JP2006232975A - Modifier for polyester resin and method for producing molded article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modifier for polyester resin improving molding properties in melt molding such as injection molding, extrusion molding, contour extrusion molding, direct flow molding and calender molding, and improving mechanical properties and to provide a molded article of polyester using the agent. <P>SOLUTION: The invention relates to the modifier for polyester resin comprising a polylactic acid resin (I) and a reactive compound (II) having at least two glycidyl groups and/or isocyanate groups per molecule and having molecular weight of 200 to 500,000. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a modifier that is particularly suitable for modifying polyester resins. Specifically, the present invention provides a polyester resin molded article having improved moldability in injection molding, extrusion molding, profile extrusion molding, T-die extrusion molding, direct blow molding, and calendering molding and improved mechanical properties.

  In recent years, for example, there is a movement to replace vinyl chloride resin with other materials due to environmental problems. Among the many alternative materials, polyester resin is a powerful material in terms of its physical properties, environmental suitability, adhesive properties, price, and the like.

  Among the polyester resins, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyester elastomer, aliphatic polyester, poly Crystalline polyester resins such as caprolactone or polylactic acid are molded into heat-resistant parts by injection molding, films, sheets by extrusion molding, beverage bottles by blow molding, fibers by melt spinning, and the like.

  On the other hand, amorphous polyester resin is superior in gloss, impact resistance, and stress whitening suppression compared to crystalline polyester typified by PET, and moreover, it is easy to process, so it is easy to form a single layer by extrusion molding. Multi-layer sheets, lamination films, shrink films, miscellaneous goods, stationery, cosmetic containers by injection molding, price rails, IC tubes, etc. by profile extrusion molding.

  However, these polyester resins undergo thermal decomposition and hydrolysis during hot melt molding, resulting in a decrease in molecular weight. In particular, when the polyester resin is not sufficiently dried, the molecular weight is remarkably reduced, so that there is a problem that the mechanical properties of the product are greatly reduced.

  Furthermore, in the case of direct blow molding, this molecular weight reduction causes a noticeable drawdown phenomenon and increases unevenness in thickness and burrs, resulting in a decrease in yield rate. At the same time, since the parison formation state is not stable, the continuous production stability is also lowered. Further, since mechanical properties such as impact resistance of the molded product are lowered, the bottle strength is insufficient when the bottle container is filled with the contents, and the contents are projected by bursting when the bottle is dropped.

  In recent years, PET bottles are used in large quantities in various soft drinks such as mineral water. On the other hand, the PET bottle disposal problem has attracted attention, and PET bottle scrap processing has become a social problem. From such a background, recycling of used PET bottles has been intensively studied.

  In order to recycle PET bottles, after collecting used PET bottles, they are crushed and washed to obtain recycled PET flakes, which are used as raw materials for molding products and once pelletized by melt extrusion. A product may be formed from the pellets through melt molding.

  This regenerated PET flake is difficult to be molded because it has a low molecular weight due to thermal history, it contains a large amount of moisture by the washing process, and because it is in the form of flakes, it is difficult to mold into the screw of the molding machine. With flakes alone, only quality unstable and brittle products can be obtained. Also, PET is usually susceptible to hydrolysis, and when molded in an undried state, hydrolysis is accelerated and molecular weight is reduced during melting, so that mechanical properties such as impact resistance are greatly reduced. Accordingly, molded articles using recycled PET flakes often do not satisfy the performance required for ordinary plastic products.

  As a study for improving impact resistance, a method of melt-molding polyester with an impact resistance improver is known. An impact modifier effective for polyester is disclosed in Patent Document 1. In this publication, a rubbery polymer obtained by grafting or copolymerizing a compound having a functional group capable of chemically reacting with polyester is used. Particularly effective are polymers based on olefinic and styrenic block polymers. Patent Document 2 shows that the drawdown at the time of molding is improved by blending a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene and an organic polymer with respect to the polyester resin. Yes. Patent Document 3 shows that the impact resistance of a polyester resin molded product produced from recycled PET flakes is improved by blending a polyester resin with multilayer structure particles composed of rubber components. Patent Document 4 discloses that impact resistance is improved by blending a polyester resin with polypropylene and an unsaturated carboxylic acid-modified ethylene-based or styrene-based polymer. Patent Documents 5 and 6 show that impact resistance is improved by blending a polyester resin with a thickener (rubber-based resin) and a polymerizing agent (ethylene-based or styrene-based elastomer).

  In the kneading of the impact resistance improver and the polyester resin as described above, the molecular weight decrease due to re-extrusion further proceeds. Therefore, the impact resistance improvement is not sufficient with the addition of a small amount of the impact resistance improver. Further, since the addition of a different polymer, the transparency inherent in the polyester resin is hindered by the difference in refractive index between the two. Therefore, the current situation is that transparency must be sacrificed to improve impact resistance.

  Patent Document 7 shows that by adding a polymer composed of a vinyl polymer to a thermoplastic resin, particularly a polyester resin, the fluidity is improved while maintaining transparency. However, in this case, even when applied to a polyester resin, transparency can be maintained, but it remains difficult to suppress a decrease in molecular weight, and the impact resistance cannot be improved.

  Although it is a blow extrusion application, a melt strength enhancer having a reactivity with a weight average molecular weight of 1,000,000 to 4,000,000 has been proposed as a reactive melt strength improver (Patent Document 8). However, since this type of melt strength enhancer must disperse a very high molecular weight vinyl aromatic modifier in the polyester resin, it is necessary to thoroughly adjust its blending amount and processing conditions. is there. For example, in order to achieve the target melt strength, the processing conditions are limited to a narrow range, and when deviating from these conditions, the melt strength will fluctuate greatly. Also, because of the poor compatibility between the melt strength enhancer and the polyester resin, there was a problem that voids were generated even when the molding was applied even if it was bent slightly, and this portion was whitened.

  As described above, there has been a demand for a modifier capable of stabilizing the melt viscosity property at the same time while suppressing the decrease in physical properties due to the decrease in molecular weight, and particularly improving the impact resistance. It has not been.

JP 59-28223 A JP-A-11-269360 JP 2001-2903 A JP 2001-114995 A JP 2002-146167 A JP 2002-249649 A JP 2000-355657 A Japanese Patent No. 3237913

  The object of the present invention is to improve the moldability in melt molding using polyester resin, in particular, injection molding, extrusion molding, profile extrusion molding, direct blow molding, calendering molding, and improve mechanical properties. The object is to provide a modifier, and to provide a polyester molded article using the modifier.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors contain at least two polylactic acid resins (I), glycidyl groups and / or isocyanate groups per molecule, and have a weight average molecular weight of 200 to 500,000. Reactive compound (II) is kneaded in advance and partially reacted to obtain a modifier, and then blended with amorphous polyester resin (III) and / or crystalline polyester resin (IV) and molded. The present invention has been completed by finding that all the above problems can be solved. That is, this invention is the manufacturing method of the polyester molded product using the following modifiers for polyester resins, and this.

  1st invention contains polylactic acid resin (I) and the reactive compound (II) which contains 2 or more glycidyl group and / or isocyanate group per molecule, and is the weight average molecular weights 200-500,000. It is the modifier for polyester resins.

  The second invention relates to a polylactic acid resin (I), a reactive compound (II) containing two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000, amorphous It is a polyester resin composition in which the reactive polyester resin (III) is contained.

  The third invention comprises a polylactic acid resin (I), a reactive compound (II) containing two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000, crystallinity, A polyester resin composition containing polyester resin (IV).

  A fourth invention is a modification comprising a polylactic acid resin (I) and a reactive compound (II) containing two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000. This is a method for producing a molded article in which an agent is mixed with amorphous polyester (III) and / or crystalline polyester resin (IV) and melt-molded.

  By blending the modifier of the present invention with a polyester resin, it is possible to improve moldability in melt molding, in particular, injection molding, T-die extrusion molding, profile extrusion molding, direct blow molding, and calendering molding. A polyester resin molded product having specific physical properties can be obtained.

  The modifier for polyester resin of the present invention contains a reactive compound (II) containing polylactic acid resin (I) and two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000. ), And by mixing the modifier with amorphous polyester resin (III) and / or crystalline polyester resin (IV) and molding the above, it is possible to impart excellent characteristics to the molded product. I can do it.

  That is, in this formulation, when the molecular weights before molding and after molding are compared, the molecular weight of the resin increases after molding, so that it is possible to prevent a decrease in molecular weight during melt molding. Furthermore, since the compatibility between the polyester resins is good, mechanical properties such as impact resistance of the molded product can be improved. At the same time, since it is the same kind of polyester material blending system, the compatibility of the polyester resin is good and the melt viscosity characteristic can be stabilized.

  For example, in the case of profile extrusion molding, the resin that is discharged from the mold is prevented from being drawn down, and `` the resin discharged through the extrusion process and profile mold process adheres to the sizing mold and clogging occurs, resulting in continuous production. ”Problems to stop the product”, “Problems to deteriorate the dimensional accuracy of the product shape in the sizing process”, “Problems that cause chattering (streaks parallel to the progress method) on the surface of the molded product due to the resin melting characteristics in the sizing mold ”,“ Problem of product warping in the direction of profile extrusion molding ”, and the like can be improved.

