Polyester resin composition and polyester resin molded article

Abstract

Provided is a polyester resin composition capable of exhibiting excellent melt properties and excellent mechanical properties. Also provided is a polyester-based resin molded article obtained by molding such a polyester-based resin composition. A polyester resin composition according to an embodiment of the present invention is a polyester resin composition containing a polyester resin (A), a polyolefin resin (B), a glycidyl group-containing resin (C), and a polycarbodiimide (D), the glycidyl group-containing resin (C) containing 2-30 wt% of a glycidyl methacrylate unit in a molecule.

Description

Technical Field

[0001] The present invention relates to a polyester resin composition and a polyester resin molded product. Background Art

[0002] To improve the physical properties of polyester resins, they have traditionally been alloyed with polyolefin resins. However, this process can lead to a decrease in physical properties, such as reduced toughness, due to the polarity difference between the polyolefin resin and the polyester resin. Therefore, research is underway to improve polyolefin resins or add compatibilizers.

[0003] For example, there are reports of using modified polyolefin resins as polyolefin resins or using modified polyolefin resins as compatibilizers (Patent Documents 1 to 4). Furthermore, there are reports of using epoxy-containing acrylic-styrene copolymers and ethylene-methacrylic acid copolymer resins (NUCREL 1207) as compatibilizers (Patent Documents 5 and 6).

[0004] However, the polyester resins obtained using the above-mentioned techniques still have room for improvement in terms of melt properties and mechanical properties.

[0005] Furthermore, polycarbodiimide having a carbodiimide group reacts with a carboxylic acid or a hydroxyl group at the terminal of a polyester resin and can therefore be used as an anti-hydrolysis agent or a chain extender (Patent Documents 7 to 9).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 2005-343971

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2004-18592

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 2005-23095

[0011] Patent Document 4: Japanese Patent Application Laid-Open No. 2005-105055

[0012] Patent Document 5: Japanese Patent Application Laid-Open No. 2005-200534

[0013] Patent Document 6: Japanese Patent Application Laid-Open No. 2012-111818

[0014] Patent Document 7: Japanese Patent Application Laid-Open No. 1-174557

[0015] Patent Document 8: Japanese Patent Application Laid-Open No. 2003-313410

[0016] Patent Document 9: Japanese Patent Application Laid-Open No. 2016-56314 Summary of the Invention

[0017] Problems to be solved by the invention

[0018] The technical problem of the present invention is to provide a polyester resin composition that exhibits excellent melt properties and excellent mechanical properties, and also to provide a polyester resin molded article molded from such a polyester resin composition.

[0019] Solutions for solving problems

[0020] [1] The polyester resin composition according to an embodiment of the present invention is a polyester resin composition comprising a polyester resin (A), a polyolefin resin (B), a glycidyl group-containing resin (C) and a polycarbodiimide (D), wherein the glycidyl group-containing resin (C) contains 2% to 30% by weight of a glycidyl methacrylate unit in the molecule.

[0021] [2] In the polyester resin composition described in [1], the glycidyl group-containing resin (C) may have an MFR of 1 g / 10 min to 500 g / 10 min at a temperature of 190° C. and a load of 2.16 kg.

[0022] [3] In the polyester resin composition described in [1] or [2] above, the glycidyl group-containing resin (C) may contain an ethylene unit.

[0023] [4] In the polyester resin composition described in any one of [1] to [3] above, the total content of the polyester resin (A), the polyolefin resin (B), the glycidyl group-containing resin (C) and the polycarbodiimide (D) in the polyester resin composition may exceed 90% by weight.

[0024] [5] In the polyester resin composition described in any one of [1] to [4] above, the content ratio of the polyester resin (A) in the total of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) can be 50% by weight to 98% by weight.

[0025] [6] In the polyester resin composition described in any one of [1] to [5] above, the content ratio of the polyolefin resin (B) in the total of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) can be 1% by weight to 45% by weight.

[0026] [7] In the polyester resin composition described in any one of [1] to [6] above, the content ratio of the glycidyl group-containing resin (C) in the total of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) can be 0.1 wt% to 20 wt%.

[0027] [8] In the polyester resin composition described in any one of [1] to [7] above, when the total amount of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) is set to 100 parts by weight, the amount of the polycarbodiimide (D) can be 0.1 parts by weight to 3.0 parts by weight.

[0028] [9] In the polyester resin composition described in any one of [1] to [8] above, the MFR of the polyester resin (A) at a temperature of 285°C and a load of 2.16 kg may be 100 g / 10 min to 300 g / 10 min.

[0029]

[10] In the polyester resin composition described in any one of [1] to [9] above, the polyester resin (A) may be polyethylene terephthalate.

[0030]

[11] In the polyester resin composition described in any one of [1] to

[10] above, the polyolefin resin (B) may be an ethylene-α-olefin copolymer.

[0031]

[12] In the polyester resin composition described in

[11] above, the polyolefin resin (B) may be a linear low-density polyethylene.

[0032]

[13] In the polyester resin composition described in any one of [1] to

[12] above, the MFR of the polyolefin resin (B) at a temperature of 190°C and a load of 2.16 kg can be 0.5 g / 10 min to 50 g / 10 min.

[0033]

[14] In the polyester resin composition described in any one of [1] to

[13] above, the weight average molecular weight of the polycarbodiimide (D) may be 500 to 6000.

[0034]

[15] In the polyester resin composition described in any one of [1] to

[14] above, the polyester resin composition may contain 0.5 wt% to 30 wt% of an impact modifier (E).

[0035]

[16] In the polyester resin composition described in

[15] above, the impact modifier (E) has a core / shell structure having a core and a shell, and the core may contain a rubber component.

[0036]

[17] The polyester resin composition according to an embodiment of the present invention comprises a polyester resin (A), a polyolefin resin (B), a glycidyl group-containing resin (C) and an impact modifier (E), wherein the glycidyl group-containing resin (C) contains 2 wt% to 30 wt% of glycidyl methacrylate units in the molecule.

[0037]

[18] The polyester resin molded article according to an embodiment of the present invention is obtained by molding the polyester resin composition described in any one of [1] to

[17] above by injection molding.

[0038] Effects of the Invention

[0039] According to the present invention, a polyester resin composition exhibiting excellent melt properties and excellent mechanical properties can be provided. Furthermore, a polyester resin molded article formed from such a polyester resin composition can be provided. According to the present invention, a polyester resin composition exhibiting excellent melt properties and excellent mechanical properties can be provided. Therefore, for example, a polyester resin composition exhibiting excellent melt properties and excellent mechanical properties can be produced using recycled PET as a raw material. DETAILED DESCRIPTION

[0040] In this specification, whenever the expression "weight" appears, it can be replaced with "mass," which is a commonly used SI unit for expressing weight. Conversely, whenever the expression "mass" appears in this specification, it can be replaced with "weight," which is a commonly used unit for expressing weight.

[0041] In this specification, the expression “(meth)acrylic acid” means “acrylic acid and / or methacrylic acid”, the expression “(meth)acrylate” means “acrylate and / or methacrylate”, the expression “(meth)allyl” means “allyl and / or methallyl”, and the expression “(meth)acrolein” means “acrolein and / or methacrolein”.

