JP2006321908A - Polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition of melt-molding mainly using reclaimed flakes of PET bottles, which composition is softened by decreasing rigidity at room temperature and gives environment-friendly moldings having high surface hardness. <P>SOLUTION: The polyester resin composition obtained by melt-mixing two or more polyester resins comprises a thermoplastic polyester elastomer resin as an essential component of the component and has 10/90 to 99/1 mass ratio of Ge/Sb contained in the whole composition as the catalyst. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyester resin composition for providing an environment-friendly molded product that is softened by lowering the rigidity at room temperature and has a high surface hardness.

  In recent years, among polyester resins, especially polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is carbonated beverages, juices, mineral waters, etc. due to its excellent transparency, mechanical strength, heat resistance, gas barrier properties, etc. It is used as a material for hollow molded articles (containers) such as soft drinks, cosmetics, pharmaceuticals, and detergents, and its spread is remarkable.

  As a method for producing a hollow molded body made of polyester, an injection molding method in which molten polyester is directly injected into a mold to directly form a molded product, or a molten resin is injected into a mold to form a sealed parison (preform) once. An injection blow method or a stretch blow molding method in which air is blown by inserting it into a blow mold after being formed is generally employed.

  However, the injection molding method, the injection blow method, or the stretch blow molding method requires a high level of technology in the production and molding of molds, and is a container with a complicated shape having fine objects, deep objects, large objects, handles, etc. Is difficult to manufacture. In addition, these molding methods are suitable for mass-produced containers due to high equipment costs such as molds and molding equipment, but have a problem that they are not suitable for multi-product / small-volume production. For these reasons, a PET extrusion blow molding method (direct blow molding method) is adopted for molding of pharmaceutical containers such as eye drops.

  Direct blow molding (extrusion blow molding) is a molding method in which melt-plasticized resin is extruded through a die orifice to form a cylindrical parison, which is sandwiched between molds and air is blown into the interior. It has features such as ease, high productivity, and relatively low equipment costs for molding machines and molds. In the case of this direct blow molding, it is necessary to avoid that the parison extruded in the molten state is drawn down during blow molding in order to perform the molding smoothly, and a high melt viscosity is required for the resin used. For this reason, vinyl chloride resins and polyolefins having a high melt viscosity are generally suitable for this direct blow molding, and polyester resins have not been particularly suitable for molding large containers.

  In general, PET is produced mainly using terephthalic acid and ethylene glycol as raw materials, and using a germanium compound, an antimony compound, a titanium compound, a tin compound, an aluminum compound, and a mixture thereof as a polycondensation catalyst.

  The obtained PET has a relatively high elastic modulus and thus has a good rigidity, and can be developed for various uses. It is still used for containers, packaging, films, fibers, engineering plastics, and the like. However, when this PET is deployed in applications where flexibility is required, a certain degree of effect is manifested by making ultrafine fibers and thinning, but it is extremely difficult to realize flexibility such as rubber and polyolefin. It is difficult.

  Patent Document 1 shows that by blending multilayer structure particles made of rubber-based components, the elastic modulus of the recycled PET flakes is lowered and the impact resistance is improved. Patent Document 2 shows that by blending polypropylene and an unsaturated carboxylic acid-modified ethylene-based or styrene-based polymer, the elastic modulus is lowered and the impact resistance is improved. In Patent Document 3 and Patent Document 4, a rubber-based resin as a thickener and an ethylene-based or styrene-based elastomer as a polymerizing agent are blended to lower the elastic modulus and improve impact resistance. It is shown.

  Kneading of the above impact resistance improver and recycled PET flakes reduces the gloss inherent in PET due to the addition of different polymers, and because the compatibility between polymer materials is not good, The formulation is accompanied by the occurrence of many secondary problems such as volatilization of degradation products and mixtures from polymers added to PET.

  Moreover, since the above-mentioned impact resistance improver is formulated to improve the impact resistance by reducing the elastic modulus of the recycled PET flake resin composition, it gives the flexibility of the molded product as a result. However, the surface hardness of the surface of the molded product is lowered. This is thought to be because the impact modifier, which is a different polymer added to the R-PET flakes, has a relatively large amount, and thus inhibits crystallization of R-PET.

  On the other hand, the PET bottle disposal problem has attracted attention, and PET bottle scrap processing has become a social problem as an environmental problem. From such a background, recycling of used PET bottles has been intensively studied. However, since the reuse of recycled PET flakes is centered on products made by spinning and film formation similar to PET, a resin composition that can effectively utilize the resin characteristics of this recycled PET bottle and impart a new function is provided. It has become necessary to propose and promote expansion of applications. As an example, an environment-friendly polyester resin composition and molded article having low rigidity at room temperature and high surface hardness have been demanded, but have not been proposed yet.

JP 2001-2903 A (pages 2-7) JP 2001-114995 A (pages 2 to 3) JP 2002-146167 A (pages 2 to 3) JP 2002-249649 A (pages 2 to 4)

  An object of the present invention is to provide a polyester resin composition having a high surface hardness and particularly suitable for producing a flexible polyester resin molded article. In particular, it is an object of the present invention to provide an environment-friendly molded product having a high surface hardness that is softened by reducing the rigidity at room temperature with respect to a resin composition containing PET bottle recycled flakes as a main raw material.

As a result of intensive studies to achieve the above problems, the present inventors have completed the present invention. That is, this invention is the following polyester resin compositions.
(1) In a polyester resin composition obtained by melt-mixing two or more kinds of polyester resins, a thermoplastic polyester elastomer resin is an essential component of the composition, and germanium atoms / antimony atoms contained as a catalyst in the entire composition The polyester resin composition characterized by having a mass ratio of 10/90 to 99/1.
(2) In a polyester resin composition obtained by melt-mixing two or more polyester resins, a thermoplastic polyester elastomer resin is an essential component of the composition, and is contained as a catalyst in the entire composition (germanium atom + antimony A polyester resin composition having a mass ratio of (atoms) / titanium atoms of 10/90 to 99/1.

