Resin composition and mixture, and molded article comprising the same

Abstract

To provide a resin composition capable of yielding a molded article having superior moldability and superior impact resistance.SOLUTION: A resin composition comprises a polyester (A) and a polyester (B) having specific structures, wherein the intrinsic viscosity IV(A) of polyester (A) is 0.8-1.3 dl / g, the intrinsic viscosity IV(B) of polyester (B) is 0.6-0.9 dl / g, the absolute value of the difference between IV(A) and IV(B), |IV(A)-IV(B)|, is 0.5 dl / g or less, and the mass ratio (A / B) of polyester (A) to polyester (B) is 0.1 / 99.9 to 50 / 50.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to resin compositions and mixtures containing specific polyesters.

Background Art

[0002] Polyesters are excellent in various properties such as transparency, mechanical properties, gas barrier properties, and flavor barrier properties. Moreover, when formed into molded products, there is little concern about residual monomers and harmful additives, and they are excellent in hygiene and safety. For these reasons, polyesters have been widely used in recent years as hollow containers and the like for filling juices, soft drinks, seasonings, oils, cosmetics, detergents, and other products, replacing the conventionally used vinyl chloride resins.

[0003] In recent years, the environmental impact of plastic waste has been regarded as a problem, and the recycling of polyesters has also been promoted. For example, many PET bottles made of polyethylene terephthalate (PET) are collected and recycled into food trays such as egg cartons and fibers. On the other hand, if PET bottles can be manufactured again from the collected PET bottles, the PET bottles can be circulated many times as resources, leading to a reduction in fossil-derived resources and carbon dioxide emissions. In fact, a part of the collected PET bottles is used as a raw material for manufacturing PET bottles again, but the recycling rate by such a method is not high. The reason is that when molding the raw material derived from the collected PET bottles, the limiting viscosity decreases due to the influence of moisture, making it difficult to maintain the same quality as the original PET bottles. The same problem exists in the recycling of containers made of polyesters, not limited to PET bottles.

[0004] As one means of solving such problems, a method of adding a specific polyester to the recycled polyester can be considered. Patent Document 1 describes an extrusion blow molded article containing a specific polyester, the extrusion blow molded article having a melting point temperature of 230 to 245°C when blended with a PET recycled standard product at a ratio of 1:1.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] In Patent Document 1, the physical properties of the container formed by extrusion blow molding are not evaluated. According to the study by the inventors, when a container such as a bottle is produced using a mixture of polyester and recycled PET described in Patent Document 1 as a raw material, the moldability may be inferior compared to the case of producing a container using the original PET as a raw material, or the impact resistance may be inferior compared to the container made of the original PET.

[0007] The present disclosure has been made to solve the above problems, and an object thereof is to provide a resin composition capable of providing a molded product having excellent moldability and excellent impact resistance.

Means for Solving the Problems

[0008] The above problems are solved by [1] to

[16] . [1] A resin composition containing polyester (A) and polyester (B), wherein polyester (A) is at least one selected from the group consisting of polyester (A - 1) containing 35 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 15 mol% of units derived from cyclohexanedimethanol, and 45 to 50 mol% of units derived from terephthalic acid with respect to all monomer units, and polyester (A - 2) containing 43 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 7 mol% of units derived from bisphenol A ethylene oxide adduct, and 45 to 50 mol% of units derived from terephthalic acid with respect to all monomer units, Polyester (B) contains, based on all monomer units, 40 to 50 mol% of units derived from ethylene glycol and 40 to 50 mol% of units derived from terephthalic acid, the content of units derived from isophthalic acid in polyester (B) based on all monomer units is 10 mol% or less, the content of units derived from cyclohexanedimethanol is less than 1.5 mol%, and the content of units derived from bisphenol A ethylene oxide adduct is less than 1.5 mol%, the intrinsic viscosity IV(A) of polyester (A) is 0.8 to 1.3 dl / g, and the intrinsic viscosity IV(B) of polyester (B) is 0.6 to 0.9 dl / g, the absolute value of the difference between the intrinsic viscosity IV(A) and the intrinsic viscosity IV(B) (|IV(A) - IV(B)|) is 0.5 dl / g or less, a resin composition wherein the mass ratio (A / B) of polyester (A) to polyester (B) is 0.1 / 99.9 to 50 / 50; [2] The resin composition according to [1], wherein the content of units derived from isophthalic acid in polyester (B) is 1.5 to 5 mol% based on all monomer units; [3] The resin composition according to [1] or [2], wherein polyester (A) is polyester (A-1), and the content of units derived from cyclohexanedimethanol in polyester (A-1) is 1.5 mol% or more and less than 3.5 mol% based on all monomer units; [4] The resin composition according to any one of [1] to [3], wherein polyester (A) further contains 0.001 to 0.2 mol% of units derived from a compound represented by the following formula (I) based on all monomer units;

[0009] [Chemical formula]

[0010] [In formula (I), the sum of x, y, z, and w is 1 to 50, and R 1 ~R 4 each independently represents a hydrogen atom or an acyl group having 1 to 18 carbon atoms.] [5] The resin composition according to [4], wherein the compound represented by the formula (I) is at least one selected from the group consisting of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan trioleate; [6] The resin composition according to any one of [1] to [5], wherein the polyester (A) and / or the polyester (B) further contains units derived from a hindered phenol antioxidant in an amount of 0.0005 to 0.2 mol% based on all monomer units; [7] The resin composition according to any one of [1] to [6], wherein at least one of the polyester (A) and the polyester (B) contains a recovered material; [8] A mixture containing the polyester (A) and the polyester (B), wherein the forms of the polyester (A) and the polyester (B) are pellets, flakes or powders, the polyester (A) consists of at least one selected from the group consisting of a polyester (A-1) containing, based on all monomer units, 35 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 15 mol% of units derived from cyclohexanedimethanol, and 45 to 50 mol% of units derived from terephthalic acid, and a polyester (A-2) containing, based on all monomer units, 43 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 7 mol% of units derived from a bisphenol A ethylene oxide adduct, and 45 to 50 mol% of units derived from terephthalic acid, the polyester (B) contains, based on all monomer units, 40 to 50 mol% of units derived from ethylene glycol and 40 to 50 mol% of units derived from terephthalic acid, the content of the units derived from isophthalic acid in the polyester (B) based on all monomer units is 10 mol% or less, the content of the units derived from cyclohexanedimethanol is less than 1.5 mol%, and the content of the units derived from a bisphenol A ethylene oxide adduct is less than 1.5 mol%, The intrinsic viscosity IV(A) of polyester (A) is 0.8 to 1.3 dl / g, and the intrinsic viscosity IV(B) of polyester (B) is 0.6 to 0.9 dl / g, and the absolute value of the difference between the intrinsic viscosity IV(A) and the intrinsic viscosity IV(B) (|IV(A) - IV(B)|) is 0.5 dl / g or less, a mixture in which the mass ratio (A / B) of polyester (A) to polyester (B) is 0.1 / 99.9 to 50 / 50; a molded article obtained by extrusion molding any of the resin compositions or mixtures of [9][1] to [8]; a molded article obtained by blow molding any of the resin compositions or mixtures of

[10] [1] to [8]; a molded article obtained by injection molding any of the resin compositions or mixtures of

[11] [1] to [8]; a film or sheet made of the molded article of

[12] [9]; a thermoformed article obtained by thermoforming the film or sheet of

[13]

[12] ; a container made of any of the molded articles of

[14] [9] to

[11] ;

[15] A step of pulverizing and drying the recovered product of polyester (A) and the recovered product of polyester (B), and a method for producing any of the resin compositions of [1] to [7], including a step of melt-kneading the dried product obtained in the above step;

[16] A step of pulverizing and drying the recovered product of polyester (B), and a method for producing any of the resin compositions of [1] to [7], including a step of melt-kneading the dried product obtained in the above step and polyester (A).

