Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/14—Copolymers of styrene with unsaturated esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/062—Copolymers with monomers not covered by C08L33/06
  • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups

Definitions

• the present invention relates to an aliphatic polyester resin composition having excellent thermal stability and molding processability, and a molded body thereof.
• biodegradable polymers that can be decomposed in the natural environment and molded articles thereof have been demanded. ing.
• polylactic acid is recently gaining attention as a bioplastic because it is obtained from plant-derived raw materials such as corn, sugar cane, and sweet potato. Materials obtained from these plant raw materials are easily converted into water and carbon dioxide by combustion (pyrolysis) or biodegradation. This carbon dioxide is originally stored in the plant by photosynthesis. Therefore, bioplastics are environmentally friendly plastics because they do not increase the concentration of carbon dioxide in the atmosphere during combustion or biodegradation.
• polylactic acid has a feature that its melting point is higher than that of other aliphatic polyester resins and it has excellent heat resistance.
• the melted polylactic acid Since the melted polylactic acid has a low melt viscosity and melt tension, it causes necking during molding of, for example, a finale or a sheet, resulting in unstable thickness and width of the film, and breakage of the yarn during fiber molding. Or cause Also, problems can easily occur when the frost line of inflation molding becomes unstable, or when the blow molding nozzle is drawn down and the molded product becomes uneven.
• Patent Document 1 discloses a biodegradable polyester resin composition comprising a biodegradable polyester resin, a biodegradable aliphatic monoaromatic copolymer polyester resin, and a (meth) acrylate compound.
• Patent Document 2 discloses a biodegradable resin film or sheet in which a specific epoxy compound is blended with a biodegradable resin and has excellent hydrolysis resistance.
• Patent Document 3 discloses a biodegradable resin composition comprising a biodegradable polyester resin containing polylactic acid and a layered silicate, and further containing a reactive compound having an epoxy group.
• Patent Document 4 discloses a polylactic acid resin composition comprising polylactic acid, an aliphatic polyester other than polylactic acid, and a modified olefin compound.
• the modified olefin compound contains an ethylene-glycidyl metatalylate copolymer.
• Patent Document 5 discloses a crystalline biodegradable resin composition obtained by annealing a composition containing an aliphatic polyester and a modified elastomer.
• the aliphatic polyester contains polylactic acid
• the modified elastomer contains an acrylic elastomer.
• the biodegradable polyester resin composition described in Patent Document 1 is not suitable for biodegradable polyester resins, biodegradable aliphatic monoaromatic polyester resins, and (meth) acrylate esters. It is manufactured by adding an oxide and melt-kneading. In that case, the use of a (meth) acrylic acid ester compound having a functional group such as a glycidinole group causes a hydrogen abstraction reaction and a crosslinking reaction of a polylactic acid resin as a biodegradable polyester resin, resulting in a partially crosslinked product. Is produced and coloration such as yellowing is likely to occur.
• Patent Document 2 a long chain branched polymer is produced by the reaction of a hydroxyl group and a carboxyl group at the terminal of a polylactic acid molecule with an epoxy group-containing polymer.
• the effect of improving sex is recognized.
• the number of epoxy groups per molecule is too large (for example, Patent Document 2 uses a homopolymer of glycidyl metatalylate, and Patent Document 3 uses 50% glycidyl metatalylate and 50% styrene in Example 3).
• % Of the copolymer is used), the reaction of the hydroxyl group and carboxyl group at the polylactic acid molecule terminal with the epoxy group is local, and its control is difficult.
• the crosslinking reaction proceeds excessively in the molding machine, the resin composition reaches a gelled state, and the discharge becomes unstable. There arises a problem that the surface of the obtained molded body becomes non-uniform. That is, the resin composition has a problem of lacking thermal stability.
• the amount of the modified olefin compound is 5% by weight or more based on the aliphatic polyester.
• the blending amount of the acrylic elastomer is 10% by weight or more based on the aliphatic polyester such as polylactic acid.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2004-67894
• Patent Document 2 JP 2004-10693 A
• Patent Document 3 Japanese Patent Laid-Open No. 2003-261756
• Patent Document 4 Japanese Patent Laid-Open No. 2001-123055
• Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-35691
• the present invention has been made in view of the above-mentioned problems, and while suppressing excessive crosslinking reaction, it is possible to improve molding processability by a thickening effect and to exhibit excellent thermal stability.
• An object is to provide an aliphatic polyester resin composition.
• an aliphatic polyester resin composition comprises 0.1 to 1 mass of an acrylic resin modifier (B) to 100 mass parts of an aliphatic polyester resin (A) whose main component is a polymer having a lactic acid unit. It is contained in the ratio of parts.
• the content of lactide or lactic acid in the aliphatic polyester resin (A) is less than 0.2% by mass.
• the glass transition temperature of the acrylic resin modifier (B) is 0 ° C or higher, the average number of epoxy groups per molecule is 3 to 30, and the mass average molecular weight is 1,000 to 30,000. It is.