  By using the polyester resin composition of the present invention, it is possible to provide an environment-friendly molded product that is softened by reducing the rigidity at room temperature and has a high surface hardness.

In the present invention, when the mass ratio of germanium atoms / antimony atoms contained as a polymerization catalyst for the polyester resin in the resin composition is 10/90 to 99/1, the surface glossiness of the molded product is improved, and the molding cycle Will improve. This is due to the fact that germanium atoms and antimony atoms are simultaneously contained. When an excessive amount of antimony atoms is contained as a polyester polymerization catalyst, crystallization at the time of molding is fast, the molded product is likely to be whitened, and surface unevenness occurs. Moreover, when a polyester polymerization catalyst is only an antimony atom, the heat resistance of a molded article becomes low. In addition, when only a germanium metal catalyst is used as the polyester polymerization catalyst, the heat resistance of the molded product is high and the surface glossiness of the molded product is very good, but the releasability from the mold is slow due to slow crystallization. However, various problems remain, such as a deterioration of the molding cycle, a decrease in the surface hardness of the molded product, and the external side surface being easily damaged. Therefore, it is preferable that the polyester resin composition contains germanium atoms and antimony atoms at the same time, maintains high heat resistance, high surface gloss, and molded product surface hardness, and improves mold releasability. The compounding ratio of germanium atoms and antimony atoms is preferably high in germanium atoms, and the content ratio of germanium atoms and antimony atoms in the polyester resin composition is 10/90 to 99/1% by mass. More preferably, it is 20 / 80-95 / 5 mass%, Most preferably, it is 20 / 80-90 / 10 mass%.

  The preferred content of germanium atoms and antimony atoms in the polyester resin composition is 100 ppm / 900 ppm to 990 ppm / 10 ppm. More preferably, it is 10 ppm / 90 ppm to 95 ppm / 5 ppm, and most preferably 20 ppm / 80 ppm to 90 ppm / 10 ppm.

  In the present invention, when the mass ratio of (germanium atom + antimony atom) / titanium atom contained as a polymerization catalyst for the polyester resin in the resin composition is 10/90 to 99/1, the compatibility at the time of melt kneading of the polyester And the resin fluidity during molding is improved. This is because germanium atoms, antimony atoms, and titanium atoms are simultaneously contained. When an excessive amount of antimony atoms is contained as a polyester polymerization catalyst, crystallization at the time of molding is fast, the molded product is likely to be whitened, and surface unevenness occurs. Moreover, when a polyester polymerization catalyst is only an antimony atom, the heat resistance of a molded article becomes low. In addition, when only the germanium atom is used as the polyester polymerization catalyst, the heat resistance of the molded product is high and the surface glossiness of the molded product is very good, but since the crystallization is slow, the releasability from the mold is low. Various problems remain, such as deterioration, a molding cycle being lowered, a molded product surface hardness being lowered, and an external side surface being easily damaged. In the present invention, when a mixture containing a thermoplastic polyester elastomer is melt-kneaded, compatibility with one polyester is not good in the presence of germanium atoms and antimony atoms. For this reason, when a polyester resin containing a titanium atom as a catalyst is used, the transesterification reaction during melt kneading is promoted, the resin fluidity of the polyester resin composition mainly composed of a thermoplastic polyester elastomer is improved, and the moldability is improved. And the appearance of the molded product is also improved. Containing germanium atoms, antimony atoms, and titanium atoms at the same time, maintaining high heat resistance, high surface gloss, and molded product surface hardness, improving mold releasability, resin flowability, and moldability, and appearance of molded products It is preferable to improve. The blending ratio of (germanium atom + antimony atom) / titanium atom is preferably large (germanium atom + antimony atom), and the content ratio of (germanium atom + antimony atom) / titanium atom in the polyester resin composition is 10/90 to 99/1% by mass. More preferably, it is 20 / 80-95 / 5 mass%, Most preferably, it is 20 / 80-90 / 10 mass%.

  The preferable content of (germanium atom + antimony atom) / titanium atom in the polyester resin composition is 100 ppm / 900 ppm to 990 ppm / 10 ppm. More preferably, it is 10 ppm / 90 ppm to 95 ppm / 5 ppm, and most preferably 20 ppm / 80 ppm to 90 ppm / 10 ppm.

  The polycondensation catalyst used in producing the polyester used in the present invention can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system before the start of the esterification reaction or transesterification reaction and at any stage during the reaction or immediately before the start of the polycondensation reaction or during the reaction.

  The polycondensation catalyst used in the production of the polyester used in the present invention may be added in the form of powder or neat, or in the form of a slurry or solution of a solvent such as ethylene glycol. There is no particular limitation. Moreover, you may add as a mixture or complex which mixed the other component previously, and may add these separately.

  Examples of the antimony compound that can be added include antimony trioxide, antimony pentoxide, antimony acetate, antimony glycoloxide, and the like, and the use of antimony trioxide is particularly preferable. Examples of the germanium compound include germanium dioxide and germanium tetrachloride, and germanium dioxide is particularly preferable.

  The resin composition of the present invention is obtained by melt-mixing two or more kinds of polyester resins. Therefore, germanium atoms and antimony atoms contained as a catalyst in the whole composition may be melt-mixed with a germanium catalyst polyester resin and an antimony catalyst polyester resin, or a polyester resin using a combination of a germanium catalyst and an antimony catalyst is used. May be.

