JP2008291237A - Polyester elastomer composition, use thereof, and process for producing polyester elastomer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester elastomer excellent in heat resistance, mechanical properties, color tone, and aroma retainability, and advantageously usable as a container or a packaging material for foods, drinks or the like, and fibers. <P>SOLUTION: Disclosed is a polyester elastomer composition containing ≤50 ppm free aromatic dicarboxylic acid, ≤10 ppm free butane diol, ≤10 ppm free aromatic dicarboxylic acid monobutylene glycol ester, and ≤100 ppm free aromatic dicarboxylic acid dibutylene glycol ester in a polyester elastomer produced from a dicarboxylic acid component mainly comprising an aromatic dicarboxylic acid, a glycol component mainly comprising 1,4-butane diol and having a mol.wt. lower than 250 and a polyalkylene glycol having a mol.wt. of 400-6,000. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic polyester elastomer composition, and in particular, the content of free aromatic dicarboxylic acid, free butanediol, free aromatic dicarboxylic acid monobutylene glycol ester, and free aromatic dicarboxylic acid dibutylene glycol ester in the polyester elastomer. The present invention relates to a thermoplastic polyester elastomer composition having a very low content, and is suitable for various uses such as automobiles, home appliance parts, and packaging materials.

A polyester-polyether copolymer having an aromatic polyester as a hard segment and a polyalkylene glycol as a soft segment, that is, a polyester elastomer, is prepared by firstly dicarboxylic acid diester, glycol, and polyalkylene glycol. An ester exchange polymerization method in which an ester exchange reaction is performed and then polycondensation, and an esterification polymerization method in which a dicarboxylic acid, a glycol, and a polyalkylene glycol are esterified and then polycondensed are known. A large amount of free terephthalic acid, free butanediol, free aromatic dicarboxylic acid monobutyl glycol ester content, and free aromatic dicarboxylic acid dibutyl glycol ester content remain in the polymer obtained by the legal method. Appearance mer, heat resistance, that Fureba may decrease seen as a problem. In addition, the polyester elastomer produced by this transesterification polymerization method has a problem that the time required for polycondensation is long and the production cost is low, and that the viscosity is greatly reduced during casting (polymer removal) after completion of polycondensation.
JP-A-8-302000 JP-A-8-100054 JP 57-117527 A

  An object of the present invention is to solve the above-mentioned problems of the prior art, and is excellent in heat resistance, mechanical properties and color tone, and flavor retention, and is advantageous as a container for food or beverages, packaging materials and fibers. It is to provide a polyester elastomer that can be used.

In order to solve the above-mentioned problems, the present invention has finally been completed as a result of intensive studies. That is, the present invention is as follows.
(1) In a polyester elastomer obtained from a dicarboxylic acid component mainly composed of an aromatic dicarboxylic acid, a glycol component mainly composed of 1,4-butanediol and having a molecular weight of less than 250, and a polyalkylene glycol having a molecular weight of 400 to 6000, Free aromatic dicarboxylic acid is 50 ppm or less, free butanediol is 10 ppm or less, free aromatic dicarboxylic acid monobutylene glycol ester is 10 ppm or less, and free aromatic dicarboxylic acid dibutylene glycol ester is 100 ppm or less. A polyester elastomer composition characterized by the above.
(2) The aromatic dicarboxylic acid is terephthalic acid, the aromatic dicarboxylic acid monobutylene glycol ester is terephthalic acid monobutylene glycol ester, and the aromatic dicarboxylic acid dibutylene glycol ester is terephthalic acid dibutylene glycol ester. The polyester elastomer composition according to (1), characterized in that
(3) A fibrous material obtained by extruding the polyester elastomer composition according to (1) or (2).
(4) A sheet-like product obtained by extruding the polyester elastomer composition according to (1) or (2).
(5) A molded article comprising the polyester elastomer composition according to (1) or (2).
(6) A stretched film obtained by stretching the sheet-like material according to (4) in at least one direction.
(7) The manufacturing method of the polyester elastomer composition as described in (1) or (2).

  The polyester elastomer composition of the present invention is excellent in heat resistance and highly excellent in color tone and clarity, so that the molded body has excellent heat resistance, color tone, and flavor properties, and demanding fibers and molded products. It can be suitably used as a raw material for sheets, stretched films.

  The present invention will be described in detail below.

  In the present invention, the dicarboxylic acid component mainly comprising an aromatic dicarboxylic acid is 50 mol% or more of an aromatic dicarboxylic acid or a diester thereof, and examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 2 , 6-Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, diphenyl-p, p-dicarboxylic acid, 1,3-phenylenedioxy Diacetic acid and its functional derivatives. In particular, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and diphenyl-p, p-dicarboxylic acid tend to have high crystallization speed and good moldability. Of these, terephthalic acid is most preferable from the viewpoint of cost performance. Furthermore, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, glutaric acid, dimer acid and functional derivatives thereof, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid and the like The functional derivative can also be used in less than 50 mol%. The component other than the aromatic dicarboxylic acid is preferably less than 50 mol%, more preferably less than 40 mol%, most preferably less than 30 mol%, and if it exceeds 50 mol%, the crystallinity of the polyester elastomer tends to be lowered and molding is performed. And heat resistance tend to decrease.

  The polyalkylene glycol in the present invention may have a molecular weight of 400 to 6000, and may be a copolymer obtained by copolymerizing a polyalkylene glycol with other components depending on the case. Specific examples of the polyalkylene glycol include polyethylene glycol, Poly 1,3-propylene glycol, poly 1,2-propylene glycol, polytetramethylene glycol, polyneopentyl glycol, poly 3-methylpentanediol, poly 1,5-pentanediol, bis A-ethylene oxide adduct, Bis A-propylene oxide adducts, bis S-ethylene oxide adducts and the like and derivatives thereof are exemplified, and specific derivatives include, for example, a copolymer of polyneopentyl glycol and polyethylene glycol.