• the epoxy group of the acrylic resin-based modifier (B) is a fatty acid under the specific requirements of both the aliphatic polyester resin (A) and the acrylic resin-based modifier (B). It can react with a carboxynole group or a hydroxynore group present at the terminal of the group polyester resin (A) to form an appropriate cross-linked structure.
• the epoxy group in the acrylic resin modifier (B) is a carboxyl group or hydroxy group at the terminal of the aliphatic polyester resin (A).
• the value of 15 15 5 5 is preferably from ⁇ 0.35 to 0.1. According to this configuration, it is possible to improve the molding force resistance with little change in fluidity of the aliphatic polyester resin composition.
• the epoxy equivalent of the acrylic resin-based modified homogeneous lj (B) is preferably 0.70 to 3. OOmeqZg. According to this configuration, the amount of the epoxy group contained in the acrylic resin modifier (B) is determined in consideration of the molecular weight and the average number of epoxy groups per molecule. Therefore, it is possible to easily set the degree of the crosslinking reaction within an appropriate range, and to further exert the above-described effects.
• the acrylic resin modifier (B) is preferably obtained by polymerizing a monomer mixture containing an epoxy group-containing acrylic monomer and a styrene monomer. According to this configuration, a polymer having an epoxy group can be easily obtained as the acrylic resin modifier (B).
• the acrylic resin modifier (B) is preferably produced by a continuous stirred tank polymerization method set to a temperature of 130 to 350 ° C. According to this configuration, it is possible to efficiently produce an acrylic resin-based modifier (B) having a target molecular weight.
• the value of ( ⁇ / ⁇ ) is preferably from 1.1 to 1.8. According to this configuration, acrylic resin By adding the system modifier (B), the melt viscosity can be increased, and the molding processability can be further improved.
• Rate of change with Swell (DS) when no fat modifier (B) is added A DS (DS /
• the value of DS is preferably between 1.05 and 1.3. According to this configuration, the acrylic resin-based modified
• the melt viscosity can be increased, and the molding strength can be further improved.
• the acrylic resin modifier (B) preferably polymerizes a monomer mixture containing an epoxy group-containing acrylic monomer, a styrene monomer, and other vinyl monomers. Obtained. According to this configuration, it is possible to adjust the number of epoxy groups possessed by the acrylic resin modifier, and at the same time, vinyl monomers other than epoxy group-containing acrylic monomers and styrene monomers can be used. Function can be expressed.
• a molded product obtained by melt molding the above aliphatic polyester resin composition. According to this configuration, it is possible to improve the molding processability at the time of molding and to exhibit excellent thermal stability.
• the aliphatic polyester resin composition of the present embodiment (hereinafter simply referred to as the polyester resin composition) is 100 parts by mass of the aliphatic polyester resin (A) (hereinafter simply referred to as the polyester resin (A)).
• the acrylic resin modifier (B) is contained in a proportion of 0.15 to 1 part by mass.
• the polyester resin (A) is mainly composed of a polymer having lactic acid units (hereinafter referred to as polylactic acid).
• the polyester resin (A) is a main component of the polyester resin composition, and has a basic function of a molded article obtained by molding the polyester resin composition.
• the polyester resin (A) mainly composed of polylactic acid is a polyester resin containing 50% by mass or more of a polylactic acid component. That is, if the polyester resin (A) contains 50% by mass or more of a polylactic acid component, the polylactic acid may be homopolylactic acid or other aliphatic polyester unit. Co-polymerized with lactic acid. Further, when the polyester resin (A) contains 50% by mass or more of a polylactic acid component, the polyester resin (A) is a mixture of polylactic acid and another aliphatic polyester not containing the polylactic acid. There may be.
• Polylactic acid is a ring-opening polymerization of lacti K [CH CH (COO) CHCH] or lactic acid [CH CH (COO) CHCH] or lactic acid [CH CH (COO) CHCH] or lactic acid [CH CH (COO) CHCH] or lactic acid [CH CH (COO) CHCH]
• polylactic acid As this polylactic acid, one synthesized by a conventionally known method can be used. That is, polylactic acid can be produced by direct dehydration condensation from lactic acid described in JP-A-7-33861, JP-A-59-96123, and Polymer Proceedings Proceedings No. 44, pages 3198-3199, or It is synthesized by ring-opening polymerization of lactic acid cyclic dimer lactide.
• any one of L monolactic acid, D-lactic acid, DL-lactic acid, and a mixture thereof may be used.
• any one of L-latatide, D-latactide, DL-lactide, meso-lactide, and a mixture thereof may be used.
• the synthesis, purification and polymerization operations of lactide are described, for example, in U.S. Pat. No. 4,057,537, published European Patent Application No. 261572, Polymer Bulletin, 1, 4, 491-495 (1985), and Macromol. Chem., 187, 1611—1628 (1986).