Advantages of the Invention

[0011] The resin composition of the present disclosure can provide a molded article having excellent moldability and excellent impact resistance.

Modes for Carrying Out the Invention

[0012] The resin composition of the present disclosure contains polyester (A) and polyester (B). Polyester (A) consists of at least one selected from the group consisting of polyester (A-1) containing, based on all monomer units, 35 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 15 mol% of units derived from cyclohexanedimethanol (hereinafter sometimes referred to as CHDM), and 45 to 50 mol% of units derived from terephthalic acid, and polyester (A-2) containing, based on all monomer units, 43 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 7 mol% of units derived from bisphenol A ethylene oxide adduct (hereinafter sometimes referred to as EOBPA), and 45 to 50 mol% of units derived from terephthalic acid. Polyester (A) preferably contains polyester (A-1), and more preferably is polyester (A-1).

[0013] The content of the units derived from ethylene glycol in polyester (A-1) is 35 mol% or more and 48.5 mol% or less based on all monomer units, preferably 37 mol% or more, more preferably 39 mol% or more, and even more preferably 41 mol% or more. The content of the units derived from CHDM in polyester (A-1) is 1.5 mol% or more based on all monomer units, and may preferably be 1.7 mol% or more, 2 mol% or more, or 3 mol% or more. The content of the units derived from CHDM in polyester (A-1) is 15 mol% or less based on all monomer units, more preferably 13 mol% or less, even more preferably 11 mol% or less, particularly preferably 10 mol% or less, and may preferably be 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, less than 3.5 mol%, 3.3 mol% or less, or 3 mol% or less. When the content of the units derived from CHDM is below the above upper limit value, the moldability of the resin composition is more excellent. Further, polyester (A-1) tends to have crystallinity, and even when dried at a high temperature (for example, 120 ° C), the resin pellets are less likely to weld to each other, and the drying suitability is more excellent. The content of the units derived from terephthalic acid in polyester (A-1) is 45 mol% or more and 50 mol% or less based on all monomer units, preferably 46 mol% or more, more preferably 47 mol% or more, and in some cases, preferably 48 mol% or more or 49 mol% or more.

[0014] The content of the units derived from ethylene glycol in polyester (A-2) is 43 mol% or more and 48.5 mol% or less based on all monomer units, preferably 45 mol% or more, and in some cases, more preferably 46 mol% or more. The content of the units derived from EOBPA in polyester (A-2) is 1.5 mol% or more and 7 mol% or less based on all monomer units, and in some cases, preferably 2 mol% or more and 5 mol% or less. The content of the units derived from terephthalic acid in polyester (A-2) is 45 mol% or more and 50 mol% or less based on all monomer units, preferably 46 mol% or more, more preferably 47 mol% or more, and in some cases, preferably 48 mol% or more or 49 mol% or more.

[0015] Polyester (A) preferably contains 0.001 to 0.2 mol% of units derived from the compound represented by the following formula (I) based on all monomer units.

[0016] [Chemical formula] [In formula (I), the sum of x, y, z, and w is 1 to 50, and R 1 ~R 4 each independently represents a hydrogen atom or an acyl group having 1 to 18 carbon atoms.]

[0017] The content of the unit derived from the compound represented by the formula (I) in the polyester (A) is more preferably 0.002 mol% or more, still more preferably 0.005 mol% or more, and may be preferably 0.007 mol% or more or 0.008 mol% or more, based on all monomer units. When the content is at least the above lower limit value, generation of gels and coloring are likely to be suppressed. The content of the unit derived from the compound represented by the formula (I) in the polyester (A) is more preferably 0.15 mol% or less, still more preferably 0.1 mol% or less, and may be preferably 0.05 mol% or less or 0.02 mol% or less. When the content is at most the above upper limit value, it is easy to obtain the required non-Newtonian property and coloring is likely to be suppressed.

[0018] In the above formula (I), the sum of x, y, z and w is from 1 to 50. The sum is preferably 4 or more, more preferably 8 or more, still more preferably 12 or more, particularly preferably 16 or more, and most preferably 18 or more. When the sum is at least the above lower limit value, the molecular weight between the minimum crosslinking points becomes large and gels are less likely to occur. On the other hand, the sum is preferably 40 or less, more preferably 32 or less, still more preferably 28 or less, particularly preferably 24 or less, and most preferably 22 or less. When the sum is at most the above upper limit value, it is easy to obtain the required non-Newtonian property and coloring also tends to be suppressed.

[0019] In the above formula (I), R 1 ~R 4 each independently represents a hydrogen atom or an acyl group having 1 to 18 carbon atoms. From the viewpoint of suppressing the generation of gels, the number of carbon atoms of the acyl group is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, particularly preferably 7 or more, and most preferably 8 or more. On the other hand, from the viewpoint of availability, the number of carbon atoms is 18 or less, preferably 16 or less, more preferably 14 or less, and still more preferably 12 or less. The acyl group may be linear or branched, but the former is preferred.

[0020] The compound represented by the above formula (I) is preferably at least one selected from the group consisting of polyoxyethylene sorbitan monolaurate (polysorbate 20), polyoxyethylene sorbitan monostearate (polysorbate 60), polyoxyethylene sorbitan monooleate (polysorbate 80), polyoxyethylene sorbitan tristearate (polysorbate 65), polyoxyethylene sorbitan monopalmitate (polysorbate 40), and polyoxyethylene sorbitan trioleate (polysorbate 85). Among them, polyoxyethylene sorbitan monolaurate is more preferable.

[0021] The polyester (A) preferably further contains 0.0005 to 0.2 mol% of units derived from a hindered phenol-based antioxidant based on all monomer units. Here, the units derived from the hindered phenol-based antioxidant are those contained in the polyester (A) by polycondensing the hindered phenol-based antioxidant together with ethylene glycol, terephthalic acid, and CHDM or EOBPA. The polyol units of the hindered phenol-based antioxidant and the carboxylic acid units having a hindered phenol group are contained in the polyester (A) by transesterification reaction. When the units derived from the hindered phenol-based antioxidant are contained in the polyester (A), the coloring of the resin composition is further suppressed. Examples of the hindered phenol-based antioxidant include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxy]ethyl]hexahydro-1,3,5-triazine-2,4,6-trione, and the like.