[0042] Polyester resin composition

[0043] According to one embodiment (I) of the present invention, a polyester resin composition comprises a polyester resin (A), a polyolefin resin (B), a glycidyl group-containing resin (C), and a polycarbodiimide (D). According to another embodiment (II) of the present invention, a polyester resin composition comprises a polyester resin (A), a polyolefin resin (B), a glycidyl group-containing resin (C), and an impact modifier (E). Hereinafter, the term "polyester resin composition according to an embodiment of the present invention" includes both the polyester resin composition according to embodiment (I) and the polyester resin composition according to embodiment (II).

[0044] The present invention is based on the following: a polyester resin composition that essentially contains a combination of a polyester resin (A), a polyolefin resin (B), a glycidyl group-containing resin (C), and a polycarbodiimide (D) (embodiment (I)), or a polyester resin composition that essentially contains a combination of a polyester resin (A), a polyolefin resin (B), a glycidyl group-containing resin (C), and an impact modifier (E) (embodiment (II)) can exhibit superior melt properties and excellent mechanical properties compared to conventional polyester resin compositions. In particular, the present invention is based on the following: by employing a specific glycidyl group-containing resin (C) to form the above combination, significantly superior melt properties and significantly superior mechanical properties can be exhibited. While some conventional polyester resin compositions have demonstrated improved melt properties and improved mechanical properties, these are far from sufficient. The polyester resin compositions according to the embodiments of the present invention can exhibit significantly superior melt properties and significantly superior mechanical properties, and in particular, can exhibit significantly superior toughness improvement.

[0045] The polyester resin composition according to the embodiment of the present invention can be produced by any appropriate method such as a method generally known as a method for producing a resin composition. A representative example of such a production method is production by melt kneading.

[0046] As a melt kneading method, for example, the components to be mixed are uniformly dry-mixed by a Henschel mixer, a ribbon blender, a V-type blender, a tumble mixer, etc., and then melt-kneaded by a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, a LABO PLASTOMILL (Brabender), etc. The components to be mixed may be added separately by adjusting the supply ratio, or may be added sequentially.

[0047] The temperature for melt kneading can be appropriately selected depending on the types of ingredients to be blended, the ratio of the ingredients to be blended, the type of apparatus used for melt kneading, etc. From the perspective of better exhibiting the effects of the present invention, the temperature for melt kneading is preferably set to a temperature equal to or higher than the melting point of the component with the highest melting point among the blended ingredients, more preferably (the melting point + 5°C) to (the melting point + 40°C).

[0048] After melt kneading, the molten resin may be ejected from a strand die, for example. The stranded material may be passed through a water tank for cooling and then cut into pellets using a pelletizer to prepare pellets.

[0049] The total content of the polyester resin (A), polyolefin resin (B), glycidyl group-containing resin (C), and polycarbodiimide (D) in the polyester resin composition according to embodiment (I) of the present invention is preferably 50% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, and even more preferably more than 90% by weight. The upper limit of the above content is preferably 100% by weight. If the total content of the polyester resin (A), polyolefin resin (B), glycidyl group-containing resin (C), and polycarbodiimide (D) in the polyester resin composition according to embodiment (I) of the present invention is within the above range, the effects of the present invention can be more effectively exhibited. The total content of the polyester resin (A), polyolefin resin (B), glycidyl group-containing resin (C), and polycarbodiimide (D) in the polyester resin composition according to embodiment (I) of the present invention can be 95% by weight or more, or 98% by weight or more, for example, when the impact modifier (E) described below is not included.

[0050] The polyester resin composition according to embodiment (I) of the present invention may contain any appropriate other components in addition to the polyester resin (A), the polyolefin resin (B), the glycidyl group-containing resin (C), and the polycarbodiimide (D), within a range that does not impair the effects of the present invention. The content of the other components in the polyester resin composition according to embodiment (I) of the present invention is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, and even more preferably less than 10% by weight. The lower limit of the above content is preferably 0% by weight. The content of the other components in the polyester resin composition according to embodiment (I) of the present invention, for example, when the impact modifier (E) described below is not contained, may be 5% by weight or less, or may be 2% by weight or less.

[0051] Examples of other components that may be included in the polyester resin composition according to embodiment (I) of the present invention include impact modifiers, pigments, dyes, fillers, reinforcing materials, heat stabilizers, light stabilizers, antioxidants, UV blockers, plasticizers, flame retardants, antistatic agents, mold release agents, foaming agents, and nucleating agents. The other components may be one or more.

[0052] The total content of the polyester resin (A), the polyolefin resin (B), the glycidyl group-containing resin (C), and the impact modifier (E) in the polyester resin composition according to embodiment (II) of the present invention is preferably 50% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, further preferably 90% by weight or more, particularly preferably 95% by weight or more, and most preferably 98% by weight or more. The upper limit of the above content is preferably 100% by weight. If the total content of the polyester resin (A), the polyolefin resin (B), the glycidyl group-containing resin (C), and the impact modifier (E) in the polyester resin composition according to embodiment (II) of the present invention is within the above range, the effects of the present invention can be better exhibited.

[0053] The polyester resin composition according to embodiment (II) of the present invention may contain any appropriate other components in addition to the polyester resin (A), the polyolefin resin (B), the glycidyl group-containing resin (C), and the impact modifier (E), within a range that does not impair the effects of the present invention. The content of the other components in the polyester resin composition according to embodiment (II) of the present invention is preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less, even more preferably 10% by weight or less, particularly preferably 5% by weight or less, and most preferably 2% by weight or less. The lower limit of the above content is preferably 0% by weight.

[0054] Examples of other components that may be included in the polyester resin composition according to embodiment (II) of the present invention include polycarbodiimide, pigments, dyes, fillers, reinforcing materials, heat stabilizers, light stabilizers, antioxidants, UV blockers, plasticizers, flame retardants, antistatic agents, mold release agents, foaming agents, and nucleating agents. The other components may be one or more.

[0055] <Polyester Resin (A)>

[0056] In the polyester resin composition according to an embodiment of the present invention, the content of the polyester resin (A) in the total of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C) is preferably 50% to 98% by weight, more preferably 60% to 97% by weight, further preferably 70% to 96% by weight, further preferably 75% to 95% by weight, particularly preferably 80% to 94% by weight, and most preferably 82% to 93% by weight. If the content of the polyester resin (A) in the total of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C) is within the above range, the effects of the present invention can be better exhibited. If the content of the polyester resin (A) is outside the above range and is too low or too high, there is a concern that the melt properties of the resulting polyester resin composition may deteriorate, and the effects of the present invention may not be exhibited.

[0057] In the polyester resin composition according to an embodiment of the present invention, particularly in the polyester resin composition according to embodiment (I) of the present invention, the content of the polyester resin (A) in the total of the polyester resin (A), the polyolefin resin (B), the glycidyl group-containing resin (C), and the polycarbodiimide (D) is preferably 50% by weight to 95% by weight, more preferably 60% by weight to 93% by weight, further preferably 70% by weight to 92% by weight, particularly preferably 75% by weight to 91% by weight, and most preferably 80% by weight to 90% by weight. When the content of the polyester resin (A) in the total of the polyester resin (A), the polyolefin resin (B), the glycidyl group-containing resin (C), and the polycarbodiimide (D) is within the above range, the effects of the present invention can be more effectively exhibited.