• the catalyst used in this polymerization reaction is not particularly limited, and examples thereof include known lactic acid polymerization catalysts, such as tin compounds, powdered tin, tin oxide, zinc powder, halogenated zinc, Zinc oxide, organic zinc compounds, titanium compounds (eg, tetrapropyl titanate), zirconium compounds (eg, zirconium isopropoxide), antimony compounds (eg, antimony trioxide), bismuth compounds (eg, bismuth oxide ( ⁇ ))) And aluminum-based compounds.
• known lactic acid polymerization catalysts such as tin compounds, powdered tin, tin oxide, zinc powder, halogenated zinc, Zinc oxide, organic zinc compounds, titanium compounds (eg, tetrapropyl titanate), zirconium compounds (eg, zirconium isopropoxide), antimony compounds (eg, antimony trioxide), bismuth compounds (eg, bismuth oxide ( ⁇ ))
• tin-based compounds include tin lactate, tin tartrate, dicaprylate, dilaurate, dipalmitate, distearate, dioleate, tin naphthoate, / 3-naphthoate, and An example is tin octoate.
• the aluminum compound include aluminum oxide and aluminum isopropoxide.
• a catalyst made of tin or a tin compound is particularly preferable because it has excellent activity.
• the amount of these catalysts used is 0.001 to 5% by mass with respect to lactide.
• Polymerization reaction The reaction is usually performed at a temperature of 100 to 220 ° C. in the presence of the catalyst, although it varies depending on the type of catalyst. It is also preferable that the two-stage polymerization described in JP-A-7-247345 is performed.
• Examples of components other than polylactic acid in the polyester resin (A) include ring-opening polyaddition aliphatic polyesters and polycondensation reaction aliphatic polyesters.
• Examples of the ring-opening polyaddition aliphatic polyesters include polydaricholic acid, poly (3-hydroxybutyric acid), poly (4-hydroxybutyric acid), poly (4-hydroxyvaleric acid), and polystrength prolatatone.
• polycondensation reaction type aliphatic polyester examples include polyester carbonate, polyethylene succinate, polybutylene succinate, polyhexamethylene succinate, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, poly Examples include butylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, and polybutylene sebacate.
• the mass (weight) average molecular weight of the polyester resin (A) containing polylactic acid as a main component is a force S of 100,000 or more, preferably S, a force of 120,000 or more, more preferably S, 150, 000 More preferably, it is more preferably 180,000 or more.
• the mass average molecular weight of the polyester resin (A) is preferably 400,000 or less because the melt viscosity and melt tension of the polyester resin composition at the time of molding are high.
• the polyester resin (A) containing polylactic acid as a main component contains a small amount of unreacted lactide or lactic acid.
• lactide or lactic acid reacts with the epoxy group of the acrylic resin modifier (B) to inhibit the crosslinking reaction of the polyester resin (A) by the acrylic resin modifier (B). Therefore, the content of lactide or lactic acid in the polyester resin (A) is less than 0.2% by mass, preferably less than 0.15% by mass, and more preferably less than 0.1% by mass. It is particularly preferably less than 0.05% by mass.
• the acrylic resin modifier (B) is added to the polyester resin (A) even if the acrylic resin modifier (B) is added.
• the epoxy group in It is consumed by reacting with lactic acid or lactic acid, and the thickening effect that should be originally obtained is not fully exhibited. For this reason, an excessive amount of the acrylic resin modifier (B) is required, which not only impairs the biodegradability of the polyester resin composition but also increases the production cost.
• the ring-opening lactide which is an acid component, works as a reaction aid for the acrylic resin modifier (B), and if the amount is large, the reaction proceeds locally to generate a crosslinked product.
• the thickening effect cannot be obtained uniformly, there arises a problem that desired physical properties cannot be obtained.
• the constituent molar ratio L / D of L_lactic acid units and D_lactic acid units in polylactic acid may be any of 100/0 to 0/100.
• polylactic acid preferably contains at least 96 mol% of L-lactic acid and D_lactic acid in order to obtain a high melting point. More preferably, it contains 98 mol% or more of any unit of D-lactic acid.
• the polylactic acid may be a copolymer obtained by copolymerizing lactic acid (monomer) or lattide and other components copolymerizable therewith.
• Examples of other copolymerizable components include dicarboxylic acids having two or more ester bond-forming functional groups, polyhydric alcohols, hydroxycarboxylic acids, ratatones, and various polyesters composed of these various components. Examples include various polyethers and various polycarbonates.
• Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.
• Examples of the polyhydric alcohol include aromatic polyhydric alcohols (for example, those obtained by adding ethylene oxide to bisphenol, for example), aliphatic polyhydric alcohols, and ether glycols.
• Examples of the aliphatic polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, hexanediol, octanediol, glycerin, sonolebitan, trimethylololepropane, and neopentyldaricol.
• Examples of ether glycols include diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol.
• Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutylcarboxylic acid, and those described in JP-A-6-184417.
• Examples of Lataton include glycolide, ⁇ -force prolataton glycolide, ⁇ -force prolataton, ⁇ -propiolata Ton, ⁇ -Buchiguchi Rataton, ⁇ -Buchiguchi Rataton, ⁇ -Buchiguchi Rataton, Pivalo Rataton, and S-Valerolatataton.