  In the case of direct blow molding, the melt viscosity is increased and the drawdown is improved, so that the parison formation state is stabilized and the continuous production stability is improved. Further, the mechanical properties such as impact resistance of the molded product are improved. As a result, the bottle strength when the contents are filled in the bottle container is improved, and the problem of the protrusion of the contents due to rupture at the time of dropping is improved.

  Furthermore, in the case of calender molding, the melt viscosity increases and the drawdown is improved, so that the processability is greatly improved and the required characteristics such as product dimensions and gloss can be satisfied. Further, since the melt tension of the resin is increased, it is difficult to adhere to the roll, and the problem that the resin extends due to the take-up tension can be solved.

  The modifier of the present invention contains polylactic acid resin (I) as an essential component. As lactic acid used as a raw material for the polylactic acid resin, either L-lactic acid or D-lactic acid can be used. Further, L-lactide, D-lactide, and DL-lactide may be used. The molecular weight can be arbitrarily adjusted by changing the polymerization time and temperature of the polyester, the degree of pressure reduction during polymerization (in the case of vacuum polymerization), or changing the amount of polyalcohol component to be copolymerized, which will be described later. Can do.

  In addition to lactic acid, polylactic acid resin used in the present invention, in addition to lactic acid, oxyacids such as glycolic acid, malic acid, citric acid, gluconic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, caprolactone, Lactones such as valerolactone and butyrolactone, aliphatic dibasic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, ethylene glycol, diethylene glycol, neopentyl glycol, propylene glycol, 1,4-butanediol, 1,6 -Aliphatic glycols such as hexanediol and 1,9-nonanediol, glycerin, polyglycerin and the like can be copolymerized, but are not limited to these copolymerization components. Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and orthophthalic acid, and aromatic diols such as bisphenol A and alkylene oxide adducts of bisphenol A may be copolymerized as long as they are in a small amount, but are biodegradable. It is preferably not included from the aspect. The amount of the other monomer to be copolymerized is preferably less than 30 mol% when the total amount of lactic acid and other monomers is 100 mol%.

  In the polylactic acid resin (I), the molar ratio (L / D) of L-lactic acid residue to D-lactic acid residue is preferably 90/10 to 10/90. A particularly preferable range is 80/20 to 20/80. By adjusting to this range, the melting point of the polylactic acid resin is lowered, or by becoming amorphous, it becomes easy to control the reaction with the modifier, and is excellent in compatibility with the polyester resin described later, The mechanical strength of the molded product is improved.

  The content of the polylactic acid resin (I) in the modifier of the present invention is preferably 20% by weight or more and 99.5% by weight or less when the entire modifier is 100% by weight, and the lower limit is 30% by weight or more. The upper limit is more preferably 98% by weight or less. If it exceeds 99.5% by weight, the mechanical properties such as impact resistance and the effect of improving the melt strength may not be exhibited.

  The polylactic acid resin (I) used in the present invention preferably has polyglycerol as its copolymer segment. The polyglycerin used preferably has a degree of polymerization of 3 or more. In the case of glycerin or a dimer of glycerin, a high-molecular-weight lactic acid-based polyester may not be obtained with a sufficient hydroxyl group concentration. On the other hand, when the degree of polymerization exceeds 20, the water resistance of the resin may decrease.

  The polyglycerin segment is contained in an amount of preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, and particularly preferably 5% by mass or less. The lower limit is not particularly defined, but is preferably 0.01% by mass or more, and more preferably 0.02% by mass or more.

The hydroxyl group concentration of the polylactic acid resin (I) used in the present invention is preferably 100 equivalent / 10 ⁶ g or more. If it is less than 100 equivalents / 10 ⁶ g, good pigment dispersibility may not be obtained. On the other hand, if the concentration exceeds 500 equivalents / 10 ⁶ g, the water resistance of the resin may deteriorate. More preferably, it is 130 equivalents / 10 ⁶ g or more, more preferably 150 equivalents / 10 ⁶ g or more, and the upper limit is more preferably 450 equivalents / 10 ⁶ g or less, still more preferably 400 equivalents / 10 ⁶ g or less, Particularly preferred is 350 equivalents / 10 ⁶ g or less, and most preferred is 300 equivalents / 10 ⁶ g or less.

  As a method for producing a polylactic acid resin containing the above polyglycerin as a copolymerization component, for example, a method in which polyglycerin is collectively charged as a polymerization initiator at the time of ring-opening polymerization of lactide and melted in a nitrogen atmosphere to perform ring-opening polymerization, There is a method of depolymerizing molecular weight polylactic acid with polyglycerin and the like, and the former method is preferable in order to stably obtain a polylactic acid resin having a desired reduced viscosity. Moreover, after manufacturing a polylactic acid segment part, you may make it react with polyglycerol, or you may make it combine. As a method of bonding the polylactic acid segment part to the polyglycerin after production, a method using a urethane bond, a method using an epoxy group, or the like can be used.

  As the ring-opening polymerization catalyst of lactide, ring-opening polymerization catalysts such as tin octylate and aluminum acetylacetonate can be used, and there is no particular limitation.

  The polylactic acid resin (I) used in the present invention preferably has a glass transition temperature of 40 ° C. or higher, and preferably 60 ° C. or lower. By making it within this range, pigment dispersibility is improved. As a method of bringing the glass transition temperature to a range of 40 to 60 ° C., it can be adjusted by adjusting the polyglycerin segment, selecting other copolymerization monomers, and optimizing these amounts.

  In the polylactic acid resin (I) used in the present invention, by introducing a sulfonic acid metal base into the molecule, for example, the pigment dispersibility when coloring a molded product can be dramatically improved. In that case, it is preferable to carry out copolymerization in a concentration range where the concentration of sulfur atoms derived from the metal sulfonate group is 2500 ppm or less. More preferably, it is 2000 ppm or less, More preferably, it is 1500 ppm or less. Although a minimum is not specifically limited, If the sulfonic acid metal base is not copolymerized, dispersibility, such as an inorganic pigment and an organic pigment, may fall. If the concentration of sulfur atoms exceeds 2500 ppm, the resin melt viscosity becomes too high, the compatibility with polyester resins, particularly aliphatic polyester resins, polycaprolactone resins, and polylactic acid resins is poor, and pigment dispersibility May get worse.

  As a method of introducing a sulfonic acid metal salt into the polylactic acid resin for pigment masterbatch used in the present invention, a method of copolymerizing a compound having a sulfonic acid metal base copolymerizable with polylactic acid, the obtained polylactic acid type Examples include a method of sulfonating a resin by a known method. Although it does not specifically limit, the method of copolymerizing the compound with the sulfonic acid metal base copolymerizable with polylactic acid is preferable.

  As a preferable compound having a sulfonic acid metal base copolymerizable with the polylactic acid resin for a pigment masterbatch, there may be mentioned compounds represented by the following formula (I) or (II).

（但し、Ｒ¹、Ｒ²は炭素数２０以下のアルキル基であり同一でも異なっていても良い、ＭはＬｉ、ＮａまたはＫを表す。）

(However, R ¹ and R ² are alkyl groups having 20 or less carbon atoms and may be the same or different. M represents Li, Na or K.)

HO—R ³ —SO ₃ M Formula (II)
(However, R ³ represents an alkyl group having 20 or less carbon atoms, and M represents Li, Na, or K.)

  In addition, 0.01 mol of at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol and these three types of ethylene oxide adducts, polycaprolactone and dimer diol is added to the polylactic acid resin (I). Those included above are also preferred for enhancing the compatibility with the polyester resin and enhancing the mechanical properties of the molded product. The upper limit is not particularly limited, but is preferably less than 50 mol% in order to maintain the glass transition temperature necessary for molding.

The polylactic acid resin (I) used in the present invention preferably has an acid value of 5 to 80 equivalents / 10 ⁶ g. Within this range, it becomes easy to control the reaction with the reactive compound (II) described later, and the effect of improving moldability can be maximized.

  The reduced viscosity (ηsp / c) of the polylactic acid resin (I) is preferably 0.1 to 1.5 dl / g. If the reduced viscosity is less than 0.1 dl / g, the pigment dispersibility may be lowered, and even if it exceeds 1.5 dl / g, the pigment dispersibility may be lowered. The preferable range of the reduced viscosity is 0.15 to 1.0 dl / g, more preferably 0.2 to 0.8 dl / g. The reduced viscosity of the polylactic acid resin (I) is a value measured using a Ubbelohde viscosity tube at a sample concentration of 0.125 g / 25 ml, a measurement solvent chloroform and a measurement temperature of 25 ° C.

  The crystalline polyester as referred to in the present invention is a temperature increase from −100 ° C. to 300 ° C. at 20 ° C./min using a differential scanning calorimeter (DSC), and then the temperature is decreased to −100 ° C. at 50 ° C./min. Then, in the two temperature raising processes in which the temperature is raised from −100 ° C. to 300 ° C. at a rate of 20 ° C./min, one showing a clear melting peak in either temperature raising process. Conversely, amorphous polyester refers to a polyester that does not show a melting peak in either.