  The polycondensation catalyst used in producing the polyester used in the present invention is, for example, polymerization by transesterification of an alkyl ester of a dicarboxylic acid such as dimethyl terephthalate and a glycol such as ethylene glycol. Since the reaction is performed in the presence of a transesterification catalyst such as a compound, the catalyst used in the present invention can be used instead of these catalysts or in the presence of these catalysts. Further, the catalyst used in the present invention may be one having catalytic activity not only in melt polymerization but also in solid phase polymerization or solution polymerization. As a specific example, in addition to antimony compounds and germanium compounds, other polycondensation catalysts such as titanium compounds, tin compounds and aluminum compounds can be added to products such as polyester characteristics, processability and color tone as described above. They may be used together within the range of the added amount that does not cause a problem.

  Other polymerization catalysts such as titanium compounds and tin compounds include tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-tert-butyl titanate, tetracyclohexyl titanate, tetra Examples thereof include phenyl titanate and tetrabenzyl titanate, and tetrabutyl titanate is particularly preferable. In addition, as tin compounds, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin sulfide, Examples thereof include dibutylhydroxytin oxide, methylstannoic acid, and ethylstannic acid, and the use of monobutylhydroxytin oxide is particularly preferable.

  Specific examples of the aluminum 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, aluminum salicylate, inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, aluminum t-butoxide Any aluminum alkoxide, aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, aluminum ethyl acetoacetate diiso-propoxide, etc., aluminum chelate compounds, trimethylaluminum, triethylaluminum etc. organoaluminum compounds and their partial hydrolysis Products, aluminum oxide and the like. Of these, carboxylates, inorganic acid salts and chelate compounds are preferred, and among these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride and aluminum acetylacetonate are particularly preferred.

  The amount of aluminum or aluminum compound used is preferably 0.001 to 0.05 mol%, more preferably, based on the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the polyester obtained. Is 0.005 to 0.02 mol%. If the amount used is less than 0.001 mol%, the catalytic activity may not be sufficiently exerted. If the amount used exceeds 0.05 mol%, the thermal stability or thermal oxidation stability is lowered, resulting from aluminum. Occurrence of foreign matters or increased coloring may be a problem. As described above, the polymerization catalyst used in the present invention has a great feature in that it exhibits a sufficient catalytic activity even if the amount of the aluminum component added is small. As a result, thermal stability and thermal oxidation stability are excellent, and foreign matters and coloring caused by aluminum are reduced.

  In the case of using an aluminum polymerization catalyst, it is effective to use a phenol compound in combination for enhancing the catalytic activity. By adding a phenolic compound during the polymerization of the polyester, the catalytic activity of the aluminum compound is improved, and the thermal stability of the polymerized copolyester is also improved.

The amount of the phenolic compound used is preferably 5 × 10 ^{−7 to} 0.01 mol, more preferably based on the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the polyester obtained. Is 1 × 10 ^{−6 to} 0.005 mol. In the present invention, a phosphorus compound may be used together with the phenol compound.

  In the case of using an aluminum polymerization catalyst, it is effective to use a phosphorus compound in combination to increase the catalytic activity. Although it does not specifically limit as a phosphorus compound which comprises the polycondensation catalyst used for this invention, A phosphonic acid type compound, a phosphinic acid type compound, a phosphine oxide type compound, a phosphonous acid type compound, a phosphinic acid type compound, a phosphine Use of one or more compounds selected from the group consisting of a series compound is preferable because the effect of improving the catalytic activity is great. Among these, when one or more phosphonic acid compounds are used, the effect of improving the catalytic activity is particularly large and preferable.

The amount of the phosphorus compound used is preferably 5 × 10 ^{−7 to} 0.01 mol, more preferably relative to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the polyester obtained. 1 × 10 ^{−6 to} 0.005 mol.

  Furthermore, the phenol compound is preferably a phosphorus compound. Here, the phenol compound being a phosphorus compound means a phosphorus compound having a phenol moiety in the same molecule.

  The phosphorus compound having a phenol part constituting the polycondensation catalyst used in the present invention in the same molecule is not particularly limited as long as it is a phosphorus compound having a phenol structure, but the phosphone having a phenol part in the same molecule. When one or more compounds selected from the group consisting of acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds are used, the effect of improving catalytic activity is greatly preferred. . Among these, when a phosphonic acid compound having one or more phenol moieties in the same molecule is used, the effect of improving the catalytic activity is particularly large and preferable.

  By adding a phosphorus compound having these phenol moieties in the same molecule during the polymerization of the polyester, the catalytic activity of the aluminum compound is improved and the thermal stability of the polymerized polyester is also improved.

The amount of the phosphorus compound having a phenol moiety in the same molecule is 5 × 10 ^{−7 to} 0.0.1 with respect to the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the obtained polyester. 01 mol is preferable, More preferably, it is 1 * 10 < ^-6 > -0.005 mol.

  In the present invention, it is preferable to use a metal salt compound of phosphorus as the phosphorus compound. The phosphorus metal salt compound which is a preferred phosphorus compound constituting the polymerization catalyst used in the present invention is not particularly limited as long as it is a metal salt of a phosphorus compound, but catalytic activity is obtained when a metal salt of a phosphonic acid compound is used. The improvement effect is greatly preferred. Examples of the metal salt of the phosphorus compound include a monometal salt, a dimetal salt, and a trimetal salt.

  Further, among the above-described phosphorus compounds, when the metal portion of the metal salt is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn, the catalytic activity is improved. Is preferable. Of these, Li, Na, and Mg are particularly preferable.

  A technique of adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound to obtain a catalyst having sufficient catalytic activity is known. When such a known catalyst is used, a polyester having excellent thermal stability can be obtained. However, a known catalyst used in combination with an alkali metal compound or an alkaline earth metal compound is added in an amount to obtain a practical catalytic activity. Is necessary, and when an alkali metal compound is used, the amount of foreign matter resulting from it increases. In addition, when an alkaline earth metal compound is used in combination, the thermal stability and thermal oxidation stability of the resulting polyester are reduced when trying to obtain practical activity, coloring due to heating is large, and the amount of foreign matter generated is also low. Become more.