• the arrangement pattern of the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer.
• the acrylic resin modifier ( ⁇ ⁇ ) has a function of improving the molding processability and thermal stability of the polyester resin ( ⁇ ) containing polylactic acid as a main component.
• acrylic and methacryl are collectively referred to as (meth) acrylic and clay.
• the glass transition temperature of the acrylic resin modifier ( ⁇ ⁇ ) is 0 ° C or higher, preferably 30 ° C or higher, and preferably S is 50 ° C or higher.
• the acrylic resin modifier (B) cannot sufficiently exert the thickening effect on the polyester resin (A) during molding of the polyester resin composition, and molding is not possible. It may not be possible to improve workability.
• the upper limit of this glass transition temperature is usually 100 ° C.
• Acrylic resin modifier (B) The average number of epoxy groups per molecule is 3 to 30, 3.
• the power is preferably 5 to 20, and more preferably 4.0 to 10.
• the average number of epoxy groups is less than 3, the moldability with a small thickening effect on the polyester resin (A) cannot be sufficiently improved.
• the average number of epoxy groups exceeds 30, excessive epoxy groups cause excessive crosslinking reaction with the carboxyl groups or hydroxyl groups of the polyester resin (A), and the molding cacheability deteriorates.
• Acrylic resin modifier (B) The average number of epoxy groups per molecule (hereinafter referred to as Fn) is calculated by the following formula (1).
• a, b and c are defined as follows.
• a represents the ratio (% by mass) of the epoxy group-containing acrylic monomer unit contained in the acrylic resin modifier (B).
• b represents the number average molecular weight of the acrylic resin modifier (B).
• c represents the molecular weight of the epoxy group-containing acrylic monomer.
• the weight average molecular weight of the acrylic resin modifier (B) is 1,000 to 30,000, preferably 1,500 to 20,000, and preferably 2,000 to 15,000. Even more preferred. If this mass average molecular weight is less than 1,000, the acrylic resin modifier (B) Since the average number of poxy groups decreases, the thickening effect on the polyester resin (A) becomes insufficient. If the weight average molecular weight exceeds 30,000, the average number of epoxy groups per molecule of the acrylic resin modifier (B) increases, and the polyester resin (A) undergoes an excessive crosslinking reaction, resulting in moldability. Getting worse.
• the molecular weight distribution (mass average molecular weight / number average molecular weight) of the acrylic resin modifier (B) is preferably 1.5 to 5.0, more preferably 1.6 to 4.5. Mashi 1. It is more preferable that it is 7 to 4.0.
• the acrylic resin modifier (B) is obtained by polymerization of a monomer mixture containing an epoxy group-containing acrylic monomer and a styrene monomer.
• the acrylic resin modifier (B) can also be obtained by polymerization of a monomer mixture containing an epoxy group-containing acrylic monomer, a styrene monomer, and other vinyl monomers.
• the epoxy group-containing acryl-based monomers include (meth) acrylic acid glycidyl or (meth) acrylic acid ester having a cyclohexenoxide structure, and (meth) acrylic glycidinoreether.
• a preferable epoxy group-containing acrylic monomer is (meth) acrylic acid glycidinole having high reactivity.
• the styrenic monomer has the same properties as the polylactic acid, and thus has an affinity for polylactic acid.
• the styrene monomer include styrene and ⁇ -methylstyrene.
• butyl monomers other than epoxy group-containing acrylic monomers and styrene monomers include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid Pill, (meth) butyl acrylate, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid cyclohexyl, stearyl (meth) acrylate, alkyl group having carbon number:!
• (Meth) acrylic acid alkyl ester for example, (meth) acrylic acid methoxyethyl), (meth) acrylic acid polyalkylene glycol ester, (meth) acrylic acid alkoxyalkyl ester , (Meth) acrylic acid hydroxyalkyl esters, (meth) acrylic acid dialkylaminoalkyl esters, (meth) acrylic esters
• acrylic acid alkyl ester for example, (meth) acrylic acid methoxyethyl), (meth) acrylic acid polyalkylene glycol ester, (meth) acrylic acid alkoxyalkyl ester , (Meth) acrylic acid hydroxyalkyl esters, (meth) acrylic acid dialkylaminoalkyl esters, (meth) acrylic esters
• Examples include benzyl laurate, phenoxyalkyl (meth) acrylate, isobornyl (meth) acrylate, and alkoxysilylalkyl (meth) acrylate.
• (meth) atalinoleamide, (meth) acrylic dialkylamide, buleste can be used as bulur monomers other than epoxy group-containing acrylic monomers and styrene monomers.
• Aromatic monomers such as butyl acetate, butyl ethers, (meth) aryl ethers, and ⁇ -olefin monomers may also be used.
• ⁇ -olefin monomers include ethylene and propylene. These may be used alone or in combination of two or more.