  Any amorphous polyester resin (III) may be used as long as it comprises a dicarboxylic acid component and a glycol component.

  As an amorphous polyester resin (III) used for this invention, it is desirable to have as a main component a C8-C14 aromatic dicarboxylic acid and a C2-C10 aliphatic or alicyclic glycol. As used herein, the main component refers to 50 mol% or more, preferably 60 mol%, and more preferably 65 mol% or more of each component when the total acid component and glycol component are each 100 mol%. When both components are less than 50 mol%, the elongation and mechanical properties of the molded product may be lowered.

  Furthermore, it is desirable that the aromatic dicarboxylic acid having 8 to 14 carbon atoms in the amorphous polyester resin (III) is terephthalic acid and / or isophthalic acid. When these dicarboxylic acids are used, the elongation and mechanical properties of the molded product are further improved. Preferably, the terephthalic acid is preferably contained in an amount of 50 mol% or more, more preferably 60 mol% or more, and more preferably contains both terephthalic acid and isophthalic acid.

  The amorphous polyester resin (III) may be copolymerized with other polycarboxylic acids other than the above-mentioned terephthalic acid and isophthalic acid. For example, orthophthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, Known materials such as sebacic acid, decanoic acid, dimer acid, cyclohexanedicarboxylic acid and trimellitic acid can be used.

  The amorphous polyester resin (III) used in the present invention is preferably composed mainly of an aliphatic or alicyclic glycol having 2 to 10 carbon atoms. The aliphatic or alicyclic glycol having 2 to 10 carbon atoms is ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3- In view of the versatility and cost of obtaining raw materials and the mechanical properties of the molded product, at least one selected from the group consisting of propanediol is preferable.

  Among these, ethylene glycol and neopentyl glycol (60/40 to 90/10 (molar ratio)), ethylene glycol and 1,4-cyclohexanedimethanol (60/40 to 90/10 (molar ratio)), ethylene glycol and A combination of 1,2-propanediol (90/10 to 10/90 (molar ratio)) is easy to realize melt molding processability.

  Amorphous resin polyester resin (III) is a polyhydric alcohol other than the above-mentioned ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,3-propanediol, and 2-methyl-1,3-propanediol. The components may be copolymerized, such as 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Hexanediol, nonanediol, dimer diol, ethylene oxide adduct or propylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 2-butyl-2-ethyl-1,3-propanediol, tricyclo Decanji Pentanol, neopentyl hydroxypivalic acid ester, 2,2,4-trimethyl-1,5-pentanediol, trimethylolpropane and the like can be used.

  The amorphous polyester resin (III) used in the present invention includes a polyfunctional compound having three or more carboxyl groups and / or hydroxyl groups as monomer components (for example, trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane, etc.) ) Is preferably included in an amount of 0.001 to 5 mol% of each of the acid component and / or glycol component of the polyester to improve moldability.

  The reduced viscosity of the amorphous polyester resin (III) used in the present invention is preferably 0.40 to 1.50 dl / g, more preferably 0.50 to 1.20 dl / g, and still more preferably 0.60. 1.00 dl / g. When the reduced viscosity is less than 0.40 dl / g, the strength of the molded product is insufficient due to insufficient resin cohesive strength, and the resulting product may become brittle and cannot be used. On the other hand, if it exceeds 1.50 dl / g, the melt viscosity becomes too high, so that the optimum temperature for molding also rises, and as a result, the molding processability may be deteriorated.

The acid value of the amorphous polyester resin (III) used in the present invention is preferably 100 equivalents / 10 ⁶ g or less, more preferably 50 equivalents / 10 ⁶ g or less, and even more preferably 40 equivalents / 10 ⁶ g or less. is there. On the other hand, the lower the lower limit, the better. When the acid value exceeds 100 equivalents / 10 ⁶ g, hydrolysis of the resin is further accelerated when the resin is heated during melt processing, and the mechanical strength of the finished molded product is lowered.

  Any crystalline polyester resin (IV) used in the present invention can be used as long as it comprises a dicarboxylic acid component and a glycol component.

  As the crystalline polyester resin (IV) used in the present invention, it is desirable that an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms are the main components. As used herein, the main component refers to 50 mol% or more, preferably 60 mol%, and more preferably 65 mol% or more of each component when the total acid component and glycol component are each 100 mol%. When both components are less than 50 mol%, the elongation and mechanical properties of the molded product may be lowered.

  Further, the aromatic dicarboxylic acid having 8 to 14 carbon atoms in the crystalline polyester resin (IV) is preferably terephthalic acid and / or isophthalic acid. When these dicarboxylic acids are used, the elongation and mechanical properties of the molded product are further improved. Preferably, the terephthalic acid is preferably contained in an amount of 50 mol% or more, more preferably 60 mol% or more, and more preferably contains both terephthalic acid and isophthalic acid.

  The crystalline polyester resin (IV) may be copolymerized with other polycarboxylic acids other than the above-mentioned terephthalic acid and isophthalic acid. For example, orthophthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacin Known acids such as acid, decanoic acid, dimer acid, cyclohexanedicarboxylic acid, trimellitic acid can be used.

  The crystalline polyester resin (IV) used in the present invention preferably contains an aliphatic or alicyclic glycol having 2 to 10 carbon atoms as a main component. The aliphatic or alicyclic glycol having 2 to 10 carbon atoms is ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3- In view of versatility of obtaining raw materials, cost, and mechanical properties of a molded product, at least one selected from the group consisting of propanediol, 1,4-butanediol and triethylene glycol is preferable.

  The crystalline resin polyester resin (IV) includes the above-mentioned ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexane dimethanol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol and Other polyhydric alcohol components other than triethylene glycol may be copolymerized, such as 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5- Pentanediol, hexanediol, nonanediol, dimerdiol, ethylene oxide addition product or propylene oxide addition product of bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 2-butyl-2-ethyl-1,3-propane Ol, tricyclodecane dimethanol, neopentyl hydroxypivalic acid ester, 2,2,4-trimethyl-1,5-pentanediol, trimethylolpropane and the like can be used.

  The crystalline polyester resin (IV) used in the present invention has a polyfunctional compound having three or more carboxyl groups and / or hydroxyl groups as monomer components (for example, trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane, etc.) Is preferably contained in an amount of 0.001 to 5 mol% of each of the acid component and / or glycol component of the polyester in order to improve moldability.

  The reduced viscosity of the crystalline polyester resin (IV) used in the present invention is preferably 0.40 to 1.50 dl / g, more preferably 0.50 to 1.20 dl / g, and further preferably 0.60 to 1. 0.000 dl / g. When the reduced viscosity is less than 0.40 dl / g, the strength of the molded product is insufficient due to insufficient resin cohesive strength, and the resulting product may become brittle and cannot be used. On the other hand, if it exceeds 1.50 dl / g, the melt viscosity becomes too high, so that the optimum temperature for molding also rises, and as a result, the molding processability may be deteriorated.

The acid value of the crystalline polyester resin (IV) used in the present invention is preferably 100 equivalents / 10 ⁶ g or less, more preferably 50 equivalents / 10 ⁶ g or less, and even more preferably 40 equivalents / 10 ⁶ g or less. . On the other hand, the lower the lower limit, the better. When the acid value exceeds 100 equivalents / 10 ⁶ g, hydrolysis of the resin is further accelerated when the resin is heated during melt processing, and the mechanical strength of the finished molded product is lowered.

  Any crystalline polyester resin (IV) as used in the present invention can be used as long as it comprises a dicarboxylic acid component and a glycol component. Moreover, you may use oxycarboxylic acid. In particular, at least one or more of the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyester elastomer, aliphatic polyester, polycaprolactone and polylactic acid is preferred, and the most effective crystalline polyester is polylactic acid resin. It is. The polyester elastomer is a general term for a block type resin having a polyether or an aliphatic polyester segment in a soft segment and an aromatic polyester in a hard segment. Aliphatic polyester is a general term for resins that use an aliphatic dicarboxylic acid such as adipic acid or sebacic acid as an acid component.

  About the polylactic acid resin, the same thing as what was demonstrated by the said polylactic acid resin (I) can be used. The composition of the polylactic acid resin used as the crystalline polyester resin (IV) and that of the polylactic acid resin (I) may be the same or different. However, in order to satisfy the mechanical strength of the molded product, the L-lactic acid residue And a D-lactic acid residue molar ratio (L / D) in the range of 0/100 to 10/90 and 100/0 to 90/10 are preferred.

  The reactive compound (II) used in the modifying agent of the present invention reacts with the polyester resin to increase the molecular weight, thereby expressing the “melting strength enhancement effect”, and also expands the processing condition control range to increase the melt strength. The weight average molecular weight is 200 to 500,000 in order to control the adjustment so that it can be adjusted, and further to satisfy the bending whitening resistance of the product and the suppression of bleed out of the unreacted product to the product surface layer. Is desirable. A preferred lower limit is 500 or more, more preferably 700 or more, and most preferably 1000 or more. On the other hand, the preferable upper limit is 300,000 or less, more preferably 100,000 or less, and most preferably 50,000 or less. If the weight average molecular weight of the reactive compound is less than 200, the unreacted reactive compound may bleed out on the surface of the product, which may reduce printability and adhesiveness to the product, or cause surface contamination. There is. On the other hand, if it exceeds 500,000, voids are generated due to poor compatibility between the reactive compound and the polyester at the time of bending, and the possibility of whitening by bending increases.