[0022] The content of the unit derived from the hindered phenol antioxidant in the polyester (A) is preferably 0.0005 mol% or more, more preferably 0.0006 mol% or more, still more preferably 0.0007 mol% or more, and may be preferably 0.0008 mol% or more, based on all monomer units. On the other hand, the content is preferably 0.2 mol% or less, more preferably 0.19 mol% or less, still more preferably 0.15 mol% or less, and may be preferably 0.1 mol% or less or 0.05 mol% or less. When the content is below the above upper limit value, the crystallinity is moderately high and the physical properties tend to be excellent.

[0023] From the viewpoint of further suppressing coloring, the molar ratio of the unit derived from the hindered phenol antioxidant to the unit derived from the compound represented by the above formula (I) in the polyester (A) (unit derived from the hindered phenol antioxidant / unit derived from the compound represented by formula (I)) is preferably 0.001 to 0.1. The molar ratio (unit derived from the hindered phenol antioxidant / unit derived from the compound represented by formula (I)) is more preferably 0.005 or more, still more preferably 0.01 or more, and particularly preferably 0.05 or more. On the other hand, the molar ratio (unit derived from the hindered phenol antioxidant / unit derived from the compound represented by formula (I)) is more preferably 0.095 or less, still more preferably 0.09 or less, and particularly preferably 0.085 or less.

[0024] As long as the effects of the present disclosure are not inhibited, polyester (A) may contain units derived from ethylene glycol, CHDM, EOBPA, terephthalic acid, the compound represented by the above formula (I), and other ester-forming monomers other than the hindered phenolic antioxidant. Examples of such other ester-forming monomers include isophthalic acid; monocarboxylic acids, monoalcohols, and their ester-forming derivatives; polyfunctional compounds having three or more carboxyl groups, hydroxyl groups, and / or their ester-forming groups other than the compound represented by the above formula (I). Examples of such polyfunctional compounds include trimellitic anhydride, pyromellitic anhydride, trimethylolpropane, tetramethylolmethane, pentaerythritol, trimesic acid, and the like. The content of the units of the other ester-forming monomers in polyester (A) is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and particularly preferably substantially not contained, based on all monomer units. Further, polyester (A-1) may contain units derived from EOBPA, and polyester (A-2) may contain units derived from CHDM.

[0025] The resin composition of the present disclosure contains polyester (B). Polyester (B) contains 40 to 50 mol% of units derived from ethylene glycol and 40 to 50 mol% of units derived from terephthalic acid, based on all monomer units. The content of units derived from isophthalic acid in polyester (B) based on all monomer units is 10 mol% or less, the content of units derived from CHDM is less than 1.5 mol%, and the content of units derived from EOBPA is less than 1.5 mol%. The content of units derived from ethylene glycol in polyester (B) is 40 mol% or more and 50 mol% or less, preferably 45 mol% or more, more preferably 47 mol% or more, and may be preferably 48 mol% or more or 49 mol% or more, based on all monomer units. The content of the units derived from terephthalic acid in polyester (B) is 40 mol% or more, preferably 42 mol% or more, more preferably 44 mol% or more, still more preferably 45 mol% or more, and may also be preferably 46 mol% or more or 47 mol% or more, based on all monomer units. The content of the units derived from terephthalic acid in polyester (B) is 50 mol% or less, preferably 49 mol% or less, more preferably 48.5 mol% or less, and may also be preferably 48 mol% or less or 47 mol% or less, based on all monomer units.

[0026] The content of the units derived from isophthalic acid in polyester (B) is 10 mol% or less, preferably 8 mol% or less, more preferably 6 mol% or less, still more preferably 5 mol% or less, and may also be preferably 4 mol% or less or 3 mol% or less, based on all monomer units. Polyester (B) may not contain units derived from isophthalic acid. The content of the units derived from isophthalic acid in polyester (B) is preferably 1 mol% or more, more preferably 1.5 mol% or more, and may also be preferably 2 mol% or more or 3 mol% or more, based on all monomer units. The content of the units derived from CHDM in polyester (B) is less than 1.5 mol%, preferably 1 mol% or less, more preferably 0.5 mol% or less. Polyester (B) may not contain units derived from CHDM. The content of the units derived from EOBPA in polyester (B) is less than 1.5 mol%, preferably 1 mol% or less, more preferably 0.5 mol% or less. Polyester (B) may not contain units derived from EOBPA.

[0027] Polyester (B) may further contain units derived from a hindered phenol antioxidant in an amount of 0.0005 to 0.2 mol% based on all monomer units. Here, the units derived from the hindered phenol antioxidant are those contained in polyester (B) by polycondensing the hindered phenol antioxidant together with ethylene glycol, terephthalic acid, and optionally isophthalic acid. The polyol units of the hindered phenol antioxidant and the carboxylic acid units having a hindered phenol group are contained in polyester (B) by transesterification reaction. When the units derived from the hindered phenol antioxidant are contained in polyester (B), the coloring of the resin composition is further suppressed. Examples of the hindered phenol antioxidant include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyloxy]ethyl]hexahydro-1,3,5-triazine-2,4,6-trione, and the like.

[0028] When polyester (B) contains units derived from a hindered phenol antioxidant, the content is preferably 0.0005 mol% or more, more preferably 0.0006 mol% or more, further preferably 0.0007 mol% or more, and in some cases preferably 0.0008 mol% or more, based on all monomer units. On the other hand, the content is preferably 0.2 mol% or less, more preferably 0.19 mol% or less, further preferably 0.15 mol% or less, and in some cases preferably 0.1 mol% or less or 0.05 mol% or less. When the content is below the above upper limit value, the crystallinity is moderately high and the physical properties tend to be excellent.

[0029] As long as the effects of the present disclosure are not inhibited, polyester (B) may contain units derived from ester-forming monomers other than ethylene glycol, terephthalic acid, isophthalic acid, CHDM, EOBPA, and the hindered phenolic antioxidant. Examples of such other ester-forming monomers include monocarboxylic acids, monoalcohols, and their ester-forming derivatives; the compounds represented by the above formula (I); polyfunctional compounds having three or more carboxyl groups, hydroxyl groups, and / or their ester-forming groups other than the compounds represented by the above formula (I), and the like. Examples of such polyfunctional compounds include trimellitic anhydride, pyromellitic anhydride, trimethylolpropane, tetramethylolmethane, pentaerythritol, trimesic acid, and the like. The content of the units of the other ester-forming monomers in polyester (B) is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, and particularly preferably substantially not contained, based on all monomer units.

[0030] The intrinsic viscosity IV(A) of polyester (A) is 0.8 to 1.3 dl / g. IV(A) is preferably 0.85 dl / g or more, more preferably 0.9 dl / g or more, still more preferably 0.95 dl / g or more, and may also be preferably 1.0 dl / g or more, 1.03 dl / g or more, 1.05 dl / g or more, or 1.1 dl / g or more. When IV(A) is at least the above lower limit value, the moldability of the resin composition is more excellent, or the impact resistance of the molded article made of the resin composition is more excellent. IV(A) may be preferably 1.27 dl / g or less, 1.25 dl / g or less, 1.23 dl / g or less, or 1.2 dl / g or less. The intrinsic viscosity is measured by the method described in the examples.