• the acrylic resin modifier ( ⁇ ⁇ ) preferably contains 10 to 40% by mass of an epoxy group-containing acrylic monomer unit and 90 to 20% by mass of a styrene monomer unit. Les. It is more preferable that the acrylic resin modifier ( ⁇ ) contains 15 to 35% by mass of an epoxy group-containing acrylic monomer unit and 85 to 25% by mass of a styrene monomer unit. Les. It is more preferable that the acrylic resin modifier ( ⁇ ) contains 20 to 30% by mass of an epoxy group-containing acrylic monomer unit and 80 to 30% by mass of a styrene monomer unit. ,.
• the acrylic resin modifier ( ⁇ ⁇ ) does not contain a bull monomer unit other than the epoxy group-containing acrylic monomer unit and the styrene monomer unit, or the acrylic resin modifier.
• the balance in the agent (ii) is a vinyl monomer unit other than the epoxy group-containing acrylic monomer unit and styrene monomer unit.
• a crosslinked product is formed, and a molded product having a desired shape cannot be obtained.
• the styrenic monomer unit and the epoxy monomer-containing acrylic monomer unit and the vinyl monomer unit other than the styrenic monomer unit are the above after the ratio of the acrylic monomer unit is set. Within this range, it is set as appropriate in consideration of the mechanical strength of the molded product.
• the acrylic resin modifier (i) can be produced by any method such as a bulk polymerization method, a solution polymerization method, and an emulsion polymerization method.
• the preferred polymerization method is a continuous stirred tank polymerization method, more preferred.
• a new polymerization method is a high temperature continuous stirred tank polymerization method.
• the polymerization temperature is preferably from 130 to 350 ° C, more preferably from 150 to 330 ° C, even more preferably from 170 to 270 ° C.
• a polymer having a desired molecular weight can be efficiently obtained by using a radical polymerization initiator and a chain transfer agent, or by using a very small amount.
• the polymerization temperature is less than 130 ° C, a large amount of radical polymerization initiator and chain transfer agent are required to obtain a polymer having the desired molecular weight. Therefore, impurities are present in the obtained polymer. Many are easy to include. For this reason, problems such as coloring and off-flavor may occur in the polyester resin composition and the molded body.
• the polymerization temperature exceeds 350 ° C, the polymer may be thermally decomposed and the target polymer may not be obtained.
• Such a high-temperature continuous stirring tank polymerization method is, for example, a known polymerization method disclosed in JP-T-57-502171, JP-A-59-6207, and JP-A-60-215007. It is done by. For example, after a pressurizable reactor is set to a predetermined temperature under pressure, each of the bull monomers and, if necessary, a vinyl monomer mixture composed of a polymerization solvent is added to the reactor at a constant supply rate. A method is adopted in which a polymerization reaction liquid is supplied from the reactor in an amount commensurate with the supply amount of the bull monomer mixture. Moreover, a polymerization initiator may be mix
• the blending amount of the polymerization initiator is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the vinyl monomer mixture.
• the pressure depends on the reaction temperature and the boiling point of the butyl monomer used and the polymerization solvent, and does not affect the reaction. Therefore, the pressure should be sufficient to maintain the reaction temperature. Good.
• the residence time of the monomer mixture in the reactor is preferably 1 to 60 minutes. If the residence time is less than 1 minute, the monomer may not sufficiently react, and if the residence time exceeds 60 minutes, productivity tends to decrease.
• the preferred residence time is 2 to 40 minutes.
• Such a high-temperature continuous stirring tank polymerization method can maintain the composition in the polymerization tank in a uniform state as compared with the batch polymerization method and the semi-batch polymerization method. Distribution is uniform. Therefore, the acrylic resin modifier (B) has a more uniform number of epoxy groups per molecule and molecular weight distribution, and is suitable for the purpose. In addition, high temperature The continuous polymerization method has an advantage that a desired acrylic resin modifier (B) can be obtained by a short polymerization operation, and is economical and hardly causes gelation by a crosslinking reaction.
• the acrylic resin modifier (B) is a temperature measured according to the flow test method for thermoplastics specified in ISO 1133 (International Standard 3-1 ⁇ 7 210). : It is preferable that the MFR value at 210 ° C and load: 21.2N (2.16kgf) shows the specified value. That is, the change between the MFR value (MFR) after 5 minutes and the MFR value (MFR) after 15 minutes.
• the conversion rate deviation (a MFR: (MFR -MFR) / MFR) should be _0.35 to 0.1
• the change rate deviation of the MFR value is less than 0, it means that the viscosity of the sample increases with time. That is, the reaction between the resin and the acrylic resin modifier (B) was not completed during the mixing and kneading, and the reaction further progressed during the subsequent molding cage.
• the change rate deviation of the MFR value is less than -0.35
• the reaction between the polyester resin (A) and the acrylic resin modifier (B) proceeds excessively during the molding process, increasing more than necessary. Because of stickiness, fish eyes and disappearance may occur on the surface of the resulting molded article, which may reduce the design.
• the deviation rate deviation of the MFR value exceeds 0.1, it means that the viscosity of the sample decreases with time. In this case, the viscosity of the resin is greatly reduced due to a long stay during the molding process, and drawdown occurs, making it difficult to obtain a molded body having a desired shape.