  The reactive compound (II) used in the present invention preferably has two or more functional groups that can react with the hydroxyl group or carboxyl group of the polyester per molecule. When a reaction product of the hydroxyl group or carboxyl group of the polyester and the reactive compound is produced during melt extrusion, a part of the reaction product becomes a crosslinked product, thereby obtaining an effect of improving the melt strength.

  Specific examples of the functional group possessed by the reactive compound (II) include a glycidyl group or an isocyanate group depending on the speed of the reaction. In addition to these, functional groups such as carboxyl groups, carboxylic acid metal salts, ester groups, hydroxyl groups, amino groups, carbodiimide groups, glycidyl groups, etc., and lactones, lactides, lactams, and other polyester ends and ring opening addition functional groups. It may be included.

  Any form of the functional group (II) in the reactive compound is possible. For example, those having a functional group in the main chain of the polymer, those existing in the side chain, and those existing in the terminal are all possible. Specific examples include styrene / methyl methacrylate / glycidyl methacrylate copolymer, bisphenol A type, cresol novolac, phenol novolac type epoxy compound, isocyanate compound, etc., and any of these may be used. Of course, it can be used.

  In particular, the reactive compound (II) includes (X) 20 to 99% by weight of vinyl aromatic monomer, (Y) 1 to 80% by weight of hydroxyalkyl (meth) acrylate and / or glycidylalkyl (meth). A copolymer comprising acrylate and (Z) 0 to 40% by weight of alkyl (meth) acrylate is preferred. More preferably, the resin comprises (X) of 25 to 90% by weight, (Y) of 10 to 75% by weight, and (Z) of 0 to 35% by weight, most preferably (X) of 30 to 85% by weight. %, (Y) is 15 to 70% by weight, and (Z) is 0 to 30% by weight. Since these compositions affect the content of functional groups that contribute to the reaction with the polylactic acid resin (I), the polyester resins (III), and (IV), it is necessary to adjust them appropriately as described above. When it deviates from the above-mentioned composition, there is a possibility that the reactivity with the polyester resin is lowered and the molding processability is lowered. The lower limit of (Z) is preferably 5% by weight or more.

In the present invention, the reactive compound (II) preferably has a glycidyl group. In that case, it is preferable that the epoxy value is 800 equivalents / 10 ⁶ g~3000 equivalents / 10 ⁶ g, more preferably, a 1000 equivalent / 10 ⁶ g~2800 equivalents / 10 ⁶ g, and most preferably, 1200 is equivalent / 10 ⁶ g~2500 equivalents / 10 ⁶ g. If the epoxy value is less than 800 equivalents / 10 ⁶ g, the target impact resistance or the like may not be exhibited, and if it is 3000 equivalents / 10 ⁶ g, the thickening effect is excessive and the moldability is adversely affected. There is.

  The addition amount of the reactive compound (II) can be individually selected depending on the molecular weight and the number of introduced functional groups, but preferably 0.5 wt% or more and 80 wt% or less when the entire modifier is 100 wt%. Is more preferably 1% by weight or more, and the upper limit is more preferably 70% by weight or less. If it is less than 0.5% by weight, the target melt moldability effect may not be exhibited, and if it exceeds 80% by weight, the mechanical properties of the product may be affected. Further, when the total composition of the polylactic acid resin (I), the reactive compound (II), the amorphous polyester (III) and / or the crystalline polyester (IV) is 100 parts by weight, the reactive compound (II ) Is preferably 0.1 wt% or more and 20 wt% or less, the lower limit is more preferably 0.5 wt% or more, and the upper limit is more preferably 15 wt% or less. If it is less than 0.1% by weight, the target impact resistance or the like may not be exhibited, and if it exceeds 20% by weight, the mechanical properties of the product may be affected.

  Regarding the method of adding the reactive compound (II) to the polylactic acid resin (I) when producing the modifier of the present invention, the method of press-fitting into the polylactic acid resin (I) during melt extrusion, before processing There are a method of adding and blending to a pellet of polylactic acid resin (I) and melt-kneading, a method of once adding and kneading to polylactic acid resin (I), and extruding again. A method of adding to the lactic acid resin (I) pellets, blending, and melt-kneading is preferable. The modifier is preferably pelletized for convenience when it is melt kneaded with the amorphous polyester resin (III) and the crystalline polyester resin (IV) in a later step.

  In the present invention, a molded article having excellent mechanical properties can be produced by melt-kneading the above-described modifier and amorphous polyester resin (III) and / or crystalline polyester resin (IV). Molding methods include injection molding, extrusion molding, profile extrusion molding, injection blow molding, direct blow molding, blow compression molding, stretch blow molding, calender molding, thermoforming (including vacuum and pressure molding), reaction injection molding, and foaming. Examples thereof include molding, compression molding, powder molding (including rotation / stretch molding), laminate molding, casting, and melt spinning. Among these, a molded product is manufactured by injection molding, extrusion molding, profile extrusion molding, direct blow molding, calendering molding from the viewpoint of maximizing the effects of the present invention of improving moldability and mechanical properties. It is preferable.

  The modifier of the present invention achieves improved moldability and mechanical properties by blending with amorphous polyester resin (III) and / or crystalline polyester resin (IV) and molding by melt kneading. can do. If polylactic acid resin (I), reactive compound (II), and amorphous polyester resin (III) and / or crystalline polyester resin (IV) are dry blended (mixed with pellets, the same applies hereinafter), When put into a hopper of an extruder or other molding machine and melt-kneaded and molded as it is, the tendency of the melt to thicken is remarkable and difficult to control. In the worst case, it is gelled at the time of melting (for example, in an extruder) It can happen. In addition, when the tendency of thickening of the melt is remarkable, it is difficult to change to the optimum conditions at the molding site, which makes the molding rather difficult. On the other hand, when the modifier as in the present invention is produced in advance, this is blended with the amorphous polyester resin (III) and / or the crystalline polyester resin (IV) at the molding site, and the molding state is confirmed. However, the optimum molding conditions can be selected simply by adjusting the blending ratio.

  The temperature conditions for melt-molding the amorphous polyester resin (III) and / or the crystalline polyester resin (IV) and the modifier of the present invention include the modifier and the amorphous polyester resin (III) and / or Alternatively, any temperature is acceptable as long as the crystalline polyester resin (IV) can be melt-flowed. However, it is considered that the temperature is 100 ° C. or higher and 350 ° C. or lower, more preferably 150 ° C. or higher and 300 ° C. or lower due to the properties of the polyester resin. It is. If the temperature is too low, the polymer cannot be fed out or an excessive load is applied to the extruder. Conversely, if the temperature is too high, the polymer will be thermally deteriorated, which is not preferable. The discharge amount in molding and other conditions are appropriately adjusted according to the molding machine.

  The resin composition of the modifier of the present invention and amorphous polyester (III) and / or crystalline polyester resin (IV) suppresses thermal degradation of the polyester resin during molding (resin coloring due to thermal degradation). In order to prevent the occurrence of sag or resin sag, it is desirable to use an antioxidant. As the antioxidant, for example, a phenol-based antioxidant, an organic phosphite-based compound and the like are suitable.

  In the present invention, in order to improve the heat resistance, impact resistance, dimensional stability, surface smoothness, rigidity, and other mechanical properties of the modifier and the resin composition, polylactic acid resin (I), polyester resin ( Resins other than III) and (IV) can be added.

  When calender molding is performed using the modifier of the present invention and amorphous polyester resin (III) and / or crystalline polyester resin (IV), a lubricant should be blended to improve roll releasability. Can do. In this case, the blending amount of the lubricant is preferably 0.01 to 5 parts by weight. A more preferred lower limit is 0.05 parts by weight, a more preferred lower limit is 0.1 parts by weight, and a most preferred lower limit is 0.5 parts by weight. Further, the more preferable upper limit is 4.5 parts by weight, the more preferable upper limit is 4 parts by weight, and the most preferable upper limit is 3.5 parts by weight. If the amount of the lubricant is less than 0.01 parts by weight, it is difficult to obtain the effect of improving the roll releasability, and if it exceeds 5 parts by weight, the coloring and printing properties of the sheet obtained by processing tend to be lowered.

  The lubricant is not particularly limited. For example, polyolefin wax, organophosphate metal salt, organophosphate ester, ester compound of adipic acid or azelaic acid and higher aliphatic alcohol, ethylene bis stearic acid amide, methylene bis Aliphatic amides such as stearic acid amide, ethylenebisoleic acid amide, glycerin higher fatty acid ester compounds, higher aliphatic alcohols, higher fatty acids, paraffins derived from petroleum or coal, waxes, natural or synthetic polymeric ester waxes, Examples include metal soaps with higher fatty acids. These may be used alone or in combination of two or more.