When adding an alkali metal, an alkaline earth metal and a compound thereof, the amount M (mol%) used is 1 × 10 ⁻⁶ or more and 0.1 or more relative to the number of moles of all polycarboxylic acid units constituting the polyester. it is preferably less than mol%, more preferably from 5 × ¹⁰ -6 to 0.05 mole%, more preferably 1 × ¹⁰ -5 to 0.03 mol%, particularly preferably 1 × 10 ^{- 5 to} 0.01 mol%. Since the amount of alkali metal or alkaline earth metal added is small, the reaction rate can be increased without causing problems such as a decrease in thermal stability, generation of foreign matter, and coloring. In addition, the reaction rate can be increased without causing problems such as degradation of hydrolysis resistance. When the use amount M of the alkali metal, alkaline earth metal and the compound thereof is 0.1 mol% or more, deterioration of thermal stability, generation of foreign matter, increase of coloring, deterioration of hydrolysis resistance, etc. become problems in product processing. A case occurs. When M is less than 1 × 10 ⁻⁶ mol%, the effect is not clear even if it is added.

  The polyester referred to in the present invention is composed of one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof and one or more selected from polyhydric alcohols containing glycols, or hydroxycarboxylic acids and Those consisting of these ester-forming derivatives or those consisting of cyclic esters.

  Dicarboxylic acids include succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 3-cyclobutane Illustrative examples include dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, and dimer acid. Saturated aliphatic dicarboxylic acids or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid and the like, or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid, Diphenine 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, Fragrances exemplified by 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, pamoic acid, anthracene dicarboxylic acid, etc. Group dicarboxylic acids or their ester-forming derivatives, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfo Metal sulfone exemplified by terephthalic acid Such as preparative group-containing aromatic dicarboxylic acids or their lower alkyl ester derivatives.

  Among the dicarboxylic acids described above, the use of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid is particularly preferred from the viewpoint of the physical properties of the resulting polyester, and other dicarboxylic acids are used as constituents as necessary.

  As polyvalent carboxylic acids other than these dicarboxylic acids, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid And ester-forming derivatives thereof.

  Examples of the glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1, 4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedi Methanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol, polyto Aliphatic glycols exemplified by methylene glycol and polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis (β-hydroxyethoxyphenyl) ) Sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A, bisphenol C, 2 , 5-naphthalenediol, aromatic glycols exemplified by glycols obtained by adding ethylene oxide to these glycols, and the like.

  Among the above glycols, it is particularly preferable to use ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol as the main component. Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like. Examples of hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these And ester-forming derivatives thereof.

  Examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, and lactide.

  Examples of ester-forming derivatives of polyvalent carboxylic acids and hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides, and the like.

  The polyester used in the present invention is preferably a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol.

  The polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of terephthalic acid or an ester-forming derivative thereof in total with respect to the total acid component. A polyester containing 80 mol% or more is preferable, and a polyester containing 90 mol% or more is more preferable. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is also preferably a polyester containing 70 mol% or more of naphthalenedicarboxylic acid or an ester-forming derivative thereof, more preferably 80 Polyesters containing at least mol%, more preferably polyesters containing at least 90 mol%.

  The polyester whose main glycol component is an alkylene glycol is preferably a polyester containing 70 mol% or more of the total amount of alkylene glycol with respect to all glycol components, more preferably a polyester containing 80 mol% or more, More preferably, it is a polyester containing 90 mol% or more. The alkylene glycol here may contain a substituent or an alicyclic structure in the molecular chain.

  Examples of the naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present invention include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid exemplified in the above dicarboxylic acids, 2, 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, or ester-forming derivatives thereof are preferred.

  A preferred example of the polyester used in the present invention is a polyester whose main repeating unit is composed of ethylene terephthalate, more preferably a linear polyester containing 70 mol% or more of ethylene terephthalate units, and still more preferably an ethylene terephthalate unit. A linear polyester containing 80 mol% or more is preferable, and a linear polyester containing 90 mol% or more of ethylene terephthalate units is particularly preferable.

  Another preferred example of the polyester used in the present invention is a polyester in which the main repeating unit is composed of ethylene-2,6-naphthalate, more preferably 70 mol% or more of ethylene-2,6-naphthalate unit. A linear polyester, more preferably a linear polyester containing 80 mol% or more of ethylene-2,6-naphthalate units, and particularly preferably a linear polyester containing 90 mol% or more of ethylene-2,6-naphthalate units. It is.

  Other preferable examples of the polyester used in the present invention include linear polyesters containing 70 mol% or more of propylene terephthalate units, linear polyesters containing 70 mol% or more of propylene naphthalate units, and 1,4-cyclohexanedimethylene terephthalate. A linear polyester containing 70 mol% or more of units, a linear polyester containing 70 mol% or more of butylene naphthalate units, or a linear polyester containing 70 mol% or more of butylene terephthalate units.

  The polyester resin composition of the present invention is obtained by melt mixing two or more of the above-described polyester resins. In that case, it is preferable that copolymer components other than a terephthalic acid / ethylene glycol are 1-30 mol% when the acid component / glycol component of the whole composition shall be 100/100 mol%. If the copolymerization component other than terephthalic acid / ethylene glycol is less than 1 mol%, the transparency during molding may not be improved. On the other hand, if it exceeds 30 mol%, the transparency is improved, but the moldability may be lowered, and the impact resistance of the molded product may be lowered. A preferable copolymerization amount of a copolymer component other than terephthalic acid / ethylene glycol is 2 to 25 mol%, more preferably 3 to 20 mol%. In addition, diethylene glycol produced | generated by the dimerization reaction of ethylene glycol shall not be considered in components other than the terephthalic acid / ethylene glycol said by this invention.