[0031] The intrinsic viscosity IV(B) of the polyester (B) is 0.6 to 0.9 dl / g. IV(B) is preferably 0.65 dl / g or more, more preferably 0.7 dl / g or more, still more preferably 0.75 dl / g or more, and may be preferably 0.8 dl / g or more or 0.82 dl / g or more. When IV(B) is at least the above lower limit value, the moldability of the resin composition is more excellent, or the impact resistance of the molded article made of the resin composition is more excellent. IV(B) may be preferably 0.88 dl / g or less or 0.86 dl / g or less.

[0032] The absolute value of the difference between the intrinsic viscosity IV(A) and the intrinsic viscosity IV(B) (|IV(A) - IV(B)|) is 0.5 dl / g or less, preferably 0.45 dl / g or less, and may be preferably 0.40 dl / g or less. |IV(A) - IV(B)| is 0 dl / g or more, preferably 0.05 dl / g or more, more preferably 0.1 dl / g or more, still more preferably 0.12 dl / g or more, and may be preferably 0.15 dl / g or more, 0.2 dl / g or more, or 0.25 dl / g or more. When |IV(A) - IV(B)| is within the above range, the moldability of the resin composition is more excellent, or the impact resistance of the molded article made of the resin composition is more excellent. It may be preferable that the intrinsic viscosity IV(A) is greater than the intrinsic viscosity IV(B).

[0033] It is preferable that the intrinsic viscosity IV(A) is greater than the intrinsic viscosity IV(B). When IV(A) is greater than IV(B), even when the intrinsic viscosity of the polyester (B) decreases due to the influence of moisture or the like, the intrinsic viscosity of the resin composition can be increased, and when the recovered product of the container made of polyester is recycled as a container again, the resin composition of the present disclosure can be utilized more effectively. IV(A) - IV(B) is preferably 0.05 dl / g or more, more preferably 0.1 dl / g or more, still more preferably 0.12 dl / g or more, and may be preferably 0.15 dl / g or more, 0.2 dl / g or more, or 0.25 dl / g or more.

[0034] The mass ratio (A / B) of polyester (A) to polyester (B) is from 0.1 / 99.9 to 50 / 50. A / B is preferably from 1 / 99 to 49 / 51, more preferably from 3 / 97 to 47 / 53, still more preferably from 5 / 95 to 45 / 55, and may also be preferably from 10 / 90 to 43 / 57, from 15 / 85 to 42 / 58, or from 20 / 80 to 40 / 60.

[0035] From the viewpoint of improving heat resistance, the glass transition temperature of polyester (A) and polyester (B) is preferably 75°C or higher, more preferably 77°C or higher. On the other hand, the glass transition temperature is preferably 100°C or lower. In this case, it is preferable because it is not necessary to heat the mold to a temperature equal to or higher than room temperature when the resin composition is subjected to extrusion blow molding.

[0036] From the viewpoint of further improving the draw-down resistance during extrusion blow molding, the melting point of polyester (A) and polyester (B) is preferably 225°C or higher, more preferably 230°C or higher, and still more preferably 232°C or higher. On the other hand, from the viewpoint of further improving the color tone of the molded product by keeping the cylinder temperature low during extrusion blow molding, the melting point of the polyester is preferably 260°C or lower.

[0037] It is preferable that at least one of polyester (A) and polyester (B) contains a recovered material, and it is preferably that at least polyester (B) contains a recovered material. In the present specification, the recovered material means scraps such as burrs generated when producing a molded product from polyester, off-spec products, and molded products made of used polyester (for example, molded products recovered after being circulated and used in the market).

[0038] As a method for producing the polyester (A), a method of polycondensing ethylene glycol, terephthalic acid, CHDM or EOBPA, and optionally the compound represented by the above formula (I) is preferred. The method of polycondensation is not particularly limited, but a method of polycondensing by melt-kneading ethylene glycol, terephthalic acid, CHDM or EOBPA, and optionally the compound represented by the above formula (I) is preferred. Specifically, a method in which an esterification reaction or a transesterification reaction is carried out using ethylene glycol, terephthalic acid, CHDM or EOBPA, and optionally the compound represented by the above formula (I) as raw materials, and then the obtained polyester oligomer is melt-polycondensed can be mentioned. The compound represented by the above formula (I) may be added before carrying out the esterification reaction or the transesterification reaction, or may be added after carrying out these reactions. In addition, raw materials other than the compound represented by the above formula (I) can also be added appropriately before carrying out the esterification reaction or the transesterification reaction, or after carrying out these reactions.

[0039] As a method for producing the polyester (B), a method of polycondensing ethylene glycol, terephthalic acid, and optionally isophthalic acid is preferred. The method of polycondensation is not particularly limited, but a method of polycondensing by melt-kneading ethylene glycol, terephthalic acid, and optionally isophthalic acid is preferred. Specifically, a method in which an esterification reaction or a transesterification reaction is carried out using ethylene glycol, terephthalic acid, and optionally isophthalic acid as raw materials, and then the obtained polyester oligomer is melt-polycondensed can be mentioned.

[0040] The above-mentioned esterification reaction or transesterification reaction is preferably carried out by charging the above-mentioned raw materials, a polymerization catalyst, and optionally additives such as the hindered phenol-based antioxidant into a reactor under a pressure of about 0.5 MPa or less in absolute pressure or at normal pressure, at a temperature of 160 to 280 °C, while distilling off the generated water or alcohol.

[0041] The melt polycondensation reaction following the esterification reaction or transesterification reaction is preferably carried out by adding, if necessary, the above-mentioned raw materials, polycondensation catalyst and additives such as the hindered phenol antioxidant to the obtained polyester oligomer under a reduced pressure of 1 kPa or less at a temperature of 260 to 290 °C until a polyester with a desired viscosity is obtained. When the reaction temperature of the melt polycondensation reaction is less than 260 °C, the polymerization activity of the polymerization catalyst is low, and there is a risk that a polyester with the target degree of polymerization cannot be obtained. On the other hand, when the reaction temperature of the melt polycondensation reaction exceeds 290 °C, the decomposition reaction tends to proceed, and as a result, there is a risk that a polyester with the target degree of polymerization cannot be obtained. The melt polycondensation reaction can be carried out using, for example, a tank-type batch polycondensation apparatus, a continuous polycondensation apparatus composed of a twin-screw rotary horizontal reactor, etc.

[0042] As the polymerization catalyst used in the above polycondensation, any catalyst that can be used in the production of polyester can be selected, but compounds containing metal elements such as germanium, titanium, zirconium, hafnium, antimony, tin, magnesium, calcium, zinc, aluminum, cobalt, lead, cesium, manganese, lithium, potassium, sodium, copper, barium, cadmium, etc. are preferred. Among them, compounds containing germanium element, antimony element, and titanium element are preferred. As the compound containing antimony element, antimony trioxide, antimony chloride, antimony acetate, etc. are used, as the compound containing germanium element, germanium dioxide, germanium tetrachloride, germanium tetraethoxide, etc. are used, and as the compound containing titanium element, tetraisopropyl titanate, tetrabutyl titanate, etc. are used. In addition, composite particles of hydrotalcite and titanium dioxide are also mentioned as the polymerization catalyst. Among these, antimony trioxide and germanium dioxide are preferred from the viewpoints of polymerization catalyst activity, physical properties of the obtained polyester, and cost. When using a polymerization catalyst, the addition amount is preferably in the range of 0.002 to 0.8% by mass based on the mass of dicarboxylic acid components such as terephthalic acid and isophthalic acid.