  In the present invention, other components can be appropriately added to the resin composition comprising the modifier and the amorphous polyester resin (III) and / or the crystalline polyester resin (IV) depending on the application. For example, impact resistance improvers, fillers, UV absorbers, surface treatment agents, lubricants, light stabilizers, pigments, antistatic agents, antibacterial agents, crosslinking agents, sulfur-based antioxidants, flame retardants, plasticizers, processing An auxiliary agent, a foaming agent, etc. are mentioned.

  In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to the examples. The measurement value described in the synthesis example is measured by the following method.

  Weight average molecular weight: Calculated from the results of GPC measurement at a column temperature of 35 ° C. and a flow rate of 1 ml / min using Waters Gel Permeation Chromatography (GPC) 150c with tetrahydrofuran as an eluent. Measurements were obtained. However, Showa Denko Co., Ltd. shodex KF-802, 804, 806 was used for the column.

Resin composition: The composition of the resin was determined from its integration ratio by performing ¹ H-NMR analysis using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian in a deuterated chloroform solvent.

  Glass transition temperature, melting point: 5 mg of sample was put in an aluminum sample pan and sealed, and a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Inc. was used. The maximum peak temperature of heat of fusion was determined as the crystalline melting point. The glass transition temperature was determined by the temperature at the intersection of the base line extension below the glass transition temperature and the tangent that indicates the maximum slope at the transition.

  Acid value: Obtained by dissolving 1 g of resin in 30 ml of chloroform and titrating with 0.1N potassium hydroxide ethanol solution. Phenolphthalein was used as the indicator.

  Reduced viscosity of polyester: 0.1 g of sample was dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane (weight ratio 6/4) and measured at 30 ° C. using an Ubbelohde viscosity tube. The unit was expressed in dl / g.

  Reduced viscosity of polylactic acid: 0.125 mg of a sample was dissolved in 25 cc of a measurement solvent chloroform and measured with a measurement temperature of 25 ° C. and an Ubbelohde viscosity tube.

Epoxy value: A sample was weighed in a 100 ml Erlenmeyer flask, 10 ml of methylene chloride was added, and the mixture was stirred and dissolved with a magnetic stirrer. 10 ml of tetraethylammonium bromide reagent was added followed by 6-8 drops of crystal violet indicator and titrated with 0.1 N perchloric acid. The end point was changed from blue to green and stable for 2 minutes. The amount (ml) of perchloric acid required for titration was read, and the epoxy value was calculated according to the following formula.
Epoxy value (equivalent / 10 ⁶ g) = (N × A × 1000) / W
W: Weight of sample (g)
A: Amount of perchloric acid required for titration (ml)
N: Normality of the perchloric acid reagent

<Synthesis example of polylactic acid resin (a)>
400 parts by weight of L-lactide, 0.04 part by weight of stannous octoate, and 0.12 part by weight of lauryl alcohol are sealed in a thick cylindrical stainless steel polymerization vessel equipped with a stirrer and degassed for 2 hours in a vacuum. I worried. After replacing with nitrogen gas, the mixture was heated and stirred at 200 ° C./10 mmHg for 2 hours. After completion of the reaction, the polylactic acid melt was extracted from the lower outlet, air-cooled, and cut with a pelletizer. The obtained polylactic acid resin (a) had a yield of 340 parts by weight, a yield of 85%, and a weight average molecular weight (Mw) of 138,000. The resin properties and composition are shown in Table 1.

<Synthesis example of polylactic acid resin (b)>
A reactor equipped with a Dien-Stark trap was charged with 100 parts by weight of 90% L-lactic acid and 0.45 parts by weight of tin powder, and after distilling water with stirring at 150 ° C./50 mmHg for 3 hours, The mixture was further oligomerized by stirring at 150 ° C./30 mmHg for 2 hours. To this oligomer, 210 parts by weight of diphenyl ether was added, and an azeotropic dehydration reaction at 150 ° C./35 mmHg was performed. The distilled water and the solvent were separated by a water separator, and only the solvent was returned to the reactor. After 2 hours, the organic solvent to be returned to the reactor was passed through a column packed with 46 parts by weight of molecular sieve 3A and then returned to the reactor. The reaction was carried out at 130 ° C./17 mmHg for 20 hours, and the weight average molecular weight (Mw) A 155,000 polylactic acid solution was obtained. The solution was diluted by adding 440 parts by weight of dehydrated diphenyl ether, cooled to 40 ° C., and the precipitated crystals were filtered. 120 parts by weight of 0.5N HCl and 120 parts by weight of ethanol were added to the crystals, stirred for 1 hour at 35 ° C., filtered, dried at 60 ° C./50 mmHg, and 61 parts by weight of polylactic acid powder (yield 85% ) This powder was melted and pelletized with an extruder to obtain polylactic acid pellets. The weight average molecular weight (Mw) of this polymer was 1470,000.

  The polylactic acid resins (c) to (f) were produced by using (or using) DL-lactide as a raw material in the same manner as the polylactic acid resin (a). Bisethylene glycol, caprolactone, and polyglycerin of 5-sodium sulfoisophthalic acid were copolymerized using respective amounts as initiators. The composition and measurement results are shown in Table 1. (Figures are mol% in resin)

<Synthesis Example of Crystalline Polyester (A); I-PET>
Add 145.8 parts by weight of terephthalic acid, 16.2 parts by weight of isophthalic acid, and 124 parts by weight of ethylene glycol in a reactor equipped with a stirrer, thermometer, and cooler for outflow, and dissolve crystalline germanium dioxide in water. Then, a catalyst solution obtained by adding ethylene glycol and heat treatment, and an ethylene glycol solution of phosphoric acid are added so that germanium and phosphorus metal atoms remain at 30 ppm, and the esterification reaction is performed at 260 ° C. for 2 hours. Went. While raising the temperature of the reaction system from 220 ° C. to 270 ° C., the pressure inside the system was slowly reduced to 500 Pa over 60 minutes. Further, a polycondensation reaction was performed at 130 Pa or lower for 55 minutes to obtain a crystalline polyester (A).

As a result of NMR analysis, the crystalline polyester resin (A) had a composition of 90 mol% of dicarboxylic acid component, 10 mol% of isophthalic acid, and 100 mol% of ethylene glycol. The glass transition temperature was 78 ° C., the number average molecular weight was 28000, the reduced viscosity was 0.81 dl / g, and the acid value was 30 equivalents / 10 ⁶ g.

<Synthesis Example of Crystalline Polyester (B): Elastomer>
394 parts by weight of dimethyl terephthalate, 252 parts by weight of 1,4-butanediol, 247 parts by weight of polytetramethylene glycol (number average molecular weight 1000), 1.4 parts by weight of Irganox 1330 (manufactured by Ciba Specialty Chemicals), tetrabutyl titanate 0.6 part by weight was charged, the temperature was raised from room temperature to 200 ° C. over 2 hours, and then heated at 200 ° C. for 1 hour to conduct a transesterification reaction. Next, the pressure in the tube was gradually reduced and the temperature was raised, and an initial polymerization reaction was performed at 245 ° C. and 130 Pa or less over 45 minutes. Further, a polymerization reaction was performed for 3 hours at 245 ° C. and 130 Pa or less, and the polymer was taken out in a pellet form to obtain a crystalline polyester (B).

As for the crystalline polyester resin (B), as a result of NMR analysis, the dicarboxylic acid component is 100 mol% of the terephthalic acid component, the diol component is 87 mol% of 1,4-butanediol, and polytetramethylene glycol (number average molecular weight 1000). It had a composition of 13 mol%. The glass transition temperature was −60 ° C., the number average molecular weight was 28000, the reduced viscosity was 1.4 dl / g, and the acid value was 40 equivalents / 10 ⁶ g.
<Synthesis Example of Amorphous Polyester (C)>
960 parts by weight of dimethyl terephthalate, 527 parts by weight of ethylene glycol, 156 parts by weight of neopentyl glycol, 0.34 parts by weight of tetrabutyl titanate were added to a reaction vessel equipped with a stirrer, a thermometer, and an outlet cooler. The transesterification was carried out at 2 ° C. for 2 hours. After completion of the transesterification reaction, the temperature of the reaction system was raised from 220 ° C. to 270 ° C., while the pressure in the system was slowly reduced to 500 Pa over 60 minutes. Further, a polycondensation reaction was performed at 130 Pa or less for 55 minutes to obtain amorphous polyester (C).

As a result of NMR analysis, the amorphous polyester resin (C) had a composition of a dicarboxylic acid component of 100 mol% terephthalic acid, a diol component of 70 mol% ethylene glycol, and 30 mol% neopentyl glycol. The glass transition temperature was 78 ° C., the number average molecular weight was 28000, the reduced viscosity was 0.81 dl / g, and the acid value was 30 equivalents / 10 ⁶ g.