  The copolymer components other than the terephthalic acid / ethylene glycol are isophthalic acid, 2,6-naphthalenedicarboxylic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propane. It is preferably at least one selected from the group consisting of diol and 2-methyl-1,3-propanediol in order to achieve both transparency and moldability. In particular, isophthalic acid, diethylene glycol, neopentyl glycol, 1, More preferably, it is at least one selected from the group consisting of 4-cyclohexanedimethanol.

  Needless to say, a small amount (5 mol% or less) of diethylene glycol produced by dimerization of ethylene glycol may be included in the esterification (transesterification) reaction or polycondensation reaction.

  Next, the thermoplastic polyester elastomer resin used in the present invention will be described in detail. The thermoplastic polyester elastomer resin preferably has a hard segment and a soft segment in the molecule. Polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymer, polybutylene terephthalate, polybutylene terephthalate-isophthalate copolymer, polyethylene naphthalate, polyethylene naphthalate-terephthalate copolymer Polymer, polyethylene naphthalate-isophthalate copolymer, polyethylene naphthalate-terephthalate-isophthalate copolymer, polybutylene naphthalate, polybutylene naphthalate-terephthalate copolymer, polybutylene naphthalate-isophthalate copolymer And a hard segment which is at least one selected from the group consisting of a polybutylene naphthalate-terephthalate-isophthalate copolymer, and a poly (alkylene oxide) Those having a soft segment is a glycol and / or polycaprolactone in a molecule.

A: Aromatic dicarboxylic acid component used for hard segment In the thermoplastic polyester elastomer used in the present invention, the acid component is mainly composed of aromatic dicarboxylic acid. As the aromatic dicarboxylic acid, for example, it is preferable to use one or a combination of two or more acids selected from terephthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, and the like. Of these, terephthalic acid or naphthalenedicarboxylic acid is more preferred. The aromatic dicarboxylic acid is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more of the total acid component.

  Other acid components include alicyclic dicarboxylic acids and aliphatic dicarboxylic acids, and examples of the alicyclic dicarboxylic acids include cyclohexane dicarboxylic acid and tetrahydrophthalic anhydride. Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These acids are used within a range that does not significantly lower the melting point of the polyester elastomer, and the amount thereof is less than 30 mol%, preferably less than 20 mol%, more preferably less than 10 mol% of the total acid component.

B: Short-chain glycol component used for the hard segment As the short-chain glycol component in the polyester elastomer used in the present invention, glycol having 1 to 25 carbon atoms and ester-forming derivatives thereof can be used. Examples of the glycol having 1 to 25 carbon atoms include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 9-nonanediol, neopentyl glycol, dimethylol heptane, dimethylol pentane, tricyclodecane dimethanol, ethylene oxide derivatives of bisphenol X (X is A, S, F) and ester-forming derivatives thereof. Preferably, ethylene glycol, 1,4-butanediol and ester-forming derivatives thereof are used. Particularly preferred is 1,4-butanediol.

C: Soft segment Polyether glycol such as poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol having a number average molecular weight of 400 to 6,000, or aliphatic dicarboxylic acid having 2 to 12 carbon atoms And polyesters produced from aliphatic glycols having 2 to 10 carbon atoms, such as polyethylene adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebagate, polytetramethylene dodecanate, polytetramethylene azelate, polyhexamethylene Examples include azelate and poly-ε-caprolactone. The random copolymer polyether glycol component _also, -OCH 2 _CH 2 - (hereinafter also abbreviated as EO _{component), - OCH 2 CH 2 CH} 2 -, - OCH 2 CH 2 CH 2 CH 2 - ( hereinafter , there are times when abbreviated as THF _{component), - OCH 2 CH (CH} 3) - ( hereinafter also abbreviated as PO _{component), - OCH 2 C (CH} 3) 2 CH 2 - include alkylene oxide units, such as It is done. Preferred examples of the copolymerized polyether glycol component include polyether glycols in which tetramethylene oxide units (THF components) and ethylene oxide units (EO components) are randomly copolymerized. These soft segments are used in an appropriate combination depending on the balance of various characteristics.

  The content of the component C, which is the constituent component, in the thermoplastic polyester elastomer is preferably 1 to 85% by weight. More preferably, it is 2-70 weight%, More preferably, it is 5-55 weight%, Most preferably, it is 15-45 weight%. If the soft segment content is less than 1% by weight, the desired surface hardness may not be achieved or the moisture permeability may be lowered. On the other hand, if it exceeds 85% by weight, the blockability of the resulting elastomer is lowered, so that the melting point and softening point of the polymer may be lowered.

  Usually, in a thermoplastic polyester elastomer, measures such as adding a large amount of plasticizer and increasing the amount of soft segments of the thermoplastic polyester elastomer are taken when increasing flexibility. In the present invention, in order to have high flexibility, the amount of soft segments of the thermoplastic polyester elastomer can be increased to increase flexibility.

  The polyester elastomer used in the present invention can contain a tri- or higher functional polycarboxylic acid or polyol component only in a small amount. For example, trimellitic anhydride, benzophenone tetracarboxylic acid, trimethylolpropane, glycerin, pyromellitic anhydride or the like can be used at 3 mol% or less. The total amount of the tri- or higher functional polycarboxylic acid and the total polyol component is 5 mol% or less, preferably 3 mol% or less, where the total of all the polycarboxylic acid components and polyol components of the polyester is 100 mol%.