[0058] In the polyester resin composition according to the embodiment of the present invention, particularly in the polyester resin composition according to embodiment (I) of the present invention, the content ratio of the polyester resin (A) in the total of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) is preferably 50% by weight to 95% by weight, more preferably 60% by weight to 93% by weight, further preferably 70% by weight to 92% by weight, further preferably 75% by weight to 91% by weight, and particularly preferably 80% by weight to 90% by weight, from the perspective of further expressing the effects of the present invention.

[0059] In the polyester resin composition according to the embodiment of the present invention, particularly in the polyester resin composition according to embodiment (II) of the present invention, from the viewpoint of further exhibiting the effects of the present invention, the content ratio of the polyester resin (A) in the total of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) is preferably 60% by weight to 98% by weight, more preferably 70% by weight to 98% by weight, further preferably 80% by weight to 98% by weight, further preferably 85% by weight to 98% by weight, and particularly preferably 90% by weight to 98% by weight.

[0060] As the polyester resin (A), any appropriate polyester resin can be used within the scope that does not impair the effects of the present invention. The polyester resin (A) may be only one type or two or more types. From the perspective of better demonstrating the effects of the present invention, the polyester resin (A) preferably includes a polymer or copolymer obtained by a condensation reaction of an aromatic dicarboxylic acid (or its ester-forming derivative) with a diol (or its ester-forming derivative) and / or a hydroxycarboxylic acid as a main component.

[0061] Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, and 5-sodium sulfoisophthalic acid. The aromatic dicarboxylic acid may be used alone or in combination.

[0062] An aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid may be used in combination with an aromatic dicarboxylic acid. Examples of aliphatic dicarboxylic acids include adipic acid, sebacic acid, azelaic acid, and dodecanedioic acid. Examples of alicyclic dicarboxylic acids include 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. The aliphatic dicarboxylic acid may be used alone or in combination with two or more. The alicyclic dicarboxylic acid may be used alone or in combination with two or more.

[0063] Examples of the diol include aliphatic diols having 2 to 20 carbon atoms, specifically ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, and cyclohexanediol. The diol may be one or more.

[0064] Specific examples of the polyester resin (A) include, from the perspective of better exhibiting the effects of the present invention, polyalkylene terephthalates such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexylenedimethylene terephthalate, and polyhexylene terephthalate; polyethylene 2,6-naphthalate, polybutylene 2,6-naphthalate, polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, polyethylene isophthalate / ethylene terephthalate, polybutylene isophthalate / butylene terephthalate, polybutylene terephthalate / butylene decanedicarboxylate, poly(ethylene terephthalate / cyclohexylenedimethylene terephthalate), and polyethylene-4,4'-dicarboxylate / terephthalate. From the viewpoint of further exhibiting the effects of the present invention, preferred examples of the polyester resin (A) include polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate, and polyethylene terephthalate (PET) is more preferred.

[0065] As the polyester resin (A), a recycled polyester resin can be used, and recycled PET is a representative example.

[0066] As the polyester resin (A), recycled PET may be used alone or in a mixture with virgin PET.

[0067] As the recycled PET, conventionally known recycled PET can be used. As such recycled PET, for example, PET containers such as used PET films and used discarded PET bottles can be recovered and processed such as purification to obtain it.

[0068] In the present invention, even if the MFR of the polyester resin (A) varies, a polyester resin composition exhibiting excellent melt properties and excellent mechanical properties can be provided by combining a polyolefin resin (B) and a glycidyl group-containing resin (C), along with at least one selected from the group consisting of a polycarbodiimide (D) and an impact modifier (E). In particular, when recycled PET is used, the MFR varies from batch to batch due to the varying history of the recycled PET used as the main raw material. In the present invention, a polyester resin composition of stable quality can be produced without the need for fine-tuning the MFR of the polyester resin (A) each time.

[0069] As described above, in the present invention, the MFR of the polyester resin (A) does not need to be finely adjusted each time, and a polyester resin having an MFR preferably within a wide range of 100 g / 10 min to 300 g / 10 min at a temperature of 285° C. and a load of 2.16 kg may be used.

[0070] <Polyolefin Resin (B)>

[0071] In the polyester resin composition according to an embodiment of the present invention, the content of the polyolefin resin (B) in the total of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C) is preferably 1% by weight to 45% by weight, more preferably 1% by weight to 35% by weight, even more preferably 1% by weight to 25% by weight, particularly preferably 1% by weight to 20% by weight, and most preferably 1% by weight to 15% by weight. When the content of the polyolefin resin (B) in the total of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C) is within the above range, the effects of the present invention can be more effectively exhibited.

[0072] In the polyester resin composition according to the embodiment of the present invention, particularly in the polyester resin composition according to embodiment (I) of the present invention, from the viewpoint of further expressing the effects of the present invention, the content ratio of the polyolefin resin (B) in the total of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) is preferably 5% by weight to 45% by weight, more preferably 5% by weight to 35% by weight, further preferably 6% by weight to 25% by weight, particularly preferably 7% by weight to 20% by weight, and most preferably 8% by weight to 15% by weight.

[0073] In the polyester resin composition according to the embodiment of the present invention, particularly in the polyester resin composition according to embodiment (II) of the present invention, from the viewpoint of further expressing the effects of the present invention, the content ratio of the polyolefin resin (B) in the total of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) is preferably 1% by weight to 40% by weight, more preferably 1% by weight to 30% by weight, further preferably 1% by weight to 20% by weight, particularly preferably 1% by weight to 10% by weight, and most preferably 1% by weight to 8% by weight.

[0074] The polyolefin resin (B) may be any appropriate polyolefin resin (B) within the scope of not impairing the effects of the present invention. The polyolefin resin (B) may be one type or two or more types. Representative examples of the polyolefin resin (B) include copolymers of ethylene and / or propylene monomers and any monomer selected from other α-olefins, vinyl acetate, methyl (meth)acrylate, vinyl alcohol, and (meth)acrylic acid.

[0075] From the viewpoint of better exhibiting the effects of the present invention, the polyolefin-based resin (B) is preferably an ethylene-α-olefin copolymer, and more preferably a linear low-density polyethylene (LLDPE).

[0076] Any appropriate LLDPE can be used as long as the effects of the present invention are not impaired. Examples of LLDPE include C4 LLDPE (ethylene-1-butene copolymer), C6 LLDPE (ethylene-1-hexene copolymer), and C8 LLDPE (ethylene-1-octene copolymer), which can better demonstrate the effects of the present invention.

[0077] The LLDPE may be produced using a Ziegler-Natta catalyst or a metallocene catalyst.

[0078] The MFR of the polyolefin resin (B) at a temperature of 190°C and a load of 2.16 kg is preferably 0.5 g / 10 min to 50 g / 10 min, more preferably 0.6 g / 10 min to 45 g / 10 min, further preferably 0.7 g / 10 min to 40 g / 10 min, and particularly preferably 0.8 g / 10 min to 35 g / 10 min. If the MFR is within the above range, the effects of the present invention can be better exhibited. If the MFR is outside the above range and is too small, there is a concern that the dispersibility in the polyester resin (A) may be reduced. If the MFR is outside the above range and is too large, there is a concern that the domain size in the polyester resin (A) may become too small, for example, there is a concern that the mechanical properties may be reduced.