[0043] As long as the effects of the present invention are not inhibited, in the above polycondensation, for example, antioxidants other than the hindered phenol-based antioxidant such as phosphoric acid compounds including phosphorous acid or esters thereof may be used. These may be used alone or in combination of two or more. Examples of the phosphoric acid compounds include phosphorous acid, phosphorous acid esters, phosphoric acid, trimethyl phosphate, triphenyl phosphate, and the like. The amount of the anti-coloring agent used is preferably in the range of 20 to 1000 ppm based on the total of dicarboxylic acid components such as terephthalic acid and isophthalic acid and diester components such as ethylene glycol, CHDM, and EOBPA. Further, in order to suppress coloring due to thermal decomposition of the polyester, a cobalt compound such as cobalt acetate may be added, and the amount of use thereof is preferably in the range of 20 to 1000 ppm based on the total of dicarboxylic acid components such as terephthalic acid and isophthalic acid and diol components such as ethylene glycol, CHDM, and EOBPA.

[0044] The intrinsic viscosity of the polyester obtained by melt polycondensation is preferably 0.4 dl / g or more. Thereby, the handleability is improved, and when the polyester obtained by melt polycondensation is further subjected to solid-phase polymerization, the molecular weight can be increased in a short time, so that the productivity is improved. The intrinsic viscosity is more preferably 0.55 dl / g or more, and still more preferably 0.65 dl / g or more. On the other hand, from the viewpoints of easily taking out the polyester from the reactor and suppressing coloring due to thermal deterioration, the intrinsic viscosity is preferably 0.9 dl / g or less, more preferably 0.85 dl / g or less, and still more preferably 0.8 dl / g or less.

[0045] It is also preferable to further subject the thus obtained polyester to solid-phase polymerization. By carrying out solid-phase polymerization, IV(A) and IV(B) become appropriate values. The solid-phase polymerization will be described below.

[0046] The polyester obtained by melt polycondensation is extruded into a strand shape, sheet shape, etc., and after cooling, it is cut by a strand cutter, sheet cutter, etc. to produce intermediate pellets in the shape of a cylinder, elliptical cylinder, disc, die, etc. The cooling after the extrusion described above can be carried out, for example, by a water cooling method using a water tank, a method using a cooling drum, an air cooling method, etc.

[0047] Solid-phase polymerization is carried out to further increase the degree of polymerization of the intermediate pellets thus obtained. It is preferable to heat and crystallize a part of the polyester in advance before solid-phase polymerization. By doing so, it is possible to prevent the adhesion of the pellets during solid-phase polymerization. The crystallization temperature is preferably 100 to 180°C. As the crystallization method, it may be crystallized in a vacuum tumbler, or it may be heated and crystallized in an air circulation type heating device. When heating in an air circulation type heating device, the internal temperature is preferably 100 to 160°C. When heating using an air circulation type heating device, compared with the case of crystallizing using a vacuum tumbler, the heat conduction is good, so the time required for crystallization can be shortened, and the device is also inexpensive. The time required for crystallization is not particularly limited, but is usually about 30 minutes to 24 hours. Prior to crystallization, the pellets may be dried at a temperature below 100°C.

[0048] The temperature of the solid-phase polymerization is preferably 170 to 250°C. When the temperature of the solid-phase polymerization is less than 170°C, the time of the solid-phase polymerization may become long and the productivity may decrease. The temperature of the solid-phase polymerization is more preferably 175°C or higher, and even more preferably 180°C or higher. On the other hand, when the temperature of the solid-phase polymerization exceeds 250°C, there is a risk of adhesion of the pellets. The temperature of the solid-phase polymerization is more preferably 240°C or lower, and even more preferably 230°C or lower. The time of the solid-phase polymerization is usually about 5 to 70 hours. Also, the catalyst used in the melt polymerization may coexist during the solid-phase polymerization.

[0049] Furthermore, the solid-phase polymerization is preferably carried out under reduced pressure or in an inert gas such as nitrogen gas. Also, in order to prevent sticking between pellets, it is preferable to perform solid-phase polymerization while moving the pellets by an appropriate method such as a rolling method or a gas fluidized bed method. The pressure in the case of carrying out solid-phase polymerization under reduced pressure is preferably 1 kPa or less.

[0050] The resin composition of the present disclosure may contain other additives other than polyester (A) and polyester (B) as long as the effects of the present disclosure are not inhibited. Examples thereof include colorants such as dyes and pigments, stabilizers such as ultraviolet absorbers, antistatic agents, flame retardants, flame retardant aids, lubricants, plasticizers, inorganic fillers, and the like. The content of these additives in the resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, and may be preferably 2% by mass or less, 1% by mass or less, or 0.5% by mass or less in some cases.

[0051] The method for producing the resin composition of the present disclosure is not particularly limited. For example, (i) a method of dry-blending pellets made of polyester (A) and pellets made of polyester (B) and melt-kneading the obtained mixture into pellets or the like, (ii) a method of melt-kneading pellets made of polyester (A) and pellets made of polyester (B) into pellets or the like, and the like can be mentioned.

[0052] When polyester (A) and polyester (B) are recovered materials, as a method for producing the resin composition of the present disclosure, a production method including a step of pulverizing and drying the recovered material of polyester (A) and the recovered material of polyester (B), and a step of melt-kneading the dried product obtained in the above step may be used. The recovered material of polyester (A) and the recovered material of polyester (B) are The method of pulverization is not particularly limited. For example, a method of using a pulverizer to pulverize under the condition of a rotation speed of 100 to 2000 rpm to obtain flakes having a maximum diameter of 0.1 to 20 mm can be mentioned. After pulverization, the method of drying is not particularly limited. For example, a method of drying in a dryer under the condition of 80 to 150 °C for 0.5 to 48 hours can be mentioned. The method of melt-kneading the dried product is not particularly limited, and it may be melt-kneaded with a twin-screw extruder or the like, or a molded product may be continuously produced while melt-kneading using a hollow molding machine or the like. Polyester (A) and polyester (B) may be pulverized simultaneously in a mixed state, or may be mixed after being pulverized separately (or after being further dried). When the recovered products of polyester (A) and polyester (B) are of an appropriate size (for example, the maximum diameter is about 0.1 to 20 mm), they may be used without pulverization.

[0053] When at least polyester (B) is a recovered product, a production method may include a step of pulverizing and drying the recovered product of polyester (B), and a step of melt-kneading the dried product obtained in the above step and polyester (A). A production method may also include a step of pulverizing the recovered product of polyester (B), a step of dry-blending the pulverized product obtained in the above step and polyester (A), drying, and a step of melt-kneading the obtained dried product. The methods of drying, pulverizing, and melt-kneading may be the same as those described above. When the recovered product of polyester (B) is of an appropriate size (for example, the maximum diameter is about 0.1 to 20 mm), it may be used without pulverization.