<Synthesis example of crystalline polyester (D)>
In a reaction vessel equipped with a stirrer, a thermometer, and an outlet condenser, 56 parts by weight of terephthalic acid, 33 parts by weight of isophthalic acid, 67.2 parts by weight of adipic acid, 180 parts by weight of 1,4-butanediol, tetrabutyl titanate 0.34 weight part was added and transesterification was performed at 170-220 degreeC for 2 hours. After completion of the transesterification reaction, the temperature of the reaction system was raised from 220 ° C. to 270 ° C., while the pressure in the system was slowly reduced to 500 Pa over 60 minutes. Further, a polycondensation reaction was carried out at 130 Pa or lower for 55 minutes to obtain a crystalline polyester (D).

As a result of NMR analysis, the crystalline polyester resin (D) had a composition of 34 mol% terephthalic acid, 20 mol% isophthalic acid, 46 mol% adipic acid, and 100 mol% butanediol as the diol component. . The glass transition temperature was −20 ° C., the number average molecular weight was 29000, the reduced viscosity was 0.89 dl / g, and the acid value was 51 equivalents / 10 ⁶ g.

The crystalline polyester (J) was produced in the same manner as the crystalline polyester (A), and the amorphous polyester resins (E) to (I) were produced in the same manner as the amorphous polyester (C). The composition and measurement results are shown in Table 1. (Values are mol% in resin)
The polylactic acid resins (B) to (F) and the crystalline polyester (H) were produced in the same manner as the crystalline polyester (A). The composition and measurement results are shown in Table 2. (Figures are mol% in resin)

<Recycled PET flakes>
YPR flakes manufactured by Yono PET Bottle Recycle Co., Ltd. were used.

<Synthesis Example of Reactive Compound (K)>
A reactor equipped with a stirrer, a thermometer, a reflux device and two quantitative dropping devices was charged with 50 parts of methyl ethyl ketone, heated to 70 ° C., 36.4 parts by weight of styrene, 37.3 parts by weight of glycidyl methacrylate, methyl A solution of 26.3 parts by weight of methacrylate and 2 parts of azobisdimethylvaleronitrile dissolved in 50 parts of methyl ethyl ketone was simultaneously added dropwise to the reactor at 1.2 ml / min, and the mixture was further stirred for 2 hours after completion of the addition. Continued. Thereafter, by reducing the pressure, methyl ethyl ketone was removed from the reaction mixture to obtain a reactive compound (K).

As a result of NMR analysis, this reactive compound (K) was found to have a composition of monomer components of 36% by weight of styrene, 38% by weight of glycidyl methacrylate, and 26% by weight of methyl methacrylate. The glass transition temperature was 50 ° C. and the weight average molecular weight was 25,000. The epoxy value was 2627 equivalent / 10 ⁶ g.

<Synthesis Example of Reactive Compound (L)>
Prepared by emulsion polymerization in a reactor equipped with stirrer, cooler and heating device. The reactor was initially charged with a solution consisting of 900 parts by weight of deionized water, 0.2 parts by weight of acetic acid, 0.005 parts by weight of FeSO _{4 and} 0.06 parts by weight of sodium ethylenediaminetetraacetate dihydrate. The solution was heated to 75 ° C. under a nitrogen atmosphere. A solution obtained by emulsifying 182 parts by weight of styrene, 48.4 parts by weight of glycidyl methacrylate, and 25.8 parts by weight of butyl methacrylate monomer at 75 ° C. with 2.7 parts by weight of sodium dodecylbenzenesulfonate in 75 parts by weight of water. And then 0.22 parts by weight of sodium persulfate was added as an initiator. It was then allowed to proceed until more than 99.9% of the monomer was replaced by investigation of the solids content. After the reaction was complete, the emulsion was cooled to room temperature and then spray dried to give a white powder.

As a result of NMR analysis, this reactive compound (L) had a composition of 71% by weight of styrene, 19% by weight of glycidyl methacrylate, and 10% by weight of butyl methacrylate. The glass transition temperature was 55 ° C. and the weight average molecular weight was 10,000. The epoxy value was 1330 equivalent / 10 ⁶ g.

<Synthesis Example of Reactive Compound (M)>
The monomer component was synthesized by the same method as that for the reactive compound (K), and as a result of NMR analysis, the monomer component had a composition of 69% by weight of styrene, 5% by weight of glycidyl methacrylate, and 26% by weight of butyl methacrylate. The weight average molecular weight was 300,000.

<Example 1>
1. Polylactic acid resin (b) 90% by weight, reactive compound (K) 10% by weight, bis [S- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)] thioterephthalate as a stabilizer 0 parts by weight and 0.33 parts by weight of glycerin monostearate ester were mixed, and the mixture was an extruder (L / D = 30, screw diameter = 20 mm, full flight) set at a rotation speed of 30 rpm and a total barrel temperature of 230 ° C. The mixture was melt-kneaded at a compression ratio of 2.0), extruded into a string from a nozzle, cooled in water, cut with a cutter, and pelletized to obtain a polyester resin modifier.

[Evaluation by injection molding]
30 parts by weight of the modifier for polyester resin and 70 parts by weight of amorphous polyester (C) are dry blended, and the cylinder temperature is 250 ° C. with an injection molding machine (Toshiba IS-100E: mold clamping force 100 tons). Test pieces for physical property tests were molded under conditions of a mold temperature of 30 ° C. and a back pressure of 20 kg / cm ² . Using this, evaluation was performed by the following method. The results are shown in Table 3.

Reduced viscosity increase / decrease tendency:
◎: Reduced viscosity increased by 15% or more ○: Reduced viscosity not increased ×: Reduced reduced viscosity

Impact resistance test: Notched Izod impact strength (ASTM D-256) Test temperature 23 ° C
○: 40 J / m or more Δ: 25 J / m or more and less than 40 J / m ×: less than 25 J / m

[Evaluation by profile extrusion molding]
30 parts by weight of the above modifier for polyester resin and 70 parts by weight of amorphous polyester (C) are dry blended, the cylinder temperature is set to 250 ° C., and a single screw extruder (L / D = 25, full flight) 1) is attached to the screw and the diameter of the screw is 65 mm), and then a sizing die is attached to the tip of the cooling water tank to determine the final dimension of the shaped extruded product. Molded by a profile extrusion equipment equipped with a machine. Using this, evaluation was performed by the following method. The results are shown in Table 3.

Sizing mold processing status (continuous productivity):
○: Resin did not adhere in the sizing mold, the workability was smooth, and the edge shape accuracy of the molded product between the die and the sizing mold was high.
X: Resin adhesion occurred in the sizing mold, and it was not possible to proceed to the sizing process. Alternatively, the processability was poor in the sizing process, the edge accuracy of the molded product was low, and the continuous productivity was deteriorated.

Product dimensional accuracy:
○: As designed value △: Deviation occurred in the range of less than 0.3 mm from the design value ×: Deviation of 0.3 mm or more occurred from the design value

Surface smoothness: The outer surface unevenness state of the molded product was measured using an ultra-deep surface shape measuring microscope (VK-8500 manufactured by Keyence).
○: Maximum height of uneven surface is less than 100 μm Δ: Maximum height of uneven surface is 100 μm or more and less than 200 μm ×: Maximum height of uneven surface is 200 μm or more

Product warpage evaluation: With respect to the extrusion molding direction of the profile extruded product, the presence or absence of warpage in the vertical and horizontal directions was evaluated as follows.
Yes: There was warp No: No warp

[Evaluation by direct blow molding]
30 parts by weight of the above modifier for polyester resin and 70 parts by weight of amorphous polyester (C) are dry blended to produce a direct blow molding machine (single screw extruder: L / D = 25, full flight screw, screw diameter The cylinder temperature of 65 mm) was set to 245 to 260 ° C., and the bottle shown in FIG. 2 was manufactured. A parison forming die lip was attached to the tip of the cylinder, and blow air was sealed in the mold to continuously produce bottles. At this time, the parison holding state and product accuracy were evaluated according to the following criteria. The results are shown in Table 3.

Parison holding state:
○: The drawdown is very small and the shape is maintained. △: The drawdown is large and the shape collapses, but it can be blown somehow. ×: The drawdown is large and the shape collapses and cannot be blown.

Product accuracy:
○: Small burr and uniform thickness ×: Large burr and uneven thickness

[Evaluation by calendar molding]
30 parts by weight of the above modifier for polyester resin and 70 parts by weight of amorphous polyester (C) are dry blended, and 1 part by weight of a glycerin higher fatty acid ester compound is blended as a lubricant, Kneading on a 6 inch test roll. Remove the resin adhering to the test roll with an occasional spatula, mix and mix for 5 minutes, then set the roll spacing to 0.3 mm (sheet thickness set to 0.3 mm), take the molten sheet to a distance of 30 cm from the roll, The take-up property of the sheet was evaluated by visually observing the sagging at that time. Moreover, the sheet peelability from the roll at that time was also evaluated. The evaluation criteria are as follows.