  When the molecular weight of the polyalkylene glycol is less than 400, the block property of the resulting polyester elastomer is lowered, so that the melting point / softening point of the polymer is lowered. Further, when the molecular weight exceeds 6000, there is a problem that the obtained polyester elastomer is phase-separated and becomes opaque and pearly.

The glycol having a molecular weight of less than 250, mainly composed of 1,4-butanediol, used in the present invention preferably contains 60 mol% or more of 1,4-butanediol, more preferably 70 mol% or more, It is most preferable to contain 80 mol% or more. If it is less than 60 mol%, the crystallinity tends to decrease and the moldability and heat resistance tend to decrease.
Specific examples of other glycols having a molecular weight of less than 250 include ethylene glycol, propylene glycol, 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 3-methyl-1. 5-pentanediol, 2-methyl-1, 5-pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonane Diol, 1,10-decanediol, etc. are mentioned. Alicyclic glycols include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 3,8-bisbidoxymethyltricyclodicican, hydrogenated bisphenol A, hydrogenated bisphenol F, TCD glycol, and the like can be used, and these can be used alone or in combination of two or more kinds. They may be used in combination with less than 30 mol%. When the molecular weight exceeds 250, the crystallinity is lowered, and the moldability and heat resistance is improved. It tends to decrease.

  As long as the content of the invention is not impaired, a carboxylic acid may be added. A method for introducing a carboxyl group includes trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride after polymerization of the polyester resin. Acid, 1,8-naphthalic acid anhydride, 1,2-cyclohexanedicarboxylic acid, etc. are post-added to give an acid value. As a modified polyester, there is a method of chain extension with dimethylolpropionic acid, dimethylolbutanoic acid or the like. Can be mentioned. Furthermore, as other copolymerization components used by copolymerization in the aromatic polyester used in the present invention, polyfunctional compounds, acid components, trimellitic acid, pyromellitic acid and the like can be mentioned, Examples of the glycol component include glycerin and pentaerythritol. The amount of the above copolymerization component used should be such that the aromatic polyester remains substantially linear.

  In addition, as for the molar ratio of the glycol with respect to the acid component which consists of dicarboxylic acid or its diester, 1.2 or more and 2.2 or less are preferable. In particular, 1.4 or more and 2.0 or less are preferable.

  Further, the block repeating unit comprising polytetramethylene glycol and the dicarboxylic acid component relative to the produced polyester elastomer, that is, the weight% of the soft segment unit can be selected according to the required elastic properties, but generally 5 to 80 wt. %, Especially about 5 to 70% by weight is preferable.

The heat resistance of the molded article made of the polyester elastomer of the present invention and the flavor of contents such as beverages that are in direct contact, the content of free low molecular compounds remaining in the polyester material, and the contents of these compounds to the contents As a result of diligent studies on the relationship with the amount of elution, not only the specific low molecular weight compounds but also the following various free low molecular weight compounds including glycols are in very small amounts. It was found that it eluted and influenced the flavor of the contents in a composite manner, and further the heat resistance was lowered.
Specifically, the upper limit of the free low molecular weight compound is that the polyester elastomer mainly composed of an aromatic dicarboxylic acid has a free aromatic dicarboxylic acid derived from the polyester of 50 ppm or less, a free butanediol of 10 ppm or less, a free aromatic If the content of the aromatic dicarboxylic acid monobutylene glycol ester is 10 ppm or less and the content of the free aromatic dicarboxylic acid dibutylene glycol ester is 100 ppm or less and the following, the flavor of the contents such as a container obtained from the polyester elastomer composition And fragrance can be maintained over a long period of time, and heat resistance is further improved.
Here, the aromatic dicarboxylic acid monobutylene glycol ester is a compound in which one carboxyl group of the aromatic dicarboxylic acid and 1,4-butanediol are bonded through an ester bond, and the aromatic dicarboxylic acid dibutylene glycol ester Is a compound in which two carboxyl groups of an aromatic dicarboxylic acid and two 1,4-butanediols are bonded via an ester bond.

  Free aromatic dicarboxylic acid derived from polyester is 50 ppm or less, free butanediol is 10 ppm or less, free aromatic dicarboxylic acid monobutylene glycol ester content is 10 ppm or less, free aromatic dicarboxylic acid dibutylene glycol ester content is In order to be 100 ppm or less and below, it is necessary to add an antioxidant at least one of the late stage of the polymerization reaction and immediately after completion of the polymerization reaction. Thus, it is considered that the radical trap function of the antioxidant, which is usually lost during the polymerization reaction when added before the polymerization reaction, contributes to the thermal stability of the polymer without being lost.