[0054] A mixture containing polyester (A) and polyester (B), wherein the forms of polyester (A) and polyester (B) are pellets, flakes or powders, and polyester (A) is composed of at least one selected from the group consisting of polyester (A-1) containing 35 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 15 mol% of units derived from CHDM, and 45 to 50 mol% of units derived from terephthalic acid, and polyester (A-2) containing 43 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 7 mol% of units derived from EOBPA, and 45 to 50 mol% of units derived from terephthalic acid, based on all monomer units; polyester (B) contains 40 to 50 mol% of units derived from ethylene glycol and 40 to 50 mol% of units derived from terephthalic acid, the content of units derived from isophthalic acid in all monomer units of polyester (B) is 10 mol% or less, the content of units derived from CHDM is less than 1.5 mol%, and the content of units derived from EOBPA is less than 1.5 mol%; the intrinsic viscosity IV(A) of polyester (A) is 0.8 to 1.3 dl / g, the intrinsic viscosity IV(B) of polyester (B) is 0.6 to 0.9 dl / g, the absolute value of the difference between the intrinsic viscosity IV(A) and the intrinsic viscosity IV(B) (|IV(A) - IV(B)|) is 0.5 dl / g or less, and the mass ratio (A / B) of polyester (A) to polyester (B) is 0.1 / 99.9 to 50 / 50. A mixture is also one of the disclosures of the present application. The preferred embodiments of polyester (A) and polyester (B), the preferred embodiments regarding the intrinsic viscosity, and the preferred embodiments of the mass ratio (A / B) of polyester (A) to polyester (B) are the same as those described above as the preferred embodiments of the resin composition of the present application. The above mixture may contain other additives other than polyester (A) and polyester (B). The preferred embodiments of the types and contents of other additives are the same as those described above as the preferred embodiments of other additives that can be included in the resin composition of the present application. The other additives may be contained in the pellets, flakes or powders of polyester (A) or polyester (B).

[0055] The size of the pellets, flakes or powder is not particularly limited, and the longest diameter may be 0.1 to 50 mm, 0.5 to 20 mm or 1 to 10 mm.

[0056] The method for producing the mixture of the present disclosure is not particularly limited, and examples thereof include a method of dry blending pellets, flakes or powder made of polyester (A) and pellets, flakes or powder made of polyester (B).

[0057] A molded article obtained by extrusion molding the resin composition or mixture of the present disclosure, a molded article obtained by blow molding, and a molded article obtained by injection molding, as well as a container made of these molded articles, are also one of the present disclosures. Further, a film or sheet made of a molded article obtained by extrusion molding the resin composition or mixture of the present disclosure, and a thermoformed article obtained by thermoforming the above film or sheet are also one of the present disclosures.

[0058] By extrusion molding the resin composition or mixture of the present disclosure, a molded article can be obtained. The temperature of the resin composition or mixture during extrusion molding is preferably in the range of (melting point of the resin composition or mixture + 10°C) to (melting point of the resin composition or mixture + 70°C), and more preferably in the range of (melting point of the resin composition or mixture + 10°C) to (melting point of the resin composition or mixture + 40°C). By extruding at a temperature relatively close to the melting point, drawdown can be suppressed.

[0059] The resin compositions and mixtures of the present disclosure are particularly suitable for extrusion blow molding among extrusion moldings. The method of extrusion blow molding is not particularly limited and can be carried out in the same manner as the conventionally known extrusion blow molding method. For example, the resin composition or mixture of the present disclosure is melt-extruded to form a cylindrical parison, and while this parison is in a softened state, it is sandwiched between blow molds and a gas such as air is blown in to expand the parison into a predetermined hollow shape along the shape of the mold cavity.

[0060] The resin compositions and mixtures of the present disclosure are also suitable for profile extrusion molding. The method of profile extrusion molding is not particularly limited and can be carried out in the same manner as the conventionally known profile extrusion molding methods. For example, it can be carried out by a method of shaping by melt-extruding the resin composition or mixture of the present disclosure from a die of a predetermined shape.

[0061] A molded article can also be obtained by injection molding the resin composition or mixture of the present disclosure. The temperature of the resin composition or mixture during injection molding is preferably 230°C or higher, more preferably 245°C or higher. The mold cooling temperature is preferably 100°C or lower, more preferably 70°C or lower, and even more preferably 50°C or lower.

[0062] The resin compositions and mixtures of the present disclosure are particularly suitable for injection blow molding among injection moldings. The method of injection blow molding is not particularly limited and can be carried out in the same manner as the conventionally known injection blow molding methods. For example, it can be carried out by injection blow molding in which an injection molding machine and a blow molding machine are integrated, hot method injection stretch blow molding, cold method injection stretch blow molding in which an injection molding machine and a blow molding machine are independent and a stretching rod is used in the blow process, etc.

[0063] The containers of the present disclosure are preferably used as containers for filling soft drinks, seasonings, oils, cosmetics, detergents, and other products. Further, a molded article having a laminated structure of the resin composition or mixture of the present disclosure and other thermoplastic resins, etc. can also be obtained.

Examples

[0064] Hereinafter, the present invention will be described more specifically using examples.

[0065] (1) Intrinsic viscosity The intrinsic viscosities of the polyester pellets after melt polymerization, the polyester pellets after solid-phase polymerization, and the 100 ml bottles obtained in “(8) Molding property evaluation” were calculated from a calibration curve measured at a temperature of 30°C by dissolving the pellets or bottles after finely cutting them using an equal-mass mixture of phenol and 1,1,2,2-tetrachloroethane as a solvent and changing the concentration at three points.

[0066] (2) Content of each monomer unit The content (mol%) of each monomer unit constituting the polyester is 1 determined by 1H-NMR spectrum (apparatus: "JNM-GX-500 type" manufactured by JEOL Ltd., solvent: deuterated trifluoroacetic acid).

[0067] (3) Melting point Tm and glass transition temperature Tg The melting point Tm and glass transition temperature Tg of the polyester were measured using a differential scanning calorimeter (TA Q2000 type manufactured by TA Instruments). The melting point Tm and glass transition temperature Tg were calculated from the data when the temperature was raised from 30°C to 280°C at a heating rate of 10°C / min, then rapidly cooled to 30°C at -50°C / min, and then the temperature was raised again at a heating rate of 10°C / min.

[0068] (4) Blending of resins 20 kg of polyester pellets mixed at a predetermined ratio were put into a tumbler MT-50 manufactured by Matsui Seisakusho Co., Ltd., blended for 5 minutes, and then taken out to obtain a mixture of pellets.

[0069] (5) Production of bottles Using an electric hollow molding machine MSE-40E / 32M-A (T1) manufactured by Tahara Co., Ltd., extrusion blow molding of the obtained polyester was carried out at a cylinder maximum temperature of 280°C, a die temperature of 250°C, a molding cycle of 15 seconds, a screw rotation speed of 22 rpm, an extrusion resin pressure of 26 MPa, and a mold temperature of 30°C to obtain a transparent bottle with a volume of 220 ml.