Sheet peelability:
○: Good peelability from rolls △: Strong stickiness to rolls, and sometimes difficult to peel off, making stable mass production ×: Strong stickiness to rolls, difficult to peel off, collecting normal sheets Can not

Sheet take-up property ◎: No sagging occurs ○: Slight sagging occurs, but there is no problem in practical use △: Sheet production is possible by adjusting roll temperature conditions, etc., but stable mass production is not possible ×: Molten sheet is struck by its own weight The normal sheet cannot be collected

<Examples 2-9, Comparative Examples 1-12>
Molding was performed under the same conditions as in Example 1 using the raw materials described in Tables 3 and 4. In addition, about Comparative Examples 1-6, the stabilizer and the lubricant were added to the amorphous polyester resin, and various moldings were performed as they were for evaluation. Comparative Examples 7 to 9 were formed by dry blending (blending between pellets, the same applies hereinafter) of an impact modifier and amorphous polyester resin (III). In Comparative Example 10, the reactive compound (II) and the amorphous polyester resin were dry blended and molded. Comparative Example 11 was formed by dry blending homo-PET and amorphous polyester (III). In Comparative Example 12, amorphous polyester resin (III), reactive compound (II), and impact modifier were dry blended and molded.
The evaluation results are also shown in Tables 3 and 4.

The stabilizers and lubricants listed in the table mean the following compounds.
O: Bis [S- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)] thioterephthalate P: Glycerol monostearate

  For the blending ratio in the table, the total weight of {amorphous polyester resin (III) (or crystalline polyester resin (IV)) + polylactic acid resin (I) + reactive compound (II)} is described as 100. Stabilizers and additives are expressed as weights added thereto.

<Example 10>
90 parts by weight of the polylactic acid resin (d) and 10 parts by weight of the reactive compound (L) were mixed, and the mixture was an extruder (L / D = 30, screw diameter set at a rotation speed of 30 rpm and a total barrel temperature of 250 ° C. = 20 mm, full flight, compression ratio 2.0) The polyester resin modifier was obtained by melt-kneading, extruding into a string from a nozzle, and cutting into pellets by cutting with a cutter in water. Next, 20 parts by weight of the obtained modifier for polyester resin and 80 parts by weight of recycled polyethylene terephthalate (regenerated PET: YPR flakes) were dry blended, and the following various moldings were performed.
The composition of the obtained resin composition is 80 parts by weight of recycled PET, 18 parts by weight of the polylactic acid resin (d), and 2 parts by weight of the reactive compound (L).

[Evaluation by injection molding]
20 parts by weight of the resulting modifier for polyester resin and 80 parts by weight of recycled polyethylene terephthalate (recycled PET: YPR flakes) are dry blended and injected with an injection molding machine (Toshiba IS-100E: clamping force of 100 tons). Test pieces for physical property tests were molded under conditions of a cylinder temperature of 275 ° C., a mold temperature of 30 ° C., and a back pressure of 20 kg / cm ² . Using this, evaluation was performed by the following method. The results are shown in Table 5.

Reduced viscosity increase / decrease tendency:
◎: Reduced viscosity increased by 15% or more ○: Reduced viscosity not increased ×: Reduced reduced viscosity

Impact resistance test: Notched Izod impact strength (ASTM D-256) Test temperature 23 ° C
○: 50 J / m or more Δ: 30 J / m or more and less than 50 J / m ×: less than 30 J / m

[Evaluation by profile extrusion molding]
20 parts by weight of the resulting modifier for polyester resin and 80 parts by weight of recycled polyethylene terephthalate (regenerated PET: YPR flakes) were dry blended, the cylinder temperature was set at 270 ° C., and a single screw extruder (L / D = 25, full flight screw, screw diameter 65mm) is attached to the die lip that produces the molded product shown in Fig. 1, and then the sizing die that determines the final dimensions of the profile extrusion product is attached to the tip of the cooling water tank, and then passes through the water tank. And it shape | molded with the profile extrusion molding equipment equipped with the take-up machine. Using this, evaluation was performed by the following method. The results are shown in Table 5.

Sizing mold processing status (continuous productivity):
○: Resin did not adhere in the sizing mold, the workability was smooth, and the edge shape accuracy of the molded product between the die and the sizing mold was high.
X: Resin adhesion occurred in the sizing mold, and it was not possible to proceed to the sizing process. Alternatively, the processability was poor in the sizing process, the edge accuracy of the molded product was low, and the continuous productivity was deteriorated.

Product dimensional accuracy:
○: As designed value △: Deviation occurred in the range of less than 0.3 mm from the design value ×: Deviation of 0.3 mm or more occurred from the design value

Surface smoothness: The outer surface unevenness state of the molded product was measured using an ultra-deep surface shape measuring microscope (VK-8500 manufactured by Keyence), and the following evaluation was performed.
○: Maximum height of uneven surface is less than 100 μm Δ: Maximum height of uneven surface is 100 μm or more and less than 200 μm ×: Maximum height of uneven surface is 200 μm or more

Product warpage evaluation: With respect to the extrusion molding direction of the profile extruded product, the presence or absence of warpage in the vertical and horizontal directions was evaluated as follows.
Yes: There was warp No: No warp

[Evaluation by T-die extrusion sheet molding]
20 parts by weight of the obtained modifier for polyester resin and 80 parts by weight of recycled polyethylene terephthalate (recycled PET: YPR flakes) were dry blended, and a T-die extruder (single screw extruder: L / D = 25, The cylinder temperature of a full flight screw (screw diameter 65 mm) was set to 270 ° C., and a sheet having a width of 30 cm and a thickness of 400 μm was produced. The take-up property of the sheet was evaluated by visually observing the sagging of the resin up to the take-up roll at that time. Moreover, the sheet peelability from the roll at that time was also evaluated. The evaluation criteria are as follows.

Sheet peelability:
○: Good peelability from rolls △: Strong stickiness to rolls, and sometimes difficult to peel off, making stable mass production ×: Strong stickiness to rolls, difficult to peel off, collecting normal sheets Can not

Sheet take-up property ◎: No sagging occurs ○: Slight sagging occurs, but there is no problem in practical use △: Sheet production is possible by adjusting roll temperature conditions, etc., but stable mass production is not possible ×: Molten sheet is struck by its own weight The normal sheet cannot be collected

[Evaluation by direct blow molding]
20 parts by weight of the resulting modifier for polyester resin and 80 parts by weight of recycled polyethylene terephthalate (recycled PET: YPR flakes) were dry blended and a direct blow molding machine (single screw extruder: L / D = 25, full The cylinder temperature of the flight screw (screw diameter 65 mm) was set to 250 to 270 ° C., and the bottle shown in FIG. 2 was manufactured. A parison forming die lip was attached to the tip of the cylinder, and blow air was sealed in the mold to continuously produce bottles. At this time, the parison holding state and product accuracy were evaluated according to the following criteria.

Parison holding state:
○: The drawdown is very small and the shape is maintained. △: The drawdown is large and the shape collapses, but it can be blown somehow.

Product accuracy:
○: Small burr and uniform thickness ×: Large burr and uneven thickness

[Evaluation by calendar molding]
20 parts by weight of the resulting modifier for polyester resin and 80 parts by weight of recycled polyethylene terephthalate (recycled PET: YPR flakes) are dry blended, and 1 part by weight of a glycerin higher fatty acid ester compound is blended as a lubricant. It knead | mixed on two 6 inch test rolls set to the range of (degreeC). Remove the resin adhering to the test roll with an occasional spatula, mix and mix for 5 minutes, then set the roll spacing to 0.3 mm (sheet thickness set to 0.3 mm), take the molten sheet to a distance of 30 cm from the roll, The take-up property of the sheet was evaluated by visually observing the sagging at that time. Moreover, the sheet peelability from the roll at that time was also evaluated. The evaluation criteria are as follows.

Sheet peelability:
○: Good peelability from rolls △: Strong stickiness to rolls, and sometimes difficult to peel off, making stable mass production ×: Strong stickiness to rolls, difficult to peel off, collecting normal sheets Can not

Sheet take-up property ◎: No sagging occurs ○: Slight sagging occurs, but there is no problem in practical use △: Sheet production is possible by adjusting roll temperature conditions, etc., but stable mass production is not possible ×: Molten sheet is struck by its own weight The normal sheet cannot be collected

<Examples 11-18, Comparative Examples 13-17>
Using the raw materials described in Tables 5 and 6, molding was performed under the conditions described in the respective tables. Specifically, as in Example 10, the crystalline polyester resin (I), the reactive compound (II), and the stabilizers L and M were previously melt-kneaded at 200 to 250 ° C., and the resulting polyester resin was obtained. Dry blend of modifier and crystalline polyester resin (IV), and evaluated at various temperatures by injection molding, profile extrusion molding, T-die extrusion sheet molding, direct blow molding, calendar molding at a temperature 20 ° C higher than the melting point. went.

As can be seen from Tables 3 to 6, Examples 1 to 18 achieved improvements in injection moldability and mechanical properties as compared with Comparative Examples 1 to 17, and the profile extrusion processability was continuously produced. Improvement of dimensional accuracy and surface smoothness (removal of chatter), improved product warpage during continuous production, and improvement of resin sag during profile extrusion, product corners between die and sizing, It is excellent in improving the shape accuracy of the edge portion.
In direct blow molding, the holding of the parison is excellent, and the product accuracy is also improved, so that the stability during continuous production and the yield rate of non-defective products are greatly improved.
In calendering molding, the melt strength of the polyester resin composition is greatly improved, so that the sheet peelability from the roll and the sheet take-up property are improved, and a sheet with excellent dimensional accuracy and surface properties is stably produced. be able to.