The polyester elastomer composition of the present invention has a free aromatic dicarboxylic acid derived from polyester of 50 ppm or less, a free butanediol of 10 ppm or less, a free aromatic dicarboxylic acid monobutylene glycol ester content of 10 ppm or less, a free aromatic In order for the dicarboxylic acid dibutylene glycol ester content to be 100 ppm or less and below, in addition to (1) adding an antioxidant at least one of the late stage of the polymerization reaction and immediately after the completion of the polymerization reaction, (2) the dicarboxylic acid component In addition, a polyester having a number average molecular weight of 5,000 to 50,000 obtained from a glycol component having a molecular weight of less than 250 and polytetramethylene glycol having a number average molecular weight of 400 to 70000 are mixed by heating and reacted in advance to a reduced viscosity of 0.2 dl / g or more. Polyester elastomer The Tomah was transferred to a thin-film evaporator or horizontal twin-screw reactor, two hundred and thirty to two hundred and fifty-five ° C., it is necessary to perform further polymerization reaction below 2 hPa.
Here, when heated and mixed, the polyester having a number average molecular weight of 5,000 to 50,000 is partially depolymerized at the same time as being dissolved, and reacts with polytetramethylene glycol.
In the conventional DMT method or TPA method using a dicarboxylic acid component and a glycol component having a molecular weight of less than 250 as raw materials, it is necessary to increase the reaction rate or to add excessive glycol having a molecular weight of less than 250 for process stability. Unreacted substances remain and free substances increase. On the other hand, by carrying out the above (1), the function of an antioxidant that is usually lost during the polymerization reaction can be maintained if it is added before the polymerization reaction. The production of free dicarboxylic acid, free diol, free aromatic dicarboxylic acid monobutylene glycol ester, and free aromatic dicarboxylic acid dibutylene glycol ester is suppressed. In addition, by the implementation of the above (2), it is not necessary to add an excessive glycol having a molecular weight of less than 250, and even when adding a glycol having a molecular weight of less than 250 for adjusting the reaction rate, the addition amount is small. , Less frees. Furthermore, since the polymerization reaction is carried out in a thin film evaporator or a horizontal biaxial reactor with high surface renewability, the reaction time can be shortened, and free dicarboxylic acid, free diol, and free aromatic dicarboxylic acid monobutylene glycol by thermal decomposition. Formation of ester and free aromatic dicarboxylic acid dibutylene glycol ester is suppressed.
In addition, at the time of carrying out the above (2), the addition of an antioxidant means that free dicarboxylic acid, free diol, free aromatic dicarboxylic acid monobutylene glycol ester, free by thermal decomposition during heating mixing or polymerization reaction, free Since the production | generation of aromatic dicarboxylic acid dibutylene glycol ester of is suppressed, it is a preferable aspect.

  The lower limit values of the free dicarboxylic acid and the free diol are each preferably 0. However, in order to make the free dicarboxylic acid less than 3 ppm and the free diol less than 0.6 ppm, it is necessary to set the production conditions at the expense of productivity. is not.

  According to the present invention, the upper limit of the free low molecular weight compound is the polyester elastomer mainly composed of aromatic dicarboxylic acid, in which free aromatic dicarboxylic acid derived from the polyester is 50 ppm or less, free butanediol is 10 ppm or less, free The aromatic dicarboxylic acid monobutylene glycol ester content is 10 ppm or less, and the free aromatic dicarboxylic acid dibutylene glycol ester content is 100 ppm or less.

Free aromatic dicarboxylic acid is 50 ppm or less, more preferably 40 ppm or less, free butanediol is 10 ppm or less, preferably 8 ppm or less, and the content of free aromatic dicarboxylic acid monobutylene glycol ester is 10 ppm or less, preferably Is 8 ppm or less, and the content of free aromatic dicarboxylic acid dibutylene glycol ester is 100 ppm or less, preferably 90 ppm or less.
Free aromatic dicarboxylic acid exceeds 50 ppm, free butanediol exceeds 10 ppm, free aromatic dicarboxylic acid monobutylene glycol ester content exceeds 10 ppm, free aromatic dicarboxylic acid dibutylene glycol ester content exceeds 100 ppm In the case of exceeding the above, the flavor and scent of the contents in the container etc. obtained from this polyester elastomer tend to be very poor, and the heat resistance tends to be further lowered.

  Here, when the polyester having a number average molecular weight of 5000 to 50000 is polybutylene terephthalate (hereinafter may be abbreviated as PBT), the aromatic dicarboxylic acid monobutylene glycol ester and the aromatic dicarboxylic acid dibutylene glycol ester are respectively These are terephthalic acid monobutylene glycol ester and terephthalic acid dibutylene glycol ester.

  When the polyester having a number average molecular weight of 5,000 to 50,000 is polybutylene naphthalate (hereinafter sometimes abbreviated as PBN), the aromatic dicarboxylic acid monobutylene glycol ester and the aromatic dicarboxylic acid dibutylene glycol ester are Corresponding compound.

  As the polycondensation catalyst, a compound of Ge, Sb, Ti, and Al is used. In particular, it is convenient to use a Ti compound alone or a mixture thereof with a Ge compound.

  Specific examples of the Ti compound include tetraalkyl titanates such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetra-n-butyl titanate and partial hydrolysates thereof, titanium acetate, titanyl oxalate. , Titanyl ammonium oxalate, titanyl sodium oxalate, potassium titanyl oxalate, calcium titanyl oxalate, titanium strontium oxalate, titanyl oxalate, titanium trimellitate, titanium sulfate, titanium chloride, titanium halide hydrolyzate, titanium oxalate, fluorine Titanium fluoride, potassium hexafluorotitanate, ammonium hexafluorotitanate, cobalt hexafluorotitanate, manganese hexafluorotitanate, titanium acetylacetonate, titanium and silicon or zirconium Ranaru composite oxide, a reaction product of titanium alkoxide and the phosphorus compound. The Ti compound is added so that the residual amount of Ti in the produced polymer is in the range of 0.1 to 300 ppm.

  As the Ge compound, it is preferable to use amorphous germanium dioxide, crystalline germanium dioxide powder or a solution of crystalline germanium dioxide dissolved in glycol. These polycondensation catalysts can be added during the esterification step or during the transesterification step. The Ge residual amount is preferably 10 to 1000 ppm, more preferably 13 to 900 ppm, and still more preferably 15 to 800 ppm.