• the epoxy equivalent (hereinafter referred to as EV) of the acrylic resin-based modified homogeneous IJ (B) has a power of 0.70 to 3.00 meq / g.
• S is preferably 1.06 to 2.46 meq / g.
• the power of g is more preferable than S, and more preferably 1.40 to 2. l lmeq / g.
• this epoxy equivalent is less than 0.70 meq / g, a large amount of acrylic resin modifier (B) is added to the polyester resin (A) in order to sufficiently obtain the moldability and thermal stability of the polyester resin composition. It is necessary to add. As a result, there arises a problem that the mechanical strength of the molded product obtained from the polyester resin composition is lowered.
• the polyester resin composition becomes, for example, due to excessive crosslinking reaction between the carboxyl group or hydroxyl group of the polyester resin (A) and the epoxy group of the acrylic resin modifier (B).
• An excessive cross-linked state is caused in the molding machine, and a molded product having a desired shape cannot be obtained by surging or the like. There is a case.
• the addition amount of the acrylic resin modifier (B) is 0.11 to 1 part by mass, and 0.2 to 0.8 part by mass with respect to 100 parts by mass of the polyester resin (A). Is more preferably 0.3 to 0.6 parts by mass.
• the amount of the acrylic resin-based modifier (B) added is less than 0.15 parts by mass, the excellent thermal stability and molding cacheability of the polyester resin composition which is poor in the modification effect cannot be obtained.
• the amount of the acrylic resin modifier (B) exceeds 1 part by mass, the polyester resin composition is excellent in thermal stability, but the crosslinking reaction proceeds during the molding process, leading to an excessive crosslinking state. Therefore, molding becomes difficult.
• the method of mixing the acrylic resin-based modifier (B) into the polyester resin (A) and blending various additives may be carried out by a conventionally known method without particular limitations.
• powder or pellets of polyester resin (A) and each component of the additive may be mixed by dry blending, or a part of the additive may be preblended and other components may be dry blended later. Good.
• each component is mixed using a mill roll, a Banbury mixer, or a super mixer, and then kneaded using a single screw or twin screw extruder. This mixing and kneading is usually performed at a temperature of 120 to 220 ° C.
• the mixing temperature of the polyester resin (A) and the acrylic resin modifier (B) is preferably 180 to 230 ° C.
• the mixing temperature is less than 180 ° C, the reaction between the polyester resin (A) and the allyl resin modifier (B) proceeds slowly, so that the reaction takes time, and productivity and equipment are limited.
• the mixing temperature exceeds 230 ° C, depolymerization of the polyester resin (A) occurs at the same time, and the viscosity of the polyester resin (A) component in the final polyester resin composition becomes shorter and the viscosity decreases. happenss.
• the residence time is 2 minutes or more 3 to: 15 minutes.
• 3 to 10 minutes is more preferable. If the residence time is less than 2 minutes, sufficient reaction time cannot be secured, and unreacted substances remain and the reaction proceeds during the molding process. If the residence time exceeds 15 minutes, there is a concern that the polyester resin (A) will suffer heat degradation and depolymerization if the productivity decreases. Furthermore, an additive may be added in the polymerization step for obtaining the polyester resin (A). In addition, for example, a master batch containing a high concentration of additives is produced. A method in which this is added to the polyester resin (A) can also be employed.
• polyester resin composition conventionally known plasticizers, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, colorants, various fillers, antistatic agents, release agents, if necessary.
• additives such as agents, fragrances, lubricants, flame retardants, foaming agents, fillers, antibacterial agents'antifungal agents, and other nucleating agents may be blended.
• an aliphatic amide compound, an aromatic amide compound, talc or the like, which is a known crystal nucleating agent is blended.
• the polyester resin composition is a rheometer equipped with a die having a diameter of 1 mm and a length of 10 mm, specifically a capillary rheometer (Capillograph 1C, manufactured by Toyo Seiki Co., Ltd.), temperature: 200 °.
• a capillary rheometer Capillograph 1C, manufactured by Toyo Seiki Co., Ltd.
• temperature 200 °.
• the melt viscosity measured under the condition of C and shear rate: 121se C — 1 the following conditions are preferably satisfied. That is, the melt viscosity when the acrylic resin modifier (B) is added) and the melt viscosity when the acrylic resin modifier (B) is not added (add
• the rate of change ⁇ ( ⁇ / ⁇ ) is preferably 1.1 to:! This strange
• the rate of change A DS (DS / DS) with Swell (DS) at the time is 1 ⁇ 05 ⁇ : L 3
• the change rate A DS is less than 1.05, sufficient processability cannot be exhibited, which is insufficient for thickening effect.
• the rate of change A DS exceeds 1.3, the increase in viscosity during the molding process becomes excessively large, making it difficult to obtain a molded product having a desired shape. Therefore, it is particularly preferable that the conditions of the change rate ⁇ of the melt viscosity and the change rate ADS of the swell are both satisfied.