  By blending the modifier of the present invention with a polyester resin, the moldability in melt molding, in particular injection molding, extrusion molding, profile extrusion molding, direct blow molding, and calendering molding can be improved. Excellent mechanical properties.

It is sectional drawing of a profile extrusion molded product. It is a dimension drawing of a direct blow bottle.

Claims (47)

  Polyester resin containing polylactic acid resin (I) and reactive compound (II) containing at least two glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000 Modifier.   The polyester resin modifier according to claim 1, wherein the polylactic acid resin (I) has a molar ratio (L / D) of L-lactic acid residue to D-lactic acid residue of 90/10 to 10/90. The modifier for a polyester resin according to claim 1 or 2, wherein the polylactic acid resin (I) has an acid value of 5 to 80 equivalents / 10 ⁶ g.   The modifier for polyester resins according to claim 1, wherein the polylactic acid resin (I) contains a polyglycerin segment.   The modifier for polyester resins according to claim 4, wherein the degree of polymerization of polyglycerin is in the range of 3-20.   The modifier for polyester resins according to claim 1, wherein the polylactic acid resin (I) has a sulfonic acid metal base.   The polyester resin modifier according to claim 6, wherein the concentration of sulfur atoms derived from the sulfonic acid metal base is 2500 ppm or less.   The polylactic acid resin (I) contains 0.01 mol or more of at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol and these three kinds of ethylene oxide adducts, polycaprolactone and dimer diol. The modifier for polyester resins according to any one of claims 1 to 7.   Reactive compound (II) is (X) 20-99 wt% vinyl aromatic monomer, (Y) 1-80 wt% hydroxyalkyl (meth) acrylate or glycidylalkyl (meth) acrylate, and (Z) The modifier for a polyester resin according to any one of claims 1 to 8, which is a copolymer comprising 0 to 79% by weight of an alkyl (meth) acrylate.   A polylactic acid resin (I), a reactive compound (II) containing two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000, and an amorphous polyester resin (III) A polyester resin composition containing   The polyester resin composition according to claim 10, wherein the polylactic acid resin (I) has a molar ratio (L / D) of L-lactic acid residue to D-lactic acid residue of 90/10 to 10/90. 12. The polyester resin composition according to claim 10, wherein the acid value of the polylactic acid resin (I) is 5 to 80 equivalents / 10 ⁶ g.   The polyester resin composition according to any one of claims 10 to 12, wherein the polylactic acid resin (I) contains a polyglycerin segment.   The polyester resin composition according to claim 13, wherein the degree of polymerization of polyglycerol is in the range of 3-20.   The polyester resin composition according to any one of claims 10 to 14, wherein the polylactic acid resin (I) has a sulfonic acid metal base.   The polyester resin composition according to claim 15, wherein the concentration of sulfur atoms derived from the sulfonic acid metal base is 2500 ppm or less.   The polylactic acid resin (I) contains 0.01 mol or more of at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol and these three kinds of ethylene oxide adducts, polycaprolactone and dimer diol. The polyester resin composition according to any one of claims 10 to 16, wherein:   Reactive compound (II) is (X) 20-99 wt% vinyl aromatic monomer, (Y) 1-80 wt% hydroxyalkyl (meth) acrylate or glycidylalkyl (meth) acrylate, and (Z) The polyester resin composition according to any one of claims 10 to 17, which is a copolymer comprising 0 to 79% by weight of an alkyl (meth) acrylate.   The amorphous polyester resin (III) contains an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms in an amount of 50 mol% or more of each of the acid component and the glycol component. The polyester resin composition according to any one of claims 10 to 18.   The polyester resin composition according to claim 19, wherein the aromatic dicarboxylic acid having 8 to 14 carbon atoms is terephthalic acid and / or isophthalic acid.   Aliphatic or alicyclic glycols having 2 to 10 carbon atoms are ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl- The polyester resin composition according to claim 19 or 20, wherein the polyester resin composition is at least one selected from the group consisting of 1,3-propanediol 1,4-butanediol and triethylene glycol.   Amorphous polyester resin (III) is 0.01 mol of at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol and these three types of ethylene oxide adducts, polycaprolactone and dimer diol. The modifier for polyester resins according to any one of claims 10 to 21, comprising the above.   The amorphous polyester resin (III) contains 0.001 to 5 mol% of a polyfunctional compound unit having three or more carboxyl groups and / or hydroxyl groups as monomer components in each of the acid component and / or glycol component. The polyester resin composition according to any one of claims 10 to 22.   A polylactic acid resin (I), a reactive compound (II) containing two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000, and a crystalline polyester resin (IV) Polyester resin composition included.   The polyester resin composition according to claim 24, wherein the polylactic acid resin (I) has a molar ratio (L / D) of L-lactic acid residue to D-lactic acid residue of 90/10 to 10/90. The polyester resin composition according to claim 24 or 25, wherein the acid value of the polylactic acid resin (I) is 5 to 80 equivalents / 10 ⁶ g.   The polyester resin composition according to any one of claims 24 to 26, wherein the polylactic acid resin (I) contains a polyglycerin segment.   28. The polyester resin composition according to claim 27, wherein the degree of polymerization of polyglycerol is in the range of 3-20.   The polyester resin composition according to any one of claims 24 to 28, wherein the polylactic acid resin (I) has a sulfonic acid metal base.   30. The polyester resin composition according to claim 29, wherein the concentration of sulfur atoms derived from the sulfonic acid metal base is 2500 ppm or less.   The polylactic acid resin (I) contains 0.01 mol or more of at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol and these three kinds of ethylene oxide adducts, polycaprolactone and dimer diol. The polyester resin composition according to any one of claims 24 to 30, wherein   Reactive compound (II) is (X) 20-99 wt% vinyl aromatic monomer, (Y) 1-80 wt% hydroxyalkyl (meth) acrylate or glycidylalkyl (meth) acrylate, and (Z) The polyester resin composition according to any one of claims 24 to 31, wherein the polyester resin composition is a copolymer comprising 0 to 79% by weight of an alkyl (meth) acrylate.   The crystalline polyester resin (IV) is at least one member selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyester elastomer, aliphatic polyester, polycaprolactone and polylactic acid. Item 33. The polyester resin composition according to any one of Items 24 to 32.   A modifier comprising a polylactic acid resin (I) and a reactive compound (II) containing two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000. A method for producing a molded product, which is mixed with polyester (III) and / or crystalline polyester resin (IV) and melt-molded.   The method for producing a molded article according to claim 34, wherein the polylactic acid resin (I) has a molar ratio (L / D) of L-lactic acid residue to D-lactic acid residue of 90/10 to 10/90. The acid value of polylactic acid resin (I) is 5-80 equivalent / 10 < ⁶ > g, The manufacturing method of the molded article of Claim 34 or 35 characterized by the above-mentioned.   The method for producing a molded article according to any one of claims 34 to 36, wherein the polylactic acid resin (I) contains a polyglycerin segment.   The method for producing a molded article according to claim 37, wherein the degree of polymerization of polyglycerol is in the range of 3-20.   The method for producing a molded article according to any one of claims 34 to 38, wherein the polylactic acid resin (I) has a sulfonic acid metal base.   The method for producing a molded article according to any one of claims 34 to 39, wherein the concentration of sulfur atoms derived from the metal sulfonate group is 2500 ppm or less.   The polylactic acid resin (I) contains 0.01 mol or more of at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol and these three ethylene oxide adducts, polycaprolactone and dimer diol. The method for producing a molded product according to any one of claims 34 to 40, wherein:   The amorphous polyester resin (III) contains an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms in an amount of 50 mol% or more of each of the acid component and the glycol component. The method for producing a molded product according to any one of claims 34 to 41.   The method for producing a molded article according to claim 42, wherein the aromatic dicarboxylic acid having 8 to 14 carbon atoms is terephthalic acid and / or isophthalic acid.   Aliphatic or alicyclic glycols having 2 to 10 carbon atoms are ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl- 44. The method for producing a molded product according to claim 42 or 43, wherein the method is at least one selected from the group consisting of 1,3-propanediol, 1,4-butanediol and triethylene glycol.   Amorphous polyester resin (III) is 0.01 mol of at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol and these three ethylene oxide adducts, polycaprolactone and dimer diol. The method for producing a molded product according to any one of claims 34 to 44, comprising the above.   Amorphous polyester resin (III) contains, as a monomer component, 0.001 to 5 mol% of a polyfunctional compound unit having 3 or more carboxyl groups and / or hydroxyl groups in each of the acid component and / or glycol component of the polyester. The method for producing a molded product according to any one of claims 34 to 45, wherein:   The crystalline polyester resin (IV) is at least one member selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyester elastomer, aliphatic polyester, polycaprolactone, and polylactic acid. Item 47. The method for producing a molded article according to any one of Items 34 to 46.

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