[0070] (6) Crushing of bottles The bottles produced by the method described in "(5) Production of bottles" were put into the input hopper five by five using a crusher DAS-28 manufactured by Daiko Seiki Co., Ltd., and crushed under the condition of a rotation speed of 100 rpm to obtain crushed flakes of 5 mm or less.

[0071] (7) Evaluation of drying suitability A mixture (3 kg) of pellets or the like obtained in the examples and comparative examples was put into a dryer in a state of being spread over a stainless steel vat (35 cm in length, 30 cm in width, 5 cm in depth), and dried at 120°C for 6 hours. The state of the mixture after the drying treatment was visually observed, and the drying suitability was evaluated according to the following criteria. A: There is no welded product of 5 or more pellets or flakes of polyester (A) and pellets or flakes of polyester (B). B: It contains a welded product of 5 or more pellets or flakes of polyester (A) and pellets or flakes of polyester (B).

[0072] (8) Molding property evaluation As a reference example, using polyester B-1 as a raw material and an injection stretch blow molding machine ASB-12M manufactured by Nissei ASB Machine Co., Ltd., a 100 ml bottle was molded under the conditions of nozzle temperature: 290°C, cylinder temperature: 275 - 285°C, and molding cycle: 17.2 seconds. Using the mixture of pellets or the like obtained in the examples and comparative examples dried by the method described in "(7) Drying suitability evaluation" as a raw material, a 100 ml bottle was molded under the same conditions as the reference example or conditions with some modifications, and the molding property was evaluated according to the following criteria. A: It could be molded under the same conditions. B: It could not be molded under the same conditions, but could be molded by changing conditions such as temperature. C: It could not be molded even by changing conditions.

[0073] (9) Impact resistance 100 ml of water was put into the 100 ml bottle (polyester hollow container) obtained in "(8) Molding property evaluation", covered with a screw cap, and alternately dropped from a height of 1.25 m onto a concrete plate of an inclined surface / horizontal surface until the hollow container cracked, and the dropping was repeated 20 times, 10 times each. From the number of drops when the hollow container cracked, the impact resistance was evaluated according to the following criteria. A: The number of drops until cracking is 12 or more. B: The number of drops until cracking is 5 or more and less than 12. C: The number of drops until cracking is less than 5.

[0074] (10) Polyester Polyester A-4: PET resin GN001 manufactured by Eastman Chemical (CHDM-modified PET, CHDM unit content 31.6 mol%, TA unit content 50 mol%, EG unit content 18.4 mol%, Tg 79 °C, shape: pellet) Polyester B-1: PET resin 3822T manufactured by Nan Ya Plastics Industry Co., Ltd. (isophthalic acid-modified PET, isophthalic acid unit content 2.5 mol%, TA unit content 50 mol%, EG unit content 47.5 mol%, Tg 80 °C, Tm 246 °C, shape: pellet) Polyester B-2: PET resin PIFG5 manufactured by Bell Polyester Products Co., Ltd. (isophthalic acid-modified PET, isophthalic acid unit content 5 mol%, TA unit content 50 mol%, EG unit content 45 mol%, Tg 78 °C, Tm 240 °C, shape: pellet)

[0075] Production Example 1 In a polyester polymerization reaction tank, a slurry consisting of 50.97 parts by mass of terephthalic acid, 22.86 parts by mass of ethylene glycol, 2.16 parts by mass of cyclohexane-1,4-dimethanol [CHDM, mixing ratio of cis form to trans form (cis form / trans form) is 30 / 70], and 0.082 parts by mass of polyoxyethylene (20) sorbitan monolaurate was prepared. 0.00864 parts by mass of germanium dioxide was added as a catalyst, and 0.006 parts by mass of phosphoric acid was added as an antioxidant. This mixed solution was heated to 250 °C under pressure (absolute pressure 0.25 MPa) to carry out an esterification reaction to produce a low polymer. The above low polymer was melt polycondensed at 280 °C under a reduced pressure of 1 hPa to obtain a polyester having an intrinsic viscosity of 0.76 dl / g. The obtained polyester was extruded from a nozzle in a strand shape, cooled with water, and then cut into a cylindrical shape (diameter about 2.5 mm, length about 2.5 mm) to obtain polyester pellets (melt polycondensation pellets). The evaluation results of the obtained polyester pellets are shown in Table 1.

[0076] Production Example 2 In the same manner as in Production Example 1, except that 0.006 parts by mass of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] was added as an antioxidant, polyester pellets (melt polycondensation pellets) were obtained. The evaluation results of the obtained polyester pellets are shown in Table 1.

[0077] Production Example 3 In the same manner as in Production Example 2, except that a slurry consisting of 48.9 parts by mass of terephthalic acid, 19.63 parts by mass of ethylene glycol, and 7.42 parts by mass of cyclohexane-1,4-dimethanol [CHDM, mixing ratio of cis form and trans form (cis form / trans form) is 30 / 70] was used, polyester pellets (melt polycondensation pellets) were obtained. The evaluation results of the obtained polyester pellets are shown in Table 1.

[0078] Production Example 4 The polyester pellets obtained in Production Example 1 were put into a universal mixing stirrer and heated at 120°C for 2 hours with stirring to obtain pre-crystallized polyester. The obtained pre-crystallized polyester was put into a rolling type vacuum solid-phase polymerization apparatus and solid-phase polymerized at 200°C for 107 hours under 1 torr to obtain polyester pellets (solid-phase polymerization pellets, polyester A-1). The evaluation results of the obtained polyester pellets are shown in Table 2.

[0079] Production Example 5 In the same manner as in Production Example 4, except that the polyester pellets obtained in Production Example 2 were used, polyester pellets (solid-phase polymerization pellets, polyester A-2) were obtained. The evaluation results of the obtained polyester pellets are shown in Table 2.

[0080] Production Example 6 In the same manner as in Production Example 4, except that the polyester pellets obtained in Production Example 3 were used, polyester pellets (solid-phase polymerization pellets, polyester A-3) were obtained. The evaluation results of the obtained polyester pellets are shown in Table 2.

[0081] Example 1 Polyester A-1 and polyester B-1 were blended at the mixing ratios shown in Table 3 to obtain a mixture of polyester A-1 and polyester B-1. The evaluation results of the drying suitability, moldability, and bottle physical properties of the obtained mixture are shown in Table 3.

[0082] Examples 2 to 6 and 9, Comparative Examples 1 to 2 A polyester mixture was obtained in the same manner as in Example 1, except that the type of polyester (A), the type of polyester (B), and the mixing ratio of polyester (A) and polyester (B) were changed as described in Table 3. The evaluation results of the drying suitability, moldability, and bottle physical properties of the obtained mixture are shown in Table 3.

[0083] Example 7 Using polyester A-2, bottles were produced by the method described in "(5) Production of Bottles". The obtained bottles were ground into flakes by the method described in "(6) Grinding of Bottles" and blended with polyester B-1 at the mixing ratio shown in Table 3 to obtain a mixture of flakes of polyester A-2 and pellets of polyester B-1. The evaluation results of the drying suitability, moldability, and bottle physical properties of the obtained mixture are shown in Table 3.