[0079] In the present invention, by appropriately adjusting the MFR of the polyolefin resin (B), it can be applied to various purposes. For example, the more a polyolefin resin (B) with a large MFR is added, the lower the viscosity of the polyester resin composition in the high shear rate range during melt mixing, but the MFR of the polyester resin composition tends to become smaller. This is because MFR evaluates the ejection amount under a certain load. Therefore, for a resin with a viscosity as high as a certain degree, it can be said to be equivalent to measuring the viscosity in the low shear rate range. Therefore, in molding methods that need to maintain the shape after ejection, such as special-shaped extrusion molding, sheet extrusion molding, melt extrusion 3D printing, etc., a polyolefin resin (B) with a large MFR can be used well. Therefore, in molding methods that also require fluidity after ejection, for example, in injection molding, a polyolefin resin (B) with a large MFR can also be used. In this way, by appropriately adjusting the MFR of the polyolefin resin (B), various molding methods and control of mechanical properties can be adapted.

[0080] On the other hand, in the polyester resin composition according to embodiment (II) of the present invention, a polyolefin resin (B) having a low MFR may be used. The polyolefin resin (B) having a low MFR preferably has an MFR of 0.8 to 30 g / 10 min, more preferably 0.8 to 25 g / 10 min, even more preferably 0.8 to 20 g / 10 min, even more preferably 0.8 to 15 g / 10 min, even more preferably 0.8 to 10 g / 10 min, particularly preferably 0.8 to 5 g / 10 min, and most preferably 0.8 to 3 g / 10 min.

[0081] <Glycidyl Group-Containing Resin (C)>

[0082] The ends of the polyester resin (A) typically contain carboxylic acid groups or hydroxyl groups. Therefore, in order to increase the apparent molecular weight of the polyester resin (A) and improve the melt properties and mechanical properties, resins with high reactivity with carboxylic acid groups and hydroxyl groups and compatible resins have been studied. As a result, the focus was first on glycidyl group-containing resins having glycidyl groups. However, no effect of improving the melt properties and mechanical properties was observed for all glycidyl group-containing resins, nor was gelation observed, so further research was conducted. As a result, it was found that by adjusting the content ratio of glycidyl methacrylate units in the molecule to a specific range, further, by adopting a glycidyl group-containing resin (C) with an MFR adjusted to a specific range, and combining the polyolefin resin (B) with at least one selected from the group consisting of polycarbodiimide (D) and an impact modifier (E), the effect of the present invention can be exhibited. The glycidyl group-containing resin (C) may be only one type or may be two or more types.

[0083] In the polyester resin composition according to an embodiment of the present invention, the content of the glycidyl group-containing resin (C) in the total of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C) is preferably 0.1% by weight to 20% by weight, more preferably 0.5% by weight to 15% by weight, even more preferably 0.8% by weight to 10% by weight, particularly preferably 1% by weight to 7% by weight, and most preferably 1% by weight to 5% by weight. When the content of the glycidyl group-containing resin (C) in the total of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C) is within the above range, the effects of the present invention can be more effectively exhibited.

[0084] In the polyester resin composition according to the embodiment of the present invention, particularly in the polyester resin composition according to embodiment (I) of the present invention, the content ratio of the glycidyl group-containing resin (C) in the total of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) is preferably 1% by weight to 20% by weight, more preferably 1% by weight to 15% by weight, further preferably 1% by weight to 10% by weight, particularly preferably 1% by weight to 7% by weight, and most preferably 1% by weight to 5% by weight, from the viewpoint of further exhibiting the effects of the present invention.

[0085] In the polyester resin composition according to the embodiment of the present invention, particularly in the polyester resin composition according to embodiment (II) of the present invention, the content ratio of the glycidyl group-containing resin (C) in the total of the polyester resin (A), the polyolefin resin (B) and the glycidyl group-containing resin (C) is preferably 0.1% by weight to 15% by weight, more preferably 0.2% by weight to 10% by weight, further preferably 0.4% by weight to 7% by weight, particularly preferably 0.6% by weight to 5% by weight, and most preferably 0.8% by weight to 3% by weight, from the viewpoint of further expressing the effects of the present invention.

[0086] The glycidyl group-containing resin (C) contains 2% to 30% by weight of glycidyl methacrylate units in the molecule. The content of the glycidyl methacrylate units in the molecule of the glycidyl group-containing resin (C) is preferably 3% to 27% by weight, more preferably 5% to 25% by weight, further preferably 7% to 23% by weight, and particularly preferably 10% to 20% by weight. When the content of the glycidyl methacrylate units in the molecule of the glycidyl group-containing resin (C) is within the above range, the effects of the present invention can be better exhibited. When the content of the glycidyl methacrylate units in the molecule of the glycidyl group-containing resin (C) is outside the above range and is too high, it becomes a cause of gelation, and there is a concern that the physical properties of the obtained polyester resin composition will deviate. This leads to deviations in physical property values. When the content of the glycidyl methacrylate units in the molecule of the glycidyl group-containing resin (C) is outside the above range and is too low, there is a concern that excellent melt properties cannot be obtained.

[0087] The MFR of the glycidyl group-containing resin (C) at a temperature of 190°C and a load of 2.16 kg is 1 g / 10 min to 500 g / 10 min. The MFR of the glycidyl group-containing resin (C) at a temperature of 190°C and a load of 2.16 kg is preferably 5 g / 10 min to 480 g / 10 min, more preferably 10 g / 10 min to 450 g / 10 min, further preferably 30 g / 10 min to 450 g / 10 min, particularly preferably 100 g / 10 min to 450 g / 10 min, and most preferably 200 g / 10 min to 450 g / 10 min. When the MFR is within the above range, the effects of the present invention can be better exhibited. If the MFR is outside the above range and is too large, there is a possibility that the glycidyl group-containing resin (C) alone will become a domain in the polyester resin (A). If the MFR is outside the above range and is too small, there is a concern that the dispersibility in the polyester resin (A) will be reduced.

[0088] The glycidyl group-containing resin (C) contains 2 to 30 weight percent of glycidyl methacrylate units in its molecule and exhibits an MFR of 1 to 500 g / 10 minutes at a temperature of 190°C and a load of 2.16 kg. Any appropriate glycidyl group-containing resin may be employed as long as the effects of the present invention are not impaired. From the perspective of achieving better effects of the present invention, such glycidyl group-containing resin (C) preferably contains ethylene units. More preferred examples include copolymers containing essentially monomeric components of ethylene and glycidyl methacrylate, and copolymers having a copolymer structure containing essentially monomeric components of ethylene and glycidyl methacrylate in the main chain.

[0089] Examples of copolymers containing ethylene and glycidyl methacrylate as essential monomer components include ethylene-glycidyl methacrylate copolymers, ethylene-glycidyl methacrylate-methacrylic acid ester copolymers, ethylene-glycidyl methacrylate-vinyl acetate copolymers, and ethylene-glycidyl methacrylate-1-hexene copolymers. Examples of copolymers containing a copolymer structure containing ethylene and glycidyl methacrylate as essential monomer components in the main chain include copolymers having an ethylene-glycidyl methacrylate copolymer structure as the main chain and butyl acrylate-methyl methacrylate copolymers as side chains.