• the molding method of the polyester resin composition is not limited to an extrusion molding method of a film, a sheet or the like, but in the same manner as a general plastic, an injection molding method, a blow molding method, a vacuum molding method, a compression molding method, etc.
• a molding method may be employed.
• various molded objects such as a film molded object, a sheet molded object, a fiber, a foam molded object, a blow molded object, are obtained.
• Polyester resin set The composition is also suitable for molding foams and the like that require particularly high melt strength and melt tension.
• the polyester resin composition is obtained by blending the acrylic resin modifier (B) at a ratio of 0.15 to 1 part by mass with respect to 100 parts by mass of the polyester resin (A) described above. It is done.
• the polyester resin composition is heated and melted and molded according to a molding method such as an injection molding method to produce a molded body having a desired shape. Is done.
• the epoxy group contained in the acrylic resin modifier (B) reacts with a carboxyl group or a hydroxyl group present at the terminal of polylactic acid which is the main component of the polyester resin (A).
• the crosslinking reaction proceeds.
• the epoxy group in the acrylic resin-based modifier (B) is a carboxynole of polylactic acid.
• the average number of epoxy groups per molecule of the acrylic resin modifier (B) is limited to 3-30, and the mass average molecular weight is set in the range of 1,000-30,000. , Excessive progress of the crosslinking reaction is suppressed. Therefore, an appropriate thickening can be obtained during molding, and the molding can proceed smoothly to produce a molded product having good appearance and physical properties.
• This embodiment has the following advantages.
• the polyester resin composition of the present embodiment contains 0.1-15 parts by mass of the acrylic resin modifier (B) with respect to 100 parts by mass of the polyester resin (A).
• Polyester resin (A) is mainly composed of polylactic acid, and the content of lactide or lactic acid is less than 0.2% by mass.
• the glass transition temperature of the acrylic resin modifier (B) is 0 ° C or higher
• the average number of epoxy groups per molecule of the acrylate resin modifier (B) is 3 to 30
• the mass average molecular weight of the talyl resin modifier (B) is 1,000-30,000. For this reason, the epoxy group of the acrylic resin modifier (B) reacts with the carboxyl group or hydroxyl group of the polylactic acid terminal to form an appropriate crosslinked structure.
• the polyester resin composition When the polyester resin composition is molded by heating, the viscosity increases due to the crosslinking reaction, and a viscosity suitable for molding is obtained. Therefore, while suppressing excessive cross-linking reaction, it is possible to improve the molding strength due to the thickening effect, and excellent thermal stability. Qualitative can be demonstrated.
• polyester resin composition has a change rate deviation ( ⁇ MFR) value of ⁇ 0.35-0.
• the amount of epoxy groups contained in the acrylic resin modifier (B) is set by setting the epoxy equivalent of the acrylic resin modifier ( ⁇ ) to 0.70-3.00 meq / g. But with molecular weight
• the acrylic resin modifier (B) is obtained by polymerizing a monomer mixture containing an epoxy group-containing acrylic monomer and a styrene monomer, an acrylic resin-based modifier is obtained.
• a polymer having an epoxy group can be easily obtained as the modifying agent (B).
• the acrylic resin-based modifier (B) is produced by a continuous stirred tank polymerization method set at a temperature of 130 to 350 ° C, so that the acrylic resin-based modifier having a target molecular weight is modified. It is possible to manufacture the quality agent efficiently.
• the value of the change rate ⁇ 77 (77 / ⁇ 7) of the melt viscosity (77) is set to 1 ⁇ 1 to:! ⁇ 8
• the addition of the acrylic resin modifier (B) can increase the melt viscosity and can further improve the molding strength.
• the temperature dependence of the melt viscosity of the polyester resin composition can be reduced, and the viscosity change can be maintained even during long-time residence at the molding processing temperature, which can only improve the molding processability. Can be kept within a certain range.
• a molded article having an appearance and mechanical properties superior to conventional ones can be produced by melt-molding the polyester resin composition.
• the pellet was immersed in acetonitrile for 12 hours, and the extracted measurement specimen was measured with a high-performance liquid chromatograph, and the obtained results were obtained using a lactide calibration curve or a lactic acid calibration curve prepared in advance.
• the content of lactide or lactic acid was analyzed by calculation.
• the weight average molecular weight (Mw) of the polymer is a polystyrene conversion value by gel permeation chromatography (GPC) analysis, and the glass transition temperature and melting point are determined by a scanning differential calorimeter (DSC) at a rate of temperature increase of 10 ° C. It is a value measured in / min.
• the average number (Fn) of epoxy groups per molecule of the acrylic resin modifier (B) was calculated from the above-described formula (1).
• the epoxy equivalent (EV) was measured according to ASTM D-1652-73.
• the oil jacket temperature of a 1 liter pressurized stirred tank reactor equipped with an oil jacket was maintained at 200 ° C.
• 74 parts by mass of styrene hereinafter referred to as St
• 20 parts by mass of glycidyl methacrylate hereinafter referred to as GMA
• 6 parts by mass of butyl acrylate hereinafter referred to as BA
• 15 parts by mass of xylene and initiation of polymerization
• a monomer mixture consisting of 0.5 parts by mass of ditertiary butyl peroxide (hereinafter referred to as DTBP) was charged into the raw material tank as an agent.