  The polyester elastomer used in the present invention preferably has a reduced viscosity of 1.0 to 4.0 dl / g. If the reduced viscosity is less than 1.0 dl / g, the mechanical properties may be inferior. If it exceeds 4.0 dl / g, the fluidity is poor and the moldability may be inferior, and the range of use as a molding material is limited. Come. The reduced viscosity is more preferably 1.5 to 3.7 dl / g, further preferably 2.0 to 3.4 dl / g, particularly preferably 2.3 to 3.2 dl / g, still more preferably 2.5. -3.0 dl / g.

  Any known method can be applied to the production of the polyester elastomer used in the present invention. For example, any of a melt polymerization method, a solution polymerization method, a solid phase polymerization method and the like can be used as appropriate. In the case of a melt polymerization method, a transesterification method or a direct polymerization method may be used. In order to improve the viscosity of the resin, it is of course desirable to perform solid phase polymerization after melt polymerization. Further, after polymerization of the polyester, the chain may be extended with an isocyanate compound or an epoxy compound.

  As the catalyst used for the polymerization reaction, an antimony catalyst, a germanium catalyst, and a titanium catalyst are preferable. Particularly preferred are titanium catalysts, specifically tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and oxalic acid metal salts such as titanium potassium oxalate. The other catalyst is not particularly limited as long as it is a known catalyst, and examples thereof include tin compounds such as dibutyltin oxide and dibutyltin dilaurate, and lead compounds such as lead acetate.

  In the resin composition of the present invention, the two or more polyester resins to be combined are preferably a polyethylene terephthalate resin. In consideration of environmental considerations such as recycling, one type is preferably a PET bottle recycled resin.

  As the PET bottle reclaimed resin used in the present invention, any material can be used as the raw material of the present invention as long as it is a recycled PET flake after pulverizing and washing steps after collecting the used PET bottle. is there. In this case, the shape of the PET bottle recycled flakes is particularly preferably a small surface area. Moreover, it is particularly preferable that the crushed PET bottle regenerated flakes are washed under alkaline conditions.

  Using a copolymer polyester resin as a polyester resin other than the thermoplastic elastomer resin is also a preferable embodiment in terms of enhancing transparency and impact resistance. The copolymer component is isophthalic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, adipic acid, sebacic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3 -Moldability obtained by copolymerizing at least one selected from the group consisting of propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, lactone compounds, D-lactic acid and L-lactic acid And transparency are preferable. Moreover, what copolymerized 1 or more types chosen from the group which consists of isophthalic acid, diethylene glycol, neopentyl glycol, and 1, 4- cyclohexane dimethanol is more preferable. The copolymerization amount is preferably 0.5 to 50 mol%, more preferably 3 to 40 mol%, still more preferably 5 to 35 mol%, most preferably 100 mol% each of the acid component and the glycol component. Is 7 to 20 mol%.

  Among these, terephthalic acid // ethylene glycol / diethylene glycol (90/10 to 99.5 / 0.5 (molar ratio)), terephthalic acid // ethylene glycol / neopentyl glycol (60/40 to 90/10 (molar ratio)) ), Terephthalic acid // ethylene glycol / 1,4-cyclohexanedimethanol (60/40 to 90/10 (molar ratio)), terephthalic acid / isophthalic acid (95/5 to 70/30 (molar ratio)) // The combination of ethylene glycol makes it easy to achieve both melt molding processability and transparency of the molded product.

  In the resin composition of the present invention, when one of the two or more kinds of polyester resins to be combined is a PET bottle recycled resin, it is preferable that both germanium atoms and antimony atoms are included as a catalyst thereof. That is, a recycled resin of a PET bottle molded using a PET resin polymerized using a germanium catalyst and an antimony catalyst may be used, or a recycled PET bottle molded using a PET resin polymerized using a germanium catalyst. You may use the mixture of the reproduction | regeneration resin of PET bottle shape | molded using resin and the PET resin polymerized using the antimony catalyst. The latter is more preferable in order to achieve both moldability and transparency at a high level.

  The PET bottle recycled resin preferably contains two or more of germanium atoms, antimony atoms, titanium atoms, aluminum atoms, phosphorus atoms, and zinc atoms. This is because the inclusion of two or more of these catalysts improves the compatibility at the time of melt-kneading the PET bottle recycled resin and other polyester resins, and improves the resin fluidity.

  Of the two or more kinds of polyester resins, the polyester resin other than the PET bottle regenerated resin preferably contains a titanium atom as a catalyst. This is a prescription necessary for developing good compatibility at the time of melt-kneading when the polyester resin other than the PET bottle recycled resin is a thermoplastic polyester elastomer resin. Usually, the thermoplastic polyester elastomer and the polyester resin are poorly compatible, but these polyester resins are very well compatible in the melt-kneading containing titanium atoms.

  The shape of the chip of the polyester resin, the thermoplastic elastomer resin, or the resin composition made of them used in the present invention may be any of a cylinder type, a square shape, a spherical shape, a flat plate shape, etc. The range is 1.5 to 5 mm, preferably 1.6 to 4.5 mm, and more preferably 1.8 to 4.0 mm. For example, in the case of a cylinder type, it is practical that the length is about 1.5 to 4 mm and the diameter is about 1.5 to 4 mm. In the case of spherical particles, it is practical that the maximum particle size is 1.1 to 2.0 times the average particle size and the minimum particle size is 0.7 times or more the average particle size. The mass of the chip is practically in the range of 15 to 30 mg / piece.

  The reduced viscosity of the polyester resin used in the present invention is preferably 0.55 to 1.50 dl / g, more preferably 0.58 to 1.30 dl / g, still more preferably 0.60 to 1.00 dl / g. The range of g. When the reduced viscosity is less than 0.55 dl / g, the mechanical properties of the obtained molded article may be poor. On the other hand, if it exceeds 1.50 dl / g, the resin temperature becomes high at the time of melting by a molding machine or the like, resulting in severe thermal decomposition, increasing the amount of free low molecular weight compounds that affect the fragrance retention, Problems such as yellowing may occur.