[0090] <Polycarbodiimide (D)>

[0091] The polyester resin composition according to the embodiment of the present invention may contain polycarbodiimide (D). The terminal of the polyester resin (A) typically contains a carboxylic acid group and a hydroxyl group. Therefore, in order to increase the apparent molecular weight of the polyester resin (A) and improve the melt properties and mechanical properties, resins and compatible resins with high reactivity with carboxylic acid groups and hydroxyl groups have been studied. As described above, by adjusting the content ratio of the glycidyl methacrylate unit in the molecule to a specific range, and further, by using a glycidyl group-containing resin (C) that adjusts the MFR to a specific range, and combining the polyolefin resin (B) with the polycarbodiimide (D), the effect of the present invention can be exhibited. Here, in the embodiment (I) of the present invention, if the above-mentioned specific glycidyl group-containing resin (C) is not used as the glycidyl group-containing resin combined with the polyolefin resin (B) and the polycarbodiimide (D), there is a concern that the effect of the present invention cannot be exhibited. In embodiment (I) of the present invention, particularly when polycarbodiimide (D) is not combined with the specific glycidyl group-containing resin (C), gelation is likely to occur, or significantly excellent melt properties and significantly excellent mechanical properties cannot be exhibited. In embodiment (I) of the present invention, by combining polycarbodiimide (D) with the specific glycidyl group-containing resin (C), polycarbodiimide (D) reacts with the terminal carboxylic acid of the polyester resin (A), resulting in a bulky structure in which the polyester resin (A) is grafted onto the polycarbodiimide (D). It is believed that this allows excellent melt properties to be exhibited, and further, due to the synergistic effect with the specific glycidyl group-containing resin (C), even when small amounts of the specific glycidyl group-containing resin (C) and polycarbodiimide (D) are added separately, gelation can be suppressed, and significantly excellent melt properties and significantly excellent mechanical properties can be exhibited.

[0092] In the polyester resin composition according to embodiment (I) of the present invention, the amount of polycarbodiimide (D) is preferably 0.1 to 3.0 parts by weight, more preferably 0.15 to 2.5 parts by weight, further preferably 0.2 to 2 parts by weight, and particularly preferably 0.25 to 1.5 parts by weight, based on 100 parts by weight of the total amount of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C). When the amount of polycarbodiimide (D) is within the above range relative to 100 parts by weight of the total amount of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C), the effects of the present invention can be more effectively exhibited.

[0093] The polyester resin composition according to embodiment (II) of the present invention may contain polycarbodiimide (D). In the polyester resin composition according to embodiment (II) of the present invention, the amount of polycarbodiimide (D) is preferably 3.0 parts by weight or less, more preferably 2.5 parts by weight or less, even more preferably 2 parts by weight or less, and particularly preferably 1.5 parts by weight or less, based on 100 parts by weight of the total amount of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C). The lower limit of the amount of polycarbodiimide (D) is preferably 0 parts by weight.

[0094] The molecular structure of the polycarbodiimide (D) may be any of aromatic, alicyclic, and aliphatic, and may also be a cyclic structure.

[0095] The weight molecular weight of polycarbodiimide (D) is preferably 800 to 6000, more preferably 800 to 5800, and even more preferably 1000 to 5500. If the weight molecular weight of polycarbodiimide (D) is within the above range, the effects of the present invention can be better exhibited. If the weight molecular weight of polycarbodiimide (D) is outside the above range and is low in molecular weight, there is a concern that a bulky structure cannot be formed even after grafting with the polyester resin (A). If the weight molecular weight of polycarbodiimide (D) is outside the above range and is high in molecular weight, there is a concern that the reactivity of carbodiimide is reduced.

[0096] Examples of the polycarbodiimide (D) include poly(4,4'-dicyclohexylmethanecarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), poly(3,5'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(1,3-diisopropylphenylenecarbodiimide), poly(1-methyl-3,5-diisopropylphenylenecarbodiimide), poly(1,3,5-triethylphenylenecarbodiimide), and poly(triisopropylphenylenecarbodiimide). The polycarbodiimide (D) may be used alone or in combination of two or more.

[0097] <Impact Modifier (E)>

[0098] The polyester resin composition according to the embodiment of the present invention may contain an impact modifier (E). If the impact modifier (E) is an impact modifier that can improve the impact resistance of the resin composition containing it, any appropriate impact modifier may be used within the scope that does not impair the effect of the present invention. The impact modifier (E) may be only one type or two or more types. Such an impact modifier typically includes a rubber component. As the rubber component, for example, conjugated diene polymers such as polybutadiene, polyisoprene, butadiene-polyisoprene copolymer, acrylonitrile-isoprene copolymer, (meth)acrylate-butadiene copolymer, (meth)acrylate-butadiene-styrene copolymer, and (meth)acrylate-isoprene copolymer can be listed; hydrogenated products of the conjugated diene polymer; olefin rubbers such as ethylene-propylene copolymer; (meth)acrylic rubbers such as poly(meth)acrylate; silicone-(meth)acrylic polymer composite rubber; and polyorganosiloxane. Among them, conjugated diene polymers, hydrogenated conjugated diene polymers, (meth)acrylic rubbers, and silicone-(meth)acrylic polymer composite rubbers are preferably used. Examples of (meth)acrylic esters used to obtain (meth)acrylic rubbers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate.

[0099] In order to exhibit rubber elasticity, the impact modifier (E) may have a cross-linked molecular chain structure. The impact modifier (E) has a rubber layer and an adjacent layer adjacent thereto, and the molecular chains of the rubber layer and the molecular chains of the adjacent layer may be grafted by chemical bonds.

[0100] The impact modifier (E) is preferably a core / shell structure having a core and a shell, wherein the core may contain a rubber component. For example, such a core / shell structure may be one formed by graft polymerization of a polymerizable monomer for forming the shell in the presence of a polymer for forming the core.

[0101] Examples of the polymer forming the core portion include the aforementioned rubber components.

[0102] Examples of polymerizable monomers that can be used to form the shell include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, naphthyl (meth)acrylate, and isobornyl (meth)acrylate; (meth)acrylic acid of acrylic or methacrylic acid; aromatic vinyl compounds such as styrene and α-methylstyrene; and acrylonitrile. The shell layer may also be a modified form (e.g., epoxy-modified) of a polymer obtained from these polymerizable monomers.

[0103] Preferred examples of the shell portion include polymers obtained from at least one selected from (meth)acrylates and styrenes, and modified products of such polymers (for example, epoxy-modified products).

[0104] As the content of the core portion in the core / shell type structure, any appropriate content can be adopted within the scope that does not damage the effect of the present invention. As such content, for example, it can be in the range of 25 wt % to 90 wt %, or it can be in the range of 40 wt % to 80 wt %. When the content of the core portion is too little, the flexibility is insufficient, and there is a concern that sufficient impact resistance cannot be demonstrated. When the content of the core portion is too much, the content of the shell portion becomes relatively too little, and the compatibility with the polyester resin (A) is reduced. There is a concern that sufficient impact resistance cannot be demonstrated due to a reduction in interfacial bonding strength and a reduction in uniform dispersibility.