• the monomer mixture is continuously supplied from the raw material tank to the reactor at a constant supply rate (48 g / min, residence time: 12 minutes), and the reaction liquid is kept constant at approximately 580 g. Was continuously extracted from the outlet of the reactor. At that time, the internal temperature of the reactor was kept at about 210 ° C.
• MMA methyl metatalylate
• a polymer 3 was produced by the same production method as that for the polymer 1 except that the composition of the raw material monomer was as shown in Table 1. (Production Examples 4-7, production of acrylic polymers 4-7)
• Polymers 4 to 7 were produced by the same production method as that for polymer 1 except that the composition of the raw material monomers and the polymerization temperature were as shown in Table 1.
• the following two types of polylactic acid resin were used. Each molecular weight shown below is a polystyrene conversion value by GPC method, and Tg is by DSC. The lactide content is a result measured by liquid chromatography according to the above method.
• PLA1 Polylactic acid resin B_2 (hereinafter referred to as PLA1) manufactured by Toyota Motor Corporation
• PLA2 Polylactic acid resin # 5000 (hereinafter referred to as PLA2) manufactured by Toyota Motor Corporation
• each component is uniformly premixed with a Henschel mixer, It was melt kneaded at 200 ° C. in a parallel twin screw extruder (ST-40, manufactured by Plastics Engineering Laboratory).
• Denacol EX-313 Polyglycidyl etherate manufactured by Nagase ChemteX Corporation
• GS-Pla Aliphatic polyester resin (polybutylene succinate) “G” manufactured by Mitsubishi Chemical Corporation
• AO-50 Phenolic antioxidant manufactured by Asahi Denka Kogyo Co., Ltd .: “ADK STAB A ⁇ -50”
• WX-1 JI Ken Fine Chemical Co., Ltd.
• Bisamide lubricant “WX_ 1”
• LA-1 Nisshinbo Carpositimide Stabilizer: “LA_ 1”
• the temperature was 210 ° C and the load was 21.2N (2.)
• the load was 21.2N (2.)
• the MFR value at 16 kgf was measured.
• Example 1 -0.18 1.15 1.07 A ⁇ and DS are calculated based on the value of standard 1
• Example 2 -0.26 1.37 1.15 ⁇ ⁇ and DS are calculated based on the value of standard 1
• Example 3 -0.34 1.29 1.25 AV and DS are calculated based on the value of standard 1
• Example 4 0.05 1.30 1.05 ⁇ ⁇
• lDS is calculated based on the value of standard 1
• lDS is standard
• IDS is calculated based on the standard 3 value
• DS is calculated based on the standard 3 value Comparative Example 1 0.39 1.00 1.00 Standard 1
• Comparative Example 3 -0.53 1.77 1.54 ⁇ ⁇
• lDS is calculated based on the value of Reference 1 Comparative Example 4 0.03 1.05 1.01 A ⁇
• DS is calculated based on the value of Reference 1 Comparative Example 5 0.08 1.07 1.01 ⁇ ⁇
• DS is calculated based on the value of standard 1.Comparative example 6 1 0.01 1.20 1.01 ⁇ ⁇
• DS is based on the value of standard 1
• Calculation Comparative Example 8 1.41 0.76 0.98 A ⁇
• DS is calculated based on the value of Standard 1. Comparative Example 9 0.12 1.17 1.04 An.
• DS is calculated based on the value of Standard 1.
• Example 1 When the value of the change in melt viscosity of Example 1 was compared with the value of the change in melt viscosity of Comparative Example 11 in which a polylactic acid resin having a high lactide content was used, the addition of polymer 1 as an acrylic resin modifier was added. Despite the same amount and compounding conditions, the thickening effect of the viscosity change value of Example 1 was higher than that of Comparative Example 11.
• Example 1 From the results of Example 1, Example 4 and Example 5, the appearance of the PLA compound was good and a sufficient thickening effect as a PLA resin was confirmed. However, the amount of the acrylic resin-based modifier added was small. In Comparative Example 9 with a small amount, a sufficient thickening effect was not confirmed based on the values of ⁇ and ADS. On the other hand, in Comparative Example 10 in which the acrylic resin modifier was excessively added, a crosslinking reaction occurred in the extruder, the melt reached gelation, and a stable extrusion could not be achieved. However, it was confirmed that the reaction proceeds excessively and the viscosity change of MFR measurement is large, so that the thermal stability during molding calorie is lacking.
• a compound that reacts with the hydroxyl group or carboxynole group of polylactic acid may be added to the polyester resin composition.
• this compound include acid anhydrides, alkoxy compounds, and amide group-containing compounds.
• An aromatic polyester resin may be added to the polyester resin composition in order to improve the mechanical strength and heat resistance of the molded body.
• an epoxy compound such as bisphenol A may be blended in the polyester resin composition.

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