  For the polyester resin used in the present invention, a polyfunctional compound having 3 or more carboxyl groups, hydroxyl groups or ester-forming groups thereof (for example, trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane, etc.) is added to the polyester acid. It is preferable to contain 0.001-5 mol% of each of a component and a glycol component when improving a moldability.

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

  The thermoplastic polyester elastomer resin preferably has a hard segment and a soft segment in the molecule. In order to increase the flexibility and impact resistance of the molded product, polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymer, polybutylene terephthalate, polybutylene terephthalate-isophthalate copolymer, polyethylene naphthalate, polyethylene naphthalate-terephthalate copolymer Polymer, polyethylene naphthalate-isophthalate copolymer, polyethylene naphthalate-terephthalate-isophthalate copolymer, polybutylene naphthalate, polybutylene naphthalate-terephthalate copolymer, polybutylene naphthalate-isophthalate copolymer And a hard segment which is one or more selected from the group consisting of a polybutylene naphthalate-terephthalate-isophthalate copolymer, and a poly (alkylene oxide) Having a soft segment which is glycol and / or polycaprolactone in the molecule, and poly (alkylene oxide) glycol and terephthalic acid // ethylene glycol / diethylene glycol (90/10 to 99.5 / 0.5 (molar ratio)) ), Terephthalic acid // ethylene glycol / neopentyl glycol (60/40 to 90/10 (molar ratio)), terephthalic acid // ethylene glycol / 1,4-cyclohexanedimethanol (60/40 to 90/10 (mol) Ratio)), terephthalic acid / isophthalic acid (95/5 to 70/30 (molar ratio)) /// two or more polyester compositions selected from polyesters such as ethylene glycol are preferred.

  Specifically, as the thermoplastic polyester elastomer, [polyethylene terephthalate / poly (alkylene oxide) glycol copolymer] / (terephthalic acid // ethylene glycol / diethylene glycol = 90/10 to 99.5 / 0.5 (mol) Ratio)) in a weight ratio of 40/60 to 95/5 (weight ratio), [polybutylene terephthalate / poly (alkylene oxide) glycol copolymer] / (terephthalic acid // ethylene glycol / diethylene glycol = 90/10 to 99.5 / 0.5 (molar ratio)) is a composition having a weight ratio of 40/60 to 95/5 (weight ratio), [polybutylene terephthalate-isophthalate copolymer] / ( Terephthalic acid // ethylene glycol / diethylene glycol = 90/10 to 99.5 / 0.5 Molar ratio)) is 40/60 to 95/5 (weight ratio) by weight, [polybutylene terephthalate / polycaprolactone] / (terephthalic acid // ethylene glycol / diethylene glycol = 90/10 to 99.99). 5 / 0.5 (molar ratio)) in a weight ratio of 40/60 to 95/5 (weight ratio), [polybutylene terephthalate-isophthalate copolymer / polycaprolactone] / (terephthalic acid / / Ethylene glycol / diethylene glycol = 90/10 to 99.5 / 0.5 (molar ratio)) in a weight ratio of 40/60 to 95/5 (weight ratio), [polyethylene terephthalate / poly (alkylene Oxide) glycol copolymer] / (terephthalic acid // ethylene glycol / diethylene glycol) / (terephthalic acid / b) A composition or the like in which phthalic acid (95/5 to 70/30 (molar ratio)) // ethylene glycol) is 50/25/25 / to 99.5 / 0.25 / 0.25 (weight ratio) Although not limited to these, combinations can be freely made within the scope of the present invention.

  In the polyester resin composition of the present invention, the content of the copolymerized polyester resin is copolymerized with the polyethylene terephthalate resin (PET bottle recycled resin) in the ratio of the mixture of the polyethylene terephthalate resin (PET bottle recycled resin) and the copolymerized polyester resin. When the polyester resin is 100% by mass, it is preferably 0.01% by mass or more and 99.5% by mass or less, the lower limit is preferably 0.1% by mass or more, and the upper limit is more preferably 98% by mass or less. If it exceeds 99.5% by mass, mechanical properties such as impact resistance may not be exhibited, and if it is less than 0.01% by mass, improvement effects such as transparency may not be exhibited.

  Molding methods using the polyester resin composition of the present invention include injection molding, extrusion molding, profile extrusion molding, injection blow molding, direct blow molding, blow compression molding, stretch blow molding, calender molding, thermoforming (vacuum / compressed air) Molding), reaction injection molding, foam molding, compression molding, powder molding (including rotation / stretch molding), laminate molding, casting, melt spinning, and the like. Of these, blow molding, particularly preferably injection blow molding, is preferred from the viewpoint of maximizing the effects of the present invention such as improvement of transparency and improvement of molding cycle of the present invention.

  As a temperature condition for melt molding the polyester resin composition of the present invention, any temperature is acceptable as long as the entire composition can be melt-flowed. However, due to the nature of the polyester resin, it is considered to be 100 ° C. or higher and 350 ° C. or lower. More preferably, 150 ° C. or higher and 300 ° C. or lower is suitable. If the temperature is too low, the polymer cannot be delivered, or an excessive load is applied to the molding machine. Conversely, if the temperature is too high, the polymer will be thermally deteriorated, which is not preferable. The discharge amount in molding and other conditions can be set by appropriately adjusting to appropriate conditions of the machine base.

  The hollow molded body manufactured using the polyester resin composition of the present invention can be manufactured by a conventionally known molding method. For example, a method for producing a polyester stretch blow hollow molded body will be specifically described below.