[0105] As a core / shell structure in which the aforementioned rubber component is used as a polymer forming the core portion and a polymer obtained from at least one selected from (meth)acrylate and styrene or a modified product of the polymer (e.g., epoxy-modified) is used as the shell portion, a commercially available core / shell structure can also be used. Examples of such commercially available core / shell structures include the "METABLEN (registered trademark) C" series (manufactured by Mitsubishi Chemical Corporation), the "METABLEN (registered trademark) E" series (manufactured by Mitsubishi Chemical Corporation), the "METABLEN (registered trademark) W" series (manufactured by Mitsubishi Chemical Corporation), the "METABLEN (registered trademark) S" series (manufactured by Mitsubishi Chemical Corporation), the "Kane Ace (registered trademark) B" series (manufactured by Kaneka Corporation), the "Kane Ace (registered trademark) FM" series (manufactured by Kaneka Corporation), and the "Kane Ace (registered trademark) M" series (manufactured by Kaneka Corporation). Among them, the "METABLEN (registered trademark) S" series (manufactured by Mitsubishi Chemical Corporation) and the "Kane Ace (registered trademark) FM" series (manufactured by Kaneka Corporation) can be preferably used.

[0106] The average particle size of the core / shell structure is preferably 10 nm to 1000 nm, more preferably 30 nm to 750 nm, and particularly preferably 50 nm to 500 nm. By setting the average particle size of the core / shell structure within the above range, impact resistance and formability can be further improved.

[0107] The content of the impact modifier (E) in the polyester resin composition according to embodiment (II) containing the impact modifier (E) is preferably 0.5% to 30% by weight, more preferably 0.5% to 25% by weight, further preferably 1% to 20% by weight, further preferably 3% to 15% by weight, and particularly preferably 4% to 8% by weight. If the content is too small outside the above range, there is a possibility that a sufficient impact modification effect may not be achieved. If the content is too large outside the above range, there is a concern that an improvement in impact modification beyond the amount commensurate with the added amount may not be achieved, leading to a decrease in other properties.

[0108] According to embodiment (I) of the present invention, in which the impact modifier (E) is not an essential component, the content of the impact modifier (E) in the polyester resin composition is preferably 30% by weight or less, preferably 25% by weight or less, more preferably 20% by weight or less, further preferably 15% by weight or less, and particularly preferably 8% by weight or less. The lower limit of the content of the impact modifier (E) is preferably 0% by weight, and may be 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight or more.

[0109] It should be noted that in the injection molding process, the fluidity of the molten resin during molding is very important. By increasing the addition amounts of the glycidyl group-containing resin (C) and polycarbodiimide (D), the impact resistance of the molded product can be improved to a certain extent. However, when they are added in excess, the melt viscosity may become too high or gel components may be generated. On the other hand, when the melt viscosity is too low, there is a concern that defects such as burrs are likely to occur. Therefore, especially in applications where impact resistance is required, it is necessary to improve the impact resistance of the molded product while maintaining appropriate fluidity. In the present invention, by adding an impact modifier (E) and adding the glycidyl group-containing resin (C) and polycarbodiimide (D) in a balanced manner, these necessary characteristics can be achieved simultaneously.

[0110] <Polyester-based resin molded product>

[0111] The polyester-based resin molded product according to an embodiment of the present invention is obtained by injection molding the polyester-based resin composition according to an embodiment of the present invention.

[0112] As a method of injection molding, any suitable method known as a method of injection molding a polyester-based resin composition can be employed within a range that does not impair the effects of the present invention.

[0113] Examples

[0114] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. It should be noted that the test and evaluation methods in the examples and the like are as follows. It should be noted that when "parts" are described, unless otherwise specified, they all represent "parts by weight", and when "%" is described, unless otherwise specified, they all represent "% by weight".

[0115] <MFR (Melt Flow Rate) measurement>

[0116] According to JIS K7210 B method, using an MFR measurement device (manufactured by Toyo Seiki Seisakusho, device name: MELTINDEXER F-F01), the measurement was carried out at a load of 2.16 kg, a temperature of 190 °C and 285 °C.

[0117] The smaller the MFR value, the higher the modification effect of the resin.

[0118] <Tensile elongation (Measurement A)>

[0119] After dehumidifying and drying the pellets of the prepared resin composition, it was compression-molded at 280 °C to a thickness of 0.2 mm, and the compression plate was water-cooled while under pressure and cooled to 40 °C in about 5 minutes to obtain a sheet for evaluation.

[0120] The piece was then punched into the shape of a dumbbell No. 5 piece and subjected to a tensile test using an Autograph (manufactured by Shimadzu Corporation, device name: AG-X 20 kN). The tensile test was conducted at 23°C, a tensile speed of 50 mm / min, and a grip distance of 70 mm.

[0121] Generally, a tensile elongation value of about 4% indicates the yield point strength, so samples that exceed this value can be used as a standard for qualified products.

[0122] <Tensile Elongation (Measurement B)>

[0123] The prepared resin composition pellets were dried at 100°C for 5 hours in a dehumidifying dryer and injection molded (injection temperature 280°C, mold temperature 40°C) to produce ISO 527-2-5A test pieces (4 mm width at the narrowest part, 2 mm thickness). The resulting test pieces were subjected to a tensile test using an AUTOGRAPH (manufactured by Shimadzu Corporation, device name: AG-X 20kN). The tensile test was conducted at 23°C, a tensile speed of 50 mm / min, and a grip spacing of 40 mm.

[0124] Generally, a tensile elongation value of about 4% indicates the yield point strength, so samples that exceed this value can be used as a standard for qualified products.

[0125] <Izod impact test>

[0126] The Izod impact value was measured at 23°C using an Izod impact tester (manufactured by Yasuda Seiki Co., Ltd., device name: No. 258 Impact Tester (compliant with JIS K7110)). Test specimens were prepared by drying the prepared resin composition pellets at 100°C for 5 hours in a dehumidifying dryer, then injection-molding them (injection temperature 280°C, mold temperature 40°C) to a size of 80 mm × 10 mm × 4 mm. A notch was then machined in post-processing to produce the test specimens.

[0127] In applications requiring impact resistance, 10kJ / m 2 The samples with the above impact strength can be used as the standard for qualified products.

[0128] <Evaluation of Molded Products>

[0129] Injection molding was performed using a 180-ton injection molding machine at an injection temperature of 285°C and a mold temperature of 40°C to produce a cylindrical molded product with an inner diameter of 72 mm, an outer diameter of 74 mm, and a length of 50 mm. This molded product was circumferentially compressed using a compression tester, and its appearance after compression to 50 mm was evaluated according to the following criteria.

[0130] ○: Deformed but not cracked.

[0131] ×: The elongation is small and the film breaks before reaching the yield point.

[0132] Materials used

[0133] The materials used in Examples and Comparative Examples are as follows.

