the block copolymer (C-1). It was.

(Example 15)
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-12) obtained in Production Example 19 was used instead of the block copolymer (C-1). It was.

(Example 16)
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-13) obtained in Production Example 20 was used instead of the block copolymer (C-1). It was.

(Example 17)
A pellet of the polycarbonate resin composition was obtained in the same manner as in Example 2 except that the block copolymer (C-14) obtained in Production Example 21 was used instead of the block copolymer (C-1). It was.

(Comparative Example 1)
10.0 kg of polycarbonate (MFR (280 ° C., 21.18 N): 16 g / 10 min aromatic polycarbonate (general-purpose low viscosity type)), 5 g of a stabilizer (“Ultranox 641” manufactured by GE Chemicals) and an antioxidant ( After dry blending 5 g of “Irganox 1010” manufactured by Ciba Specialty Chemicals Co., Ltd., they were melted using a lab plast mill twin screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) having a rotation speed of 20 rpm and a temperature of 260 ° C. The mixture was mixed and extruded to obtain pellets of a polycarbonate resin composition.

(Comparative Example 2)
Except not using a copolymer, the pellet was produced by the method similar to Example 1, and the test piece was produced by the same method as Example 1 using this pellet, and evaluation was added. The results are shown in Table 1.
7.5 kg of polycarbonate (MFR (280 ° C., 21.18 N): aromatic polycarbonate (general low viscosity type) of 16 g / 10 min), 2.5 kg of polylactic acid (“Lacia H-400” manufactured by Mitsui Chemicals, Inc.), After dry blending 5 g of a stabilizer (“Ultranox 641” manufactured by GE Chemicals) and 5 g of an antioxidant (“Irganox 1010” manufactured by Ciba Specialty Chemicals Co., Ltd.), they were rotated at 20 rpm and a temperature of 260 ° C. Using a lab plast mill twin screw extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.), melt mixing was performed, and extrusion molding was performed to obtain pellets of a polycarbonate resin composition.

(Comparative Example 3)
A pellet of polycarbonate resin composition was obtained in the same manner as in Example 1 except that the block copolymer (C-15) obtained in Production Example 22 was used instead of the block copolymer (C-1). The

  The following evaluation was performed using the pellets of the polycarbonate resin compositions obtained in Examples 1 to 17 and Comparative Examples 1 to 3.

[Measurement method of Izod impact value]
The pellet of polycarbonate resin composition is subjected to an Izod impact test according to JIS K 7110 using a 1 ounce vertical molding machine (manufactured by Yamashiro Seiki Co., Ltd.) under molding conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. No. 2 test piece was prepared. Next, using a notching machine (manufactured by Techno Supply Co., Ltd.), the No. 2 test piece was notched so as to have the shape of No. 2 A in the test standard JIS K 7110. The Izod impact value of the obtained test piece was measured according to the test standard JIS K 7110 using a universal impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

[appearance]
The color tone, unevenness, presence / absence of pearly luster, and smoothness of the test piece prepared by measuring the Izod impact value were visually observed, and the appearance was evaluated according to the following criteria.
(Evaluation criteria for unevenness)
A: There is no unevenness.
○: There is almost no unevenness.
Δ: Some unevenness.
X: There is unevenness.
(Evaluation criteria for pearl luster)
A: There is no pearl luster.
X: There is pearl luster.
Xx: The pearl luster is remarkably high.
(Evaluation criteria for smoothness)
A: Smooth.
X: There are irregularities on the surface.

[Measurement method of fluidity (MFR)]
MFR (unit: g / 10 minutes) was calculated by converting the pellets of the polycarbonate resin composition using a melt indexer manufactured by Toyo Seiki Kogyo Co., Ltd., and measuring the amount of the outflow resin under the following measurement conditions.
Measurement conditions: Standard orifice (diameter: 2.096 × 8.001 mm), load: 21.18 N, temperature 280 ° C., measurement time: 60 seconds

[Method for evaluating hydrolysis resistance]
The pellet of the polycarbonate resin composition was measured for the weight average molecular weight in the same manner as in the above measurement method to obtain an initial value. In addition, the polycarbonate resin composition pellets were allowed to stand for 6 months in an atmosphere of high temperature and high humidity (temperature of 40 ° C. and humidity of 90%), and the weight average molecular weight was measured in the same manner. Hydrolysis resistance was evaluated by calculating the retention, which is the ratio between the weight average molecular weight and the initial value of the material in this hot and humid atmosphere.

  The compositions and evaluation results of the polycarbonate resin compositions obtained in Examples 1 to 17 and Comparative Examples 1 to 3 are shown in Tables 1 to 4.

  Examples 1 to 17 which are polycarbonate resin compositions of the present invention were found to have good appearance, excellent impact resistance and fluidity, and high hydrolysis resistance.

  On the other hand, Comparative Example 1 is an example of only polycarbonate, but it was found that the appearance, impact resistance and hydrolysis resistance were high, but the fluidity was poor.

  Although the comparative example 2 was an example which did not mix | blend block copolymer (C), it turned out that although fluidity | liquidity and hydrolysis resistance are high, it is inferior to an external appearance and impact resistance.

  Comparative Example 3 is an example in which polycaprolactone is used as the polyester structural unit (II) obtained by esterifying the dicarboxylic acid, which is the structural unit of the block copolymer (C) used in the present invention, with a diol. The fluidity and hydrolysis resistance were good and the impact resistance was improved as compared with that of Comparative Example 2, but it was found that the appearance was not at a satisfactory level.

Claims (10)

  Block copolymer (C) having polyester structural unit (II) obtained by esterification reaction of polycarbonate (A), polylactic acid (B), polyhydroxycarboxylic acid structural unit (I) and dicarboxylic acid and diol A polycarbonate resin composition characterized by comprising:   The polycarbonate resin composition according to claim 1, wherein the polyhydroxycarboxylic acid structural unit (I) constituting the block copolymer (C) is a structural unit derived from polylactic acid.   The polycarbonate resin composition according to claim 1 or 2, wherein a carbodiimide structural unit (III) is added to the structural unit of the block copolymer (C).   The polycarbonate resin composition according to claim 3, wherein the carbodiimide structural unit (III) is derived from polycarbodiimide.   The polycarbonate resin composition according to any one of claims 1 to 4, wherein the dicarboxylic acid that is a raw material of the polyester structural unit (II) is adipic acid or sebacic acid.   The diol which is a raw material of the polyester structural unit (II) is selected from the group consisting of 1,4-butanediol, 1,3-propanediol, 1,2-propanediol and 2-methyl-1,2-propanediol. 6. The polycarbonate resin composition according to claim 5, wherein the polycarbonate resin composition is at least one diol.   The polycarbonate resin composition according to any one of claims 1 to 6, wherein a ratio of the block copolymer (C) to the entire resin composition is 5 to 30% by mass.   To a copolymer obtained by block polymerization of a polymer having a polyhydroxycarboxylic acid structural unit (I) and a polymer having a polyester structural unit (II) obtained by esterifying a dicarboxylic acid and a diol, A method for producing a block copolymer (C), comprising reacting a compound having a carbodiimide group.   Esterification reaction of a compound having a polyhydroxycarboxylic acid structural unit (I) and a compound having a polyester structural unit (II) obtained by esterifying a dicarboxylic acid and a diol in the presence of a compound having a carbodiimide group A process for producing a block copolymer (C), wherein   The resin molded product formed by shape | molding the polycarbonate resin composition of any one of Claims 1-6.