[0084] Example 8 Using polyester B-1, bottles were produced by the method described in "(5) Production of Bottles". The obtained bottles were ground into flakes by the method described in "(6) Grinding of Bottles" and blended with pellets of polyester A-2 at the mixing ratio shown in Table 3 to obtain a mixture of flakes of polyester B-1 and pellets of polyester A-2. The evaluation results of the drying suitability, moldability, and bottle physical properties of the obtained mixture are shown in Table 3.

[0085] Example 10 Using polyester A-2, bottles were produced by the method described in "(5) Production of Bottles". Similarly, bottles were produced using polyester B-1. Each bottle was crushed by the method described in "(6) Crushing of Bottles", and the obtained flakes were blended at the mixing ratios described in Table 3 to obtain a mixture of flakes of polyester A-2 and flakes of polyester B-1. Table 3 shows the evaluation results of the drying suitability, moldability, and bottle physical properties of the obtained mixture.

[0086] Comparative Example 3 Using polyester B-2, bottles were produced by the method described in "(5) Production of Bottles". The obtained bottles were crushed by the method described in "(6) Crushing of Bottles", and the crushed flakes were blended with polyester A-2 at the mixing ratios described in Table 3 to obtain a mixture of flakes of polyester B-2 and pellets of polyester A-2. Table 3 shows the evaluation results of the drying suitability, moldability, and bottle physical properties of the obtained mixture.

[0087] [Table 1]

[0088] [Table 2]

[0089] [Table 3]

[0090] The mixtures of polyester (A) and polyester (B) obtained in Examples 1 to 10 were excellent in drying suitability and moldability, and the bottles made of the obtained resin compositions had excellent impact resistance. On the other hand, Comparative Examples 1 and 2 using polyester A-5 with a CHDM unit content of more than 15 mol% were inferior in drying suitability and moldability. Also, Comparative Example 3 with |IV(A) - IV(B)| greater than 0.5 dl / g was inferior in the impact resistance of the bottles.

Claims

1. A resin composition containing polyester (A) and polyester (B), wherein polyester (A) consists of at least one selected from the group consisting of polyester (A-1) containing, based on all monomer units, 35 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 15 mol% of units derived from cyclohexanedimethanol, and 45 to 50 mol% of units derived from terephthalic acid, and polyester (A-2) containing, based on all monomer units, 43 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 7 mol% of units derived from bisphenol A ethylene oxide adduct, and 45 to 50 mol% of units derived from terephthalic acid, polyester (B) contains, based on all monomer units, 40 to 50 mol% of units derived from ethylene glycol and 40 to 50 mol% of units derived from terephthalic acid, the content of units derived from isophthalic acid in polyester (B) based on all monomer units is 10 mol% or less, the content of units derived from cyclohexanedimethanol is less than 1.5 mol%, and the content of units derived from bisphenol A ethylene oxide adduct is less than 1.5 mol%, the intrinsic viscosity IV(A) of polyester (A) is 0.8 to 1.3 dl / g, and the intrinsic viscosity IV(B) of polyester (B) is 0.6 to 0.9 dl / g, the absolute value of the difference between the intrinsic viscosity IV(A) and the intrinsic viscosity IV(B) (|IV(A) - IV(B)|) is 0.5 dl / g or less, and the mass ratio of polyester (A) to polyester (B) (A / B) is 0.1 / 99.9 to 50 / 50. A resin composition.

2. The resin composition according to Claim 1, wherein the content of units derived from isophthalic acid in polyester (B) is 1.5 to 5 mol% based on all monomer units.

3. The resin composition according to Claim 1, wherein polyester (A) is polyester (A-1), and the content of units derived from cyclohexanedimethanol in polyester (A-1) is 1.5 mol% or more and less than 3.5 mol% based on all monomer units.

4. The resin composition according to Claim 1, wherein polyester (A) further contains, based on all monomer units, 0.001 to 0.2 mol% of units derived from a compound represented by the following formula (I). 【Chemical 1】 [In formula (I), the sum of x, y, z, and w is 1 to 50, and R １ ~R ４ each independently represents a hydrogen atom or an acyl group having 1 to 18 carbon atoms.]

5. The resin composition according to claim 4, wherein the compound represented by the formula (I) is at least one selected from the group consisting of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan trioleate.

6. The resin composition according to claim 1, wherein the polyester (A) and / or the polyester (B) further contains units derived from a hindered phenol antioxidant in an amount of 0.0005 to 0.2 mol% based on all monomer units.

7. The resin composition according to claim 1, wherein at least one of the polyester (A) and the polyester (B) contains a recovered material.

8. A mixture containing the polyester (A) and the polyester (B), wherein the forms of the polyester (A) and the polyester (B) are pellets, flakes or powders, the polyester (A) is at least one selected from the group consisting of a polyester (A-1) containing 35 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 15 mol% of units derived from cyclohexanedimethanol, and 45 to 50 mol% of units derived from terephthalic acid, and a polyester (A-2) containing 43 to 48.5 mol% of units derived from ethylene glycol, 1.5 to 7 mol% of units derived from a bisphenol A ethylene oxide adduct, and 45 to 50 mol% of units derived from terephthalic acid, based on all monomer units, the polyester (B) contains 40 to 50 mol% of units derived from ethylene glycol and 40 to 50 mol% of units derived from terephthalic acid based on all monomer units, the content of units derived from isophthalic acid in the polyester (B) based on all monomer units is 10 mol% or less, the content of units derived from cyclohexanedimethanol is less than 1.5 mol%, and the content of units derived from a bisphenol A ethylene oxide adduct is less than 1.5 mol%, the intrinsic viscosity IV(A) of the polyester (A) is 0.8 to 1.3 dl / g, and the intrinsic viscosity IV(B) of the polyester (B) is 0.6 to 0.9 dl / g, and the absolute value of the difference between the intrinsic viscosity IV(A) and the intrinsic viscosity IV(B) (|IV(A) - IV(B)|) is 0.5 dl / g or less. A mixture in which the mass ratio (A / B) of polyester (A) to polyester (B) is from 0.1 / 99.9 to 50 / 50.

9. A molded article obtained by extrusion molding the resin composition or mixture according to any one of Claims 1 to 8.

10. A molded article obtained by blow molding the resin composition or mixture according to any one of Claims 1 to 8.

11. A molded article obtained by injection molding the resin composition or mixture according to any one of Claims 1 to 8.

12. A film or sheet comprising the molded article according to Claim 9.

13. A thermoformed article obtained by thermoforming the film or sheet according to Claim 12.

14. A container comprising the molded article according to Claim 9.

15. A step of pulverizing and drying the recovered polyester (A) and the recovered polyester (B), and A method for producing the resin composition according to any one of Claims 1 to 7, comprising a step of melt-kneading the dried product obtained in the above step.

16. A step of pulverizing and drying the recovered polyester (B), and A method for producing the resin composition according to any one of Claims 1 to 7, comprising a step of melt-kneading the dried product obtained in the above step and polyester (A).

Images