[0134] 〔Polyester resin〕

[0135] Polyester resin (A1): recycled PET, MFR (load 2.16 kg, temperature 285°C) = 212 g / 10 min

[0136] Polyester resin (A2): recycled PET, MFR (load 2.16 kg, temperature 285°C) = 180 g / 10 min

[0137] Polyester resin (A3): recycled PET, MFR (load 2.16 kg, temperature 285°C) = 121 g / 10 min

[0138] 〔Polyolefin resin〕

[0139] Polyolefin resin (B1): C8-based LLDPE, trade name "Queo8230", manufactured by Borealis, MFR (load 2.16 kg, temperature 190°C) = 30 g / 10 min

[0140] Polyolefin resin (B2): C8-based LLDPE, trade name "Queo8201", manufactured by Borealis, MFR (load 2.16 kg, temperature 190°C) = 1.1 g / 10 min

[0141] Polyolefin resin (B3): C4-based LLDPE, trade name "NOVATEC LL UJ580", manufactured by Japan Polyethylene Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 20 g / 10 min

[0142] Polyolefin resin (B4): C4-based LLDPE, trade name "NOVATEC LL UJ960", manufactured by Japan Polyethylene Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 5 g / 10 min

[0143] Polyolefin resin (B5): C4-based LLDPE, trade name "NOVATEC LL UF230", manufactured by Japan Polyethylene Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 1 g / 10 min

[0144] [Glycidyl group-containing resin]

[0145] Glycidyl group-containing resin (C1): ethylene (E)-glycidyl methacrylate (GMA) copolymer, E / GMA = 81 / 19 (weight ratio), trade name "BONDFAST CG5001", manufactured by Sumitomo Chemical Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 380 g / 10 min

[0146] Glycidyl group-containing resin (C2): ethylene (E)-glycidyl methacrylate (GMA) copolymer, E / GMA = 81 / 19 (weight ratio), trade name "BONDFAST BF-30C", manufactured by Sumitomo Chemical Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 30 g / 10 min

[0147] Glycidyl group-containing resin (C3): ethylene (E)-glycidyl methacrylate (GMA) copolymer, E / GMA = 88 / 12 (weight ratio), trade name "BONDFAST BF-E", manufactured by Sumitomo Chemical Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 3 g / 10 min

[0148] Glycidyl group-containing resin (C4): ethylene (E)-glycidyl methacrylate (GMA) copolymer, E / GMA = 94 / 6 (weight ratio), trade name "BONDFAST BF-2C", manufactured by Sumitomo Chemical Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 3 g / 10 min

[0149] Glycidyl group-containing resin (C5): ethylene (E)-glycidyl methacrylate (GMA)-methacrylate (MA) copolymer, E / GMA / MA = 67 / 6 / 27 (weight ratio), trade name "BONDFAST BF-7M", manufactured by Sumitomo Chemical Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 7 g / 10 min

[0150] Glycidyl group-containing resin (C6): ethylene (E)-glycidyl methacrylate (GMA)-vinyl acetate (VA) copolymer, E / GMA / VA = 83 / 12 / 5 (weight ratio), trade name "BONDFAST BF-7B", manufactured by Sumitomo Chemical Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 7 g / 10 min

[0151] Glycidyl group-containing resin (C7): ethylene (E)-glycidyl methacrylate (GMA)-1-hexene (H) copolymer, E / GMA / H = 95 / 2 / 3 (weight ratio), trade name "ET100", manufactured by Showa Denko Building Materials Co., Ltd., MFR (load 2.16 kg, temperature 190°C) = 1 g / 10 min

[0152] Polycarbodiimide

[0153] Polycarbodiimide (D1): Trade name "Stabaxol P100", manufactured by Rhein Chemie AG, aromatic type, Mw = approximately 5000

[0154] Polycarbodiimide (D2): Trade name "CARBODILITE LA-1", manufactured by NISSHINBO CHEMICAL INC., Mw = about 2000

[0155] Polycarbodiimide (D3): Trade name "CARBODILITE HMV-15CA", manufactured by NISSHINBO CHEMICAL INC., Mw = about 2000

[0156] Impact modifier

[0157] Impact modifier (E1): A core / shell structure having a core layer of butyl acrylate polymer and a shell layer of methacrylate-styrene copolymer (trade name: Kane Ace (registered trademark) FM-40, manufactured by Kaneka Co., Ltd.)

[0158] Impact modifier (E2): A core / shell structure with a silicone-acrylic copolymer as the core layer and a methyl methacrylate polymer as the shell layer (trade name: METABLEN (registered trademark) S-2030, manufactured by Mitsubishi Chemical Corporation)

[0159] Impact modifier (E3): A core / shell structure having a silicone-acrylic acid copolymer as the core layer and a glycidyl methacrylate-modified methyl methacrylate polymer as the shell layer (trade name: METABLEN (registered trademark) S-2200, manufactured by Mitsubishi Chemical Corporation)

[0160] 〔Other resin components〕

[0161] Maleic anhydride-modified hydrogenated styrene-based thermoplastic elastomer (F1): Trade name "Tuftec M1943", manufactured by Asahi Kasei Corporation, MFR (load 2.16 kg, temperature 230°C) = 6.5 g / 10 min

[0162] Maleic anhydride-modified low-density polyethylene (F2): trade name "Plexar PX800", manufactured by Lyondell Basell, MFR (load 2.16 kg, temperature 190°C) = 2.4 g / 10 min

[0163] [Examples 1 to 24]

[0164] As shown in Tables 1 and 2, a polyester resin, a polyolefin resin, a glycidyl group-containing resin, and at least one selected from the group consisting of polycarbodiimide and an impact modifier were dry-blended and fed into a twin-screw extruder using a quantitative feeder. The polyester resin was dehumidified and dried prior to dry-blending.

[0165] After melt kneading, the molten resin is ejected from a strand die, the strand-shaped material is passed through a water tank for cooling, and then cut into pellets using a pelletizer to obtain polyester resin compositions (1) to (24).

[0166] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The mixing temperature was set to a maximum temperature of 275°C for the barrel and 260°C for the die. The screw speed was set to 300 rpm, and the material feed rate was set to 4 kg / hr.

[0167] The results are shown in Tables 1 and 2.

[0168] [Comparative Example 1]

[0169] As shown in Table 3, polyester resin (A1), polyolefin resin (B2), polycarbodiimide (D1), and maleic anhydride-modified hydrogenated styrene-based thermoplastic elastomer (F1) were dry-blended and fed into a twin-screw extruder using a quantitative feeder.

[0170] After melt kneading, the molten resin was ejected from a strand die, and the stranded material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C1).

[0171] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The kneading temperature was set at a maximum setting temperature of 275° C. for the barrel and 260° C. for the die. The screw speed was set at 300 rpm, and the material feed rate was set at 4 kg / hr.

[0172] The results are shown in Table 3.

[0173] [Comparative Example 2]

[0174] As shown in Table 3, the polyester resin (A1) and the polycarbodiimide (D3) were dry-blended and fed into a twin-screw extruder using a quantitative feeder.

[0175] After melt kneading, the molten resin was ejected from a strand die, and the stranded material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C2).

[0176] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The kneading temperature was set at a maximum setting temperature of 275° C. for the barrel and 260° C. for the die. The screw speed was set at 300 rpm, and the material feed rate was set at 4 kg / hr.

[0177] The results are shown in Table 3.

[0178] [Comparative Example 3]

[0179] As shown in Table 3, the polyester resin (A2) and the polyolefin resin (B1) were all dry-blended and fed into a twin-screw extruder using a quantitative feeder.

[0180] After melt kneading, the molten resin was ejected from a strand die, and the strand-shaped material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C3).

[0181] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The kneading temperature was set at a maximum setting temperature of 275° C. for the barrel and 260° C. for the die. The screw speed was set at 300 rpm, and the material feed rate was set at 4 kg / hr.

[0182] The results are shown in Table 3.

[0183] [Comparative Example 4]

[0184] As shown in Table 3, the polyester resin (A2), the polyolefin resin (B1), and the polycarbodiimide (D1) were all dry-blended and fed into a twin-screw extruder using a quantitative feeder.

[0185] After melt kneading, the molten resin was ejected from a strand die, and the stranded material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C4).

[0186] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The kneading temperature was set at a maximum setting temperature of 275° C. for the barrel and 260° C. for the die. The screw speed was set at 300 rpm, and the material feed rate was set at 4 kg / hr.