  Specific examples of the Al compound include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, and aluminum lactate. , Carboxylates such as aluminum citrate and aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, polyaluminum chloride, aluminum nitrate, aluminum sulfate, aluminum carbonate, aluminum phosphate and aluminum phosphonate Aluminum methoxide, Aluminum ethoxide, Aluminum n-propoxide, Aluminum iso-propoxide, Aluminum n-bub Aluminum alkoxide such as xoxide, aluminum t-butoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethylacetoacetate diiso-propoxide, etc., organoaluminum compounds such as trimethylaluminum and triethylaluminum And a partial hydrolyzate thereof, aluminum oxide and the like. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred. Al compound is added so that it may become the range of 5-500 ppm as Al residual amount in the production | generation polyester elastomer.

  In the method for producing a polyester elastomer according to the present invention, an alkali metal compound or an alkaline earth metal compound may be used in combination. The alkali metal or alkaline earth metal is preferably at least one selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba, and the use of an alkali metal or a compound thereof is preferable. More preferred. When using an alkali metal or a compound thereof, use of Li, Na, K is particularly preferable. Examples of the alkali metal and alkaline earth metal compounds include saturated aliphatic carboxylates such as formic acid, acetic acid, propionic acid, butyric acid, and succinic acid, and unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid. , Aromatic carboxylates such as benzoic acid, halogen-containing carboxylates such as trichloroacetic acid, hydroxycarboxylates such as lactic acid, citric acid and salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, phosphorus Inorganic acid salts such as acid hydrogen, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid and bromic acid, and organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid and naphthalenesulfonic acid , Organic sulfates such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butyl Alkoxides such as alkoxy, chelate compounds and the like acetylacetonate, hydrides, oxides, and hydroxides and the like.

  The alkali metal compound or alkaline earth metal compound is added to the reaction system as powder, glycol solution or the like. The alkali metal compound or alkaline earth metal compound is added so that the residual amount of these elements in the produced polyester elastomer is in the range of 1 to 100 ppm.

When an Al compound is used as the polycondensation catalyst, it is preferably used in combination with a phosphorus compound.
The P compound used in the present invention is at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is preferably a phosphorus compound. By using these phosphorus compounds during the polymerization of the polyester, an effect of improving the catalytic activity and an effect of improving the thermal stability of the polyester can be seen. Among these, use of a phosphonic acid-based compound is preferable because of its large catalytic activity improvement effect and polyester thermal stability improvement effect. Among the above-described phosphorus compounds, use of a compound having an aromatic ring structure is preferable because it has a large catalytic activity improvement effect and a polyester thermal stability improvement effect.

  Examples of the Sb compound include antimony trioxide, antimony acetate, antimony tartrate, antimony potassium tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and triphenylantimony. The Sb compound is added so that the residual amount of Sb in the produced polyester elastomer is preferably in the range of 50 to 250 ppm. Other catalysts include tin compounds such as dibutyltin oxide and dibutyltin dilaurate, and lead compounds such as lead acetate.

  Moreover, it is preferable to use phosphoric acid esters such as phosphoric acid, polyphosphoric acid and trimethyl phosphate as the stabilizer. These stabilizers can be added during the esterification reaction step from a slurry preparation tank of terephthalic acid and ethylene glycol. The P compound is added so that the residual amount of P in the produced polymer is preferably in the range of 5 to 100 ppm.

It is preferable to add 0.01 to 5 parts by weight of an antioxidant to 100 parts by weight of the polyester elastomer in the present invention, more preferably 0.05 to 3 parts by weight, and most preferably 0.1 to 2 parts by weight. It is. If the amount added is less than 0.1 parts by weight, the amount of free substances tends to increase, and if it exceeds 5% by weight, the moldability of the mold tends to deteriorate during molding.
Specific examples of the addition method include a method of adding before the start of polymerization, during the polymerization reaction, or after the polymerization reaction. Specifically, one or more kinds of antioxidants such as hindered phenols, sulfur-based antioxidants and phosphorus-based antioxidants can be added as antioxidants. In addition, known hindered amines, triazoles, benzophenones, benzoates, nickels, salicyls and other light stabilizers, antistatic agents, lubricants, peroxides and other molecular modifiers, metal deactivators, One or more organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent brighteners, fillers, flame retardants, flame retardant aids, and the like can be added.

Hindered phenolic antioxidant As the hindered phenolic antioxidant in the present invention, 3,5-di-t-butyl-4-hydroxy-toluene, n-octadecyl-β- (4′-hydroxy-3 ′) , 5'-di-t-butylphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxy) Phenyl) propionate] methane, 1,3,5-trimethyl-2,4,6′-tris (3,5-di t-butyl-4-hydroxybenzyl) benzene, calcium (3,5-di-t-butyl-4-hydroxy-benzyl-monoethyl-phosphate), triethylene glycol-bis [3- (3-t- Butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl ] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis [3,3-bis (4′hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, tocopherol, 2,2 ′ -Ethylidenebis (4,6-di-t-butylphenol), N, N'-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4- Loxyphenylpropionamide), 1,3,5-bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-t-butylphenyl) ) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, N, N′-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2′-oxamidobis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S Triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5- Di-t-butyl-4-hydroxyhydrocinnamic acid triester with-1,3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H) be able to.