  In order to produce a polyester hollow molded body, first, a preform which is a preformed body is produced from the polyester resin composition, and the preform can be produced by a conventionally known method such as injection molding or extrusion molding. it can. The formed preform is adjusted to a temperature suitable for stretching in order to be subjected to stretch blow, and subsequently stretch blow molded to produce a polyester hollow molded body.

  In the case of a polyester hollow molded body, for example, a preform is once molded by injection molding or extrusion molding, and a biaxial stretch blow molding method such as a hot parison method or a cold parison method is performed as it is or after processing a plug portion and a bottom portion. Applied. The molding temperature in this case, specifically, the temperature of each part of the cylinder of the molding machine and the nozzle is usually in the range of 260 to 290 ° C. The stretching temperature is usually 70 to 120 ° C., preferably 80 to 110 ° C., and the stretching ratio is usually 1.5 to 3.5 times in the longitudinal direction and 2 to 5 times in the circumferential direction. The obtained hollow molded body can be used as it is, but in the case of beverages that require hot filling, such as fruit juice beverages and oolong teas, the preform plug portion is heated and crystallized as described above. It is stretched and blow-molded and further heat-set in a blow mold to give heat resistance. The heat setting is usually performed at 100 to 200 ° C., preferably 120 to 180 ° C., for several seconds to several hours, preferably for several seconds to several minutes, using compressed air or the like.

  The heat setting method includes a one-mold type method in which stretch blow molding and heat setting are performed with a single mold, and a two-stage blow molding method in which a hollow molded body formed larger than the final shape is heated and contracted and re-blowed.

  Moreover, the manufacturing method of a polyester extrusion blow hollow molded object is demonstrated. The extrusion blow method (direct blow method) is a method in which a parison (or preform) formed by an extrusion molding machine or an injection molding machine is soft and does not lose its plasticity, but completes blow molding. As the molding machine, an apparatus conventionally used for blow molding of polystyrene or polyvinyl chloride can be used as it is. In this case, the molding temperature is usually 260 to 290 ° C. and melt extrusion molding at 240 to 290 ° C. to form a cylindrical parison, and this is inserted into a blow mold to form a conventional method. Thus, it is possible to employ a method in which air is blown to expand and expand the parison into a predetermined shape.

  Examples of the hollow molded article using the polyester resin composition of the present invention include injection molded articles such as blood collection tubes and test tubes, stretch blow molded articles such as soft drink bottles and aerosol containers, and extruded pharmaceutical containers such as eye drops. Examples include blow molded products. These molded bodies may be multilayer laminates containing at least one resin layer containing a gas barrier resin, an oxygen absorbing resin, an ultraviolet absorbing resin, or the like.

  When molding using the resin composition of the present invention, each polyester resin or polyester elastomer resin may be melt-mixed in advance and pelletized, or the polyester resin or polyester elastomer resin may be dry blended together. Direct melt molding may be used. The latter is more preferable from the viewpoint of impact resistance, hue, transparency and simplicity of the molded product. In particular, when a PET bottle recycled resin is used, it may be blow-molded directly using recycled flakes.

  When a softened hollow molded body is produced using the resin composition of the present invention, the effect is exhibited particularly in a large container having a capacity of 2000 ml or more. Preferably it is 5000 ml or more. In other words, if an impact modifier such as a normal olefin resin or rubber is used to soften the container, it will take a long time to cool down because of the large thickness of the container, and it will be shiny in the cooling process. This is because unevenness tends to proceed and the surface gloss tends to decrease.

  Moreover, since the preform of a large container is larger than that of a small container, it is necessary to increase the resin flow length when molding by injection molding. At this time, if an impact modifier such as a normal olefin resin or rubber is used, the compatibility as a melted material and the melt viscosity difference are too large, so that the characteristics as a molten homogeneous material are poor. As a result, the impact resistance improver was poorly dispersed and gloss unevenness occurred, and the appearance was not always poor.

  When the softened hollow molded article is produced using the resin composition of the present invention, the upper limit of the capacity is not particularly limited, but is preferably less than 5000000 ml, more preferably less than 1000000 ml, and further preferably less than 500000 ml. The preferred lower limit is preferably 5000 ml or more, more preferably 10,000 ml or more, and further preferably 15000 ml or more.

  The overall shape of such a container is appropriately selected from a cylinder including an ellipse, a prism including a rectangle, a cone and pyramid including a wharf, a drum (HOURGLASS DRAM-SHAPED), and a barrel shape, but is not particularly limited.

  The cross-sectional shape of the container body is not limited to a perfect circle, and may be an ellipse or a square. The shape in the height (length) direction may be a barrel shape or a drum shape outside the cylinder.

  The softened hollow molded article obtained by molding the resin composition of the present invention can reduce the thickness of the hollow molded article regardless of the shape. Since the thickness of the hollow molded body relates to the softening of the container body, the thinner it can contribute to the softening of the container. Therefore, the thickness of the hollow molded body is preferably 0.05 mm or more and 3 mm or less, more preferably 0.2 mm or more and 2 mm or less, and most preferably 0.25 mm or more and 1.5 mm or less.

  In addition, the polyester resin composition of the present invention includes a known ultraviolet absorber, a lubricant added from the outside, a lubricant internally precipitated during the reaction, a mold release agent, a nucleating agent, a stabilizer, an antioxidant. Various additives such as an additive capable of absorbing oxygen or capturing oxygen, an antistatic agent, a dye, and a pigment may be blended.

  In addition, organic, inorganic, and organometallic toners, fluorescent brighteners, and the like can be blended. By containing one or more of these, coloring such as yellowing of a molded product can be achieved. Furthermore, it can be suppressed to an excellent level. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphoric acid and phosphate ester-based phosphorus-based, sulfur-based, amine-based stabilizers, etc. Can be used.

  These additives can be added at any stage of polymerization of the polyester