[0187] The results are shown in Table 3.

[0188] [Comparative Example 5]

[0189] As shown in Table 3, the polyester resin (A2), the polyolefin resin (B1), and the glycidyl group-containing resin (C4) were all dry-blended and fed into a twin-screw extruder using a quantitative feeder.

[0190] After melt kneading, the molten resin was ejected from a strand die, and the stranded material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C5).

[0191] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The mixing temperature was set to a maximum temperature of 275°C for the barrel and 260°C for the die. The screw speed was set to 300 rpm, and the material feed rate was set to 4 kg / hr.

[0192] The results are shown in Table 3.

[0193] [Comparative Example 6]

[0194] As shown in Table 3, the polyester resin (A1) and the glycidyl group-containing resin (C7) were dry-blended and fed into a twin-screw extruder using a quantitative feeder.

[0195] After melt kneading, the molten resin was ejected from a strand die, and the strand-shaped material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C6).

[0196] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The kneading temperature was set at a maximum setting temperature of 275° C. for the barrel and 260° C. for the die. The screw speed was set at 300 rpm, and the material feed rate was set at 4 kg / hr.

[0197] The results are shown in Table 3.

[0198] [Comparative Example 7]

[0199] As shown in Table 3, the polyester resin (A1), the polyolefin resin (B2), and the maleic anhydride-modified low-density polyethylene (F2) were all dry-blended and fed into a twin-screw extruder using a quantitative feeder.

[0200] After melt kneading, the molten resin was ejected from a strand die, and the strand-shaped material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C7).

[0201] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The kneading temperature was set at a maximum setting temperature of 275° C. for the barrel and 260° C. for the die. The screw speed was set at 300 rpm, and the material feed rate was set at 4 kg / hr.

[0202] The results are shown in Table 3.

[0203] [Comparative Example 8]

[0204] As shown in Table 3, the polyester resin (A2), the polyolefin resin (B5), the polycarbodiimide (D2), and the impact modifier (E2) were all dry-blended and fed into a twin-screw extruder using a quantitative feeder.

[0205] After melt kneading, the molten resin was ejected from a strand die, and the strand-shaped material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C8).

[0206] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The kneading temperature was set at a maximum setting temperature of 275° C. for the barrel and 260° C. for the die. The screw speed was set at 300 rpm, and the material feed rate was set at 4 kg / hr.

[0207] The results are shown in Table 3.

[0208] [Comparative Example 9]

[0209] As shown in Table 3, the polyester resin (A2), polycarbodiimide (D2), and impact modifier (E2) were all dry-blended and fed into a twin-screw extruder using a quantitative feeder.

[0210] After melt kneading, the molten resin was ejected from a strand die, and the strand-shaped material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C9).

[0211] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The kneading temperature was set at a maximum setting temperature of 275° C. for the barrel and 260° C. for the die. The screw speed was set at 300 rpm, and the material feed rate was set at 4 kg / hr.

[0212] The results are shown in Table 3.

[0213] [Comparative Example 10]

[0214] As shown in Table 3, the polyester resin (A2) was fed into the twin-screw extruder using a quantitative feeder.

[0215] After melt kneading, the molten resin was ejected from a strand die, and the stranded material was passed through a water tank for cooling and then cut into pellets using a pelletizer to obtain a polyester resin composition (C10).

[0216] The twin-screw extruder used had a screw diameter of 15 mm and an L / D ratio of 45. The kneading temperature was set at a maximum setting temperature of 275° C. for the barrel and 260° C. for the die. The screw speed was set at 300 rpm, and the material feed rate was set at 4 kg / hr.

[0217] The results are shown in Table 3.

[0218] [Table 1]

[0219]

[0220] [Table 2]

[0221]

[0222] [Table 3]

[0223]

[0224] Industrial applicability

[0225] According to the present invention, a polyester resin composition exhibiting excellent melt properties and excellent mechanical properties can be provided. Therefore, for example, a polyester resin composition exhibiting excellent melt properties and excellent mechanical properties can be prepared using recycled PET as a raw material, and can be suitable for PET recycling.

Claims

1. A polyester resin composition comprising a polyester resin (A), a polyolefin resin (B), a glycidyl group-containing resin (C) and a polycarbodiimide (D), The glycidyl group-containing resin (C) contains 2 to 30 wt% of glycidyl methacrylate units in the molecule.

2. The polyester resin composition according to claim 1, wherein The glycidyl group-containing resin (C) has an MFR of 1 g / 10 min to 500 g / 10 min at a temperature of 190° C. and a load of 2.16 kg.

3. The polyester resin composition according to claim 1, wherein The glycidyl group-containing resin (C) contains ethylene units.

4. The polyester resin composition according to claim 1, wherein The total content of the polyester resin (A), the polyolefin resin (B), the glycidyl group-containing resin (C), and the polycarbodiimide (D) in the polyester resin composition exceeds 90% by weight.

5. The polyester resin composition according to claim 1, wherein The content ratio of the polyester resin (A) in the total of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C) is 50% by weight to 98% by weight.

6. The polyester resin composition according to claim 1, wherein The content ratio of the polyolefin-based resin (B) in the total of the polyester-based resin (A), the polyolefin-based resin (B), and the glycidyl group-containing resin (C) is 1% by weight to 45% by weight.

7. The polyester resin composition according to claim 1, wherein The content ratio of the glycidyl group-containing resin (C) in the total of the polyester-based resin (A), the polyolefin-based resin (B), and the glycidyl group-containing resin (C) is 0.1% by weight to 20% by weight.

8. The polyester resin composition according to claim 1, wherein The amount of the polycarbodiimide (D) is 0.1 to 3.0 parts by weight based on 100 parts by weight of the total amount of the polyester resin (A), the polyolefin resin (B), and the glycidyl group-containing resin (C).

9. The polyester resin composition according to claim 1, wherein The polyester resin (A) has an MFR of 100 g / 10 min to 300 g / 10 min at a temperature of 285° C. and a load of 2.16 kg.

10. The polyester resin composition according to claim 1, wherein The polyester resin (A) is polyethylene terephthalate.

11. The polyester resin composition according to claim 1, wherein The polyolefin resin (B) is an ethylene-α-olefin copolymer.

12. The polyester resin composition according to claim 11, wherein The polyolefin-based resin (B) is a linear low-density polyethylene.

13. The polyester resin composition according to claim 1, wherein The polyolefin-based resin (B) has an MFR of 0.5 g / 10 min to 50 g / 10 min at a temperature of 190° C. and a load of 2.16 kg.

14. The polyester resin composition according to claim 1, wherein The weight average molecular weight of the polycarbodiimide (D) is 500 to 6000.

15. The polyester resin composition according to claim 1, wherein The polyester resin composition contains 0.5 to 30 weight percent of an impact modifier (E).

16. The polyester resin composition according to claim 15, wherein The impact modifier (E) has a core / shell structure having a core and a shell, and the core contains a rubber component.

17. A polyester resin composition comprising a polyester resin (A), a polyolefin resin (B), a glycidyl group-containing resin (C) and an impact modifier (E), The glycidyl group-containing resin (C) contains 2 to 30 wt% of glycidyl methacrylate units in the molecule. 18 . A polyester resin molded article obtained by injection molding the polyester resin composition according to claim 1 .

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