Sulfur-based antioxidant As the sulfur-based antioxidant in the present invention, dilauryl-3,3′-thiodipropionic acid ester, dimyristyl-3,3′-thiodipropionic acid ester, distearyl-3,3′- Examples thereof include thiodipropionic acid ester, lauryl stearyl-3,3′-thiodipropionic acid ester, dioctadecyl sulfide, pentaerythritol tetra (β-lauryl-thiopropionate) ester, and the like.
Phosphorous antioxidants Phosphorous antioxidants include tris (mixed, mono and dinolylphenyl) phosphite, tris (2,3-di-t-butylphenyl) phosphite, 4,4'-butylidene- Bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-tert-butylphenyl) butane, Bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphanite, bis (2,6 -Di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) 2-ethylhexyl-phosphite, bis (2,4,6-di-t-butylphenyl) pentaerythritol-di-phosphite, triphenyl phosphite, diphenyldecyl phosphite, didecylphenyl phosphite, tridecyl phosphite Phyto, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonylphenyl phosphite, tridodecyl trithiophosphite and the like can be mentioned.

Hindered amine light stabilizer In the present invention, the hindered amine system includes a polycondensate of dimethyl oxalate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperazine, poly [ [6- (1,1,3,3-tetrabutyl) imino-1,3,5-triazine-2,4-diyl] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imyl ] Bis (1,2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate of 2-n-butylmalonic acid, bis (2,2, 6,6-tetramethyl-4-piperidyl) sebacate, polycondensate of N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane The [(N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine)-(4-monophorino-1,3,5-triazine 2,6-diyl) -bis ( 3,3,5,5-tetramitylpiperazinone), tris (2,2,6,6-tetramethyl-4-piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate, tris ( 1,2,2,6,6-pentamethyl-4-piperidyl) -dodecyl-1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sebacate, 1,6,11-tris [{4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethylpiperidin-4-yl) amino-1,3,5- Triazin-2-yl} amino] undecane 1- [2- [3-5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetromethylpiperidine, 8-benzyl-7,7,9,9-tetra Methyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, N, N′-bis ( 3-Aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine A condensate etc. can be mentioned.

  Examples of light stabilizers such as triazole, benzophenone, benzoate, nickel, and salicylic acid in the present invention include 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, p -T-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amyluphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole 2,5-bis- [5′-t-butylbenzoxazolyl- (2)]-thiophene, [bis (3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethyl ester] nickel salt, 2-ethoxy-5-t-butyl-2'-ethyloxalic acid-bis-anilide 85-90% and 2-ethoxy-5-t-butyl-2'-ethyl-4'-t-butyloxalic acid A mixture of 10-15% bis-anilide, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethyl) Benzyl) phenyl] -2H-benzotriazole, 2-ethoxy-2′-ethyloxalic acid bisanilide, 2- [2′hydroxy-5′-methyl-3 ′-(3 ″, 4 ″, '', 6 ''-tetrahydrophthalimido-methyl) phenyl] benzotriazole, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2′-hydroxy-5′-t-octylphenyl) Examples include benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and the like.

Antistatic agent In the present invention, the antistatic agent includes glycerin fatty acid (C8 to C22) ester, sorbitan fatty acid (C8 to C22) ester, propylene glycol fatty acid (C8 to C22) ester, and sucrose fatty acid (C8 to C22) ester. , Citric acid mono (di- or tri) stearyl ester, pentaerythritol fatty acid (C8-C18) ester, trimethylolpropane fatty acid (C8-C18) ester, polyglycerin fatty acid (C8-C22) ester, polyoxyethylene (20 mol) Glycerin fatty acid (C12-C18) ester, oilyoxyethylene (20 mol) sorbitan fatty acid (C12-C18) ester, polyethylene glycol fatty acid (C8-C22) ester, polyoxyethylene fatty alcohol (C12-C20) ether, polyoxyethylene (4-5 Mole) alkyl (C4 or higher) phenyl ether, N, N-bis (2-hydroxyethyl) fat (C8 -C18) amine, condensation product of fatty acid and diethanolamine, polyoxypropylene polyoxyethylene block polymer, polyethylene glycol, polypropylene Nonionic surfactants such as glycols; alkyl (C10-C20) sulfonate (Na, K, NH4), alkylnaphthalene sulfonate (Na), sodium dialkyl (C4 -C16) sulfone succinate, alkyl ( Anionic surfactants such as C8 to C20) sulfate (Na, K, NH4) and fatty acid (C8 to C22) salts (Na, K, NH4); zwitterionic such as N-acyl (C8 to C18) sarcosinate Surfactant; other auxiliaries such as polyacrylic acid and its sodium salt Rukoto can.

Lubricants Lubricants that can be incorporated into the resin composition of the present invention include hexylamide, octylamide, stearylamide, oleylamide, erucylamide ethylenebisstearylamide, laurylamide, behenylamide, methylenebisstearylamide, ricinol C3-C30 saturated or unsaturated aliphatic amides and derivatives thereof such as amides; C3-C30 saturated or unsaturated aliphatic esters and derivatives thereof such as butyl stearate, isobutyl stearate, etc .; commercially available Silicone release agents such as silicone release agents, silicone oils and silicone gums; commercially available fluorine release agents such as tetrafluoroethylene and the like.

Metal Deactivator The metal deactivator that can be blended in the resin composition of the present invention includes 3-N′-salicyloylamino-1,2,4-triazole, salicylaldehyde, salicylhydrazine, N, N′-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, oxalyl-bis [benzylidenehydrazide], 9,10-dihydro-9-oxa-10-phospha Phenanthrene-10-oxide, 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide, tris [2-tert-butyl-4-thio (2′-methyl-4′-hydroxy-) 5-t-butyl) phenyl-5-methyl] phenyl phosphite, 2,2′-oxamido-bis- [ethyl-3 (3,5-di-t-butyl-4-hydroxy) Eniru) propionate], and the like can be mentioned.

As the nucleating agent that can be blended in the resin composition of the present invention, 1,3,2,4-di-benzylidene-sorbitol, 1,3,2,4-di-di- (p- Methyl-benzylidene) sorbitol, 1,3,2,4-di- (p-ethyl-benzylidene) sorbitol, 1,3,2,4-di- (2 ′, 4′-di-methyl-benzylidene) sorbitol, 1,3-p-chloro-benzylidene-2,4-p-methyl-benzylidene-sorbitol, 1,3,2,4-di- (p-propyl-benzylidene) sorbitol, aluminum mono-hydroxy-di-p -T-butylbenzoate, sodium-bis (4-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis- (4,6-di-t-butyl-phenyl) phosphate, talc And sodium benzoate, lithium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate, and the like.

Neutralizing agent and antacid agent As the neutralizing agent and antacid agent that can be blended in the resin composition of the present invention, lithium stearate, 1,2-hydroxylithium stearate, sodium stearoyl lactate, sodium stearate , Potassium stearate, lithium behenate, lithium montan, sodium behenate, sodium montanate, calcium stearyl lactate, calcium behenate, calcium montanate, cadmium stearate, cadmium lauryl, cadmium ricinoleate, barium naphthenate, 2- Barium ethylhexoate, barium stearate, barium 2-ethylhexoate, calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, zinc stearate, lauric acid sublimation Lead, zinc ricinoleate, zinc 2-ethylhexoate, zinc stearate, dibasic lead stearate, lead naphthenate, tin stearate, aluminum stearate, magnesium stearate and other higher fatty acids, alkyl lactic acid alkali or alkaline earth Metal salts: Basic magnesium, aluminum, hydroxy, carbonate, hydrate (hydrotalcite), basic zeolite, epichlorohydrin and bisphenol A polymer, epoxidized soybean oil, epoxidized fat-modified monoester, epoxidized Examples thereof include alicyclic fatty acid esters, polycarbodiimides, and isocyanate compounds.

Fillers Fillers that can be blended in the resin composition of the present invention include magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, titanium oxide, chromium oxide (trivalent), iron oxide, zinc oxide, silica, Diatomaceous earth, alumina fiber, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, oxide such as pumice and pumice balloon, basic substance or hydroxide such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate; Carbonates such as magnesium, calcium carbonate, barium sulfate, ammonium sulfate, calcium sulfite, dolomite, and dawsonite; (sulfite) sulfates such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, and basic magnesium sulfate; sodium silicate, magnesium silicate, Silica Silicates such as luminium, potassium silicate, calcium silicate, talc, clay, mica, asbestos, glass fiber, montmorillolite, glass balloon, glass beads, pentonite; kaolin (ceramic earth), perlite, iron powder, copper powder, lead Examples thereof include powder, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, brass fiber, potassium titanate, lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, calcium borate, and sodium borate.
Flame retardant The flame retardant of the present invention includes, but is not limited to, a type in which a halogen type is added to an antimony type, and a non-halo type includes a polyphosphoric acid type and a metal hydroxide type.
Specifically, antimony compounds include antimony trioxide, antimony tetroxide, and antimony pentoxide.
Halogen-based flame retardants include chlorine-based flame retardants, and specific representative examples of brominated flame retardants include decabromomodifyl ether, hexabromobenzene, hexabromocyclododecane, tetrapromobisphenol A, tetra Bromobisphenol A-tetraprobisbisphenol A.diglycidyl ether copolymer. Specific examples of chlorinated flame retardants include chlorinated paraffin and perchlorocyclodecane.
Specific examples of polyphosphate-based compounds include ammonium polyphosphate and melamine polyphosphate.
Examples of metal hydroxides (sometimes referred to as metal hydrates) include magnesium hydroxide and aluminum hydroxide.

  The polyester elastomer of the present invention has a molecular weight of less than 250 mainly composed of an aromatic dicarboxylic acid component and 1,4-butanediol as a first stage reaction in order to carry out melt polycondensation without adding a thermal history. It is produced by a direct esterification method in which an antioxidant is added to the glycol component, esterified while directly reacting to distill off water, and then polycondensation is performed under reduced pressure. Furthermore, the polyester which suppressed thermal history can be obtained by increasing an intrinsic viscosity and adding antioxidant at the time of taking out. Further, as the second-stage reaction, the polyester obtained above is dissolved in a polyalkylene glycol having a molecular weight of 400 to 6000, and further produced by an esterification exchange method in which polycondensation is performed under reduced pressure. Further, after completion of the melt polycondensation, it is preferable to take out the antioxidant after adding it in a molten state. Further, in order to form a chip, in a molten state under a short time at a temperature as low as possible until extrusion from the pores. It is obtained by holding.

As a specific production method, an antioxidant is preferably added to a dicarboxylic acid component mainly composed of aromatics and a glycol component mainly composed of 1,4-butanediol and having a molecular weight of less than 250, and 160 ° C to 210 ° C. After direct reaction and esterification while distilling off water, the reaction is carried out at 240 ° C. to 260 ° C. and a degree of vacuum of 600 to 0.1 Torr. In the case of polycondensation in a batch-type apparatus, the final polycondensation reaction should be completed within 1.5 hours under a reduced pressure of 240 to 260 ° C. and 5 to 0.1 Torr. When polycondensation is performed using a continuous apparatus, it is important that the final polycondensation reaction is completed within 2 hours under the conditions of 240 to 260 ° C. and 5 to 0.1 Torr. Further, the holding condition in the molten state after completion of the melt polycondensation should be within 60 minutes, preferably within 50 minutes, more preferably within 40 minutes at 240 to 250 ° C. When polycondensation is carried out at a high temperature of 260 ° C. or higher, or when polycondensation is carried out for a long time of 2 hours or more, the content of the low-molecular compound such as the above free monomer is more than the above limit amount, Coloring of the obtained polyester elastomer and flavor and smell heat resistance of the contents of the packaging material tend to be very poor. The obtained polyester was heated in a polyalkylene glycol having a molecular weight of 400 to 6000 from 130 ° C. to 220 ° C. over 2 hours to carry out a normal pressure transesterification reaction. Next, the temperature was raised from 220 ° C. to 245 ° C. over 1 hour, the pressure was reduced to 2 hPa or less, and the polymerization reaction was performed at 245 ° C. to a predetermined melt viscosity. It is important that the final polycondensation reaction is completed within 1 hour under the conditions of 240 to 260 ° C. and 5 to 0.1 Torr. Moreover, it is preferable to take out after adding antioxidant in the molten state after completion | finish of melt polycondensation.
For example, after the melt polycondensation, the antioxidant is added, for example, after the melt polycondensation is completed, the antioxidant is added to the polymerization kettle and stirred and mixed, or the molten resin is directly extruded after the melt polycondensation is completed. Examples include a method of mixing with an antioxidant supplied to a machine and separately supplying to an extruder. In this case, there is no problem even at normal pressure, but a method of blending under reduced pressure after addition is preferred.
After completion of melt polycondensation, if the antioxidant is added when the resin is once cooled and then re-melted with an extruder or the like, the content of the low-molecular compound such as the above free monomer exceeds the above limit amount. The resulting polyester elastomer tends to become colored and the flavor and smell of the contents of the packaging material tend to be very poor in heat resistance. Furthermore, the holding conditions should be within 240 minutes at 240 to 250 ° C., preferably within 50 minutes, more preferably within 40 minutes. When polycondensation is carried out at a high temperature of 260 ° C. or higher, or when polycondensation is carried out for a long time of 2 hours or more, the content of the low-molecular compound such as the above free monomer is more than the above limit amount, The resulting polyester elastomer is colored and the flavor and smell of the contents of the packaging material become so bad that the heat resistance is very poor.

  Ge, Sb, and Ti compounds are used as the transesterification catalyst, esterification catalyst, and polycondensation catalyst, with Ti compounds being particularly convenient. The titanium compound is preferably used by being dissolved in alcohol or glycol, and particularly preferably, titanium butoxide is dissolved in 1-butanol and added before esterification and / or transesterification. Further, Ti and Ge are preferably used in combination, and as the Ge compound, it is preferable to use amorphous germanium dioxide, crystalline germanium dioxide powder, or a solution obtained by dissolving crystalline germanium dioxide in glycol by heating.

  The polyester melt polycondensation reaction may be performed in a batch reactor or may be performed in a continuous reactor. In any of these methods, the melt polycondensation reaction may be performed in one stage or may be performed in multiple stages. The solid phase polymerization reaction can be carried out by a batch type apparatus or a continuous type apparatus, similarly to the melt polycondensation reaction. Melt polycondensation and solid phase polymerization may be carried out continuously or separately.

  The polyester elastomer thus obtained is less free compared to polymers obtained by conventional transesterification polymerization methods and esterification polymerization methods, and does not impair the flavor and heat resistance. It is favorable and has higher productivity than conventional transesterification polymerization methods and esterification polymerization methods, and is advantageous in terms of production cost.

Hereinafter, the present invention will be described in detail by way of examples. In addition, the polymer (polyester elastomer) characteristic in this example was measured by the following method. In the examples, “parts” means parts by weight.
(1) Reduced viscosity (hereinafter sometimes abbreviated as “ηsp / c”)
20 mg of the polymer is dissolved in 10 ml of a mixed solvent (phenol / tetrachloroethane = 60/40 weight ratio) and measured at 30 ° C. using an Ostwald viscometer.
(2) Degree of appearance coloring of polyester elastomer The polyester elastomer resin was visually determined.
○: Almost not colored Δ: Slightly yellowed or grayish ×: Remarkably yellow colored (3) Free butylene glycol content (hereinafter sometimes referred to as “BD content”)
The resin pellet sample is dissolved in a hexafluoroisopropanol / chloroform mixture, and then water is added to homogenize. BD was quantified by the gas chromatography method about the solution which filtered the aqueous phase.
(4) Content of low-molecular compounds such as free monomer The resin pellet sample is dissolved in a hexafluoroisopropanol / chloroform mixture, and further diluted with chloroflum. Methanol is added to this to precipitate a polymer and then filtered. The filtrate was evaporated to dryness, made up to volume with dimethylformamide, and quantified by liquid chromatography.
(5) Heat resistance The polymer was melted at 250 ° C. for 5 minutes in an air atmosphere, and the degree of coloring was measured by the method of (2).
(6) Sensory test (flavor property)
In order to prevent moisture absorption of the chip during molding, a dry inert gas (nitrogen gas) purge was performed in the molding material hopper using a polyester elastomer chip that was previously dried under reduced pressure using a vacuum dryer DP61 manufactured by Yamato Scientific. .
The plasticizing conditions of the M-150C (DM) injection molding machine are: feed screw rotation speed = 70%, screw rotation speed = 120 rpm, back pressure 0.5 MPa, cylinder temperature from 45 ° C. to 240 ° C. in order from directly below the hopper. Set the temperature to 245 ° C including the nozzle, mold a stepped molded plate, cut out a 3mm plate, put 70 ° C ion-exchange water in it, hold it for 30 minutes, cool to room temperature, leave it for 1 month, flavor after opening Tests such as odor were conducted. Ion exchange water is used as a blank for comparison. The sensory test was carried out by 10 panelists according to the following criteria, and the average values were compared.
0: No nasty taste or odor. 1: A slight difference from the blank is felt. 2: I feel the difference from the blank. 3: I feel a considerable difference from the blank. 4: I feel a very large difference from the blank.

Example 1
A reactor equipped with a rectification column was charged with 36.9 kg of DMT (dimethyl terephthalate), 37.7 kg of BD (butanediol), 150 g of an antioxidant IRGANOX 1330 (manufactured by Ciba Geigy Japan), and 60 g of TBT (tetrabutyl titanate), To 220 ° C. over 2 hours to carry out normal pressure transesterification. Next, the temperature was raised from 220 ° C. to 245 ° C. over 1 hour, the pressure was reduced to 2 hPa or less, and the polymerization reaction was performed at 245 ° C. to a predetermined melt viscosity. The reduced viscosity of the obtained polyester was 1.10 dl / g.
41.8 kg of the obtained polyester resin, 36.5 kg of PTMG (polytetramethylene glycol, number average molecular weight 1000), 150 g of the antioxidant IRGANOX 1330, and 41 g of titanium tetrabutoxy (TBT) were charged into a reactor, and the temperature was changed from 130 ° C. to 245 The temperature was raised to 0 ° C. over 1 hour, and the pressure was reduced to 2 hPa or less simultaneously with confirmation that the polyester was dissolved in PTMG. Thereafter, polymerization was carried out at 245 ° C. at 2 hPa or less, and then 375 g of IRGANOX 1098 (manufactured by Ciba Geigy Japan) was charged into the reaction vessel as an antioxidant, and the pressure was reduced to 2 hPa or less and mixed for 5 minutes. After mixing, the polymer was pelletized by casting and collected. The resulting polyester elastomer has a reduced viscosity of 1.90 dl / g, composition PTA // BD / PTMG = 100 // 81.0 / 19.0 (molar ratio), 38 ppm free aromatic dicarboxylic acid, free butanediol Was 6 ppm, the free aromatic dicarboxylic acid monobutyl glycol ester content was 5 ppm, the free aromatic dicarboxylic acid dibutyl glycol ester content was 88 ppm, and the color tone, heat resistance and flavor were good.

Examples 2-11
The polyester elastomers of Examples 2 to 11 were synthesized in the same manner as in Example 1 and the polymer properties were measured. The color tone, heat resistance and flavor properties were good. Shown in Tables 1 and 2.

Comparative Examples 1-4
A polyester polymerization apparatus is charged with 36.9 kg of DMT, 25.8 kg of BG, 36.5 kg of PTMG (number average molecular weight 1000), 150 g of the antioxidant IRGANOX 1330, 60 g of titanium tetrabutoxy (TBT), and 130 to 230 ° C. The temperature was raised to 2 ° C. over 2 hours to carry out a normal pressure transesterification reaction. Next, the temperature was gradually raised to 245 ° C. over 1 hour, and the pressure was reduced to 10 hPa to carry out initial polymerization. Furthermore, the pressure was reduced to 2 hPa or less, and the latter polymerization was performed to a predetermined melt viscosity at 245 ° C., and then the polymer was pelletized and recovered. The composition of the obtained polyester elastomer is PTA // BG / PTMG = 100 // 81.1 / 18.9 (molar ratio), the reduced viscosity is 1.40 dl / g, the free aromatic dicarboxylic acid is 100 ppm, the free butane Diol is 30 ppm or less, free aromatic dicarboxylic acid monobutyl glycol ester content is 38 ppm or less, free aromatic dicarboxylic acid dibutyl glycol ester content is 160 ppm, color tone is slightly inferior, heat resistance and flavor properties are inferior It was. As in Comparative Example 1, when the polyester elastomers of Comparative Examples 2 to 4 were synthesized and the polymer characteristics were measured, the color tone was slightly inferior, and the heat resistance and flavor properties were both poor. Table 3 shows.

  The polyester elastomer resin of the present invention is excellent in heat resistance, moldability, mechanical properties, and aroma retention, and is suitable for various uses centering on automobiles, home appliance parts, and packaging materials.

Claims (7)

  In a polyester elastomer obtained from a dicarboxylic acid component mainly composed of an aromatic dicarboxylic acid, a glycol component mainly composed of 1,4-butanediol and having a molecular weight of less than 250, and a polyalkylene glycol having a molecular weight of 400 to 6000, free aromatic An aromatic dicarboxylic acid is 50 ppm or less, a free butanediol is 10 ppm or less, a free aromatic dicarboxylic acid monobutylene glycol ester is 10 ppm or less, and a free aromatic dicarboxylic acid dibutylene glycol ester is 100 ppm or less. A polyester elastomer composition.   The aromatic dicarboxylic acid is terephthalic acid, the aromatic dicarboxylic acid monobutylene glycol ester is terephthalic acid monobutylene glycol ester, and the aromatic dicarboxylic acid dibutylene glycol ester is terephthalic acid dibutylene glycol ester The polyester elastomer composition according to claim 1.   A fibrous material obtained by extruding the polyester elastomer composition according to claim 1 or 2.   A sheet-like product obtained by extruding the polyester elastomer composition according to claim 1 or 2.   A molded article comprising the polyester elastomer composition according to claim 1.   A stretched film obtained by stretching the sheet-like material according to claim 4 in at least one direction. The manufacturing method of the polyester elastomer composition of Claim 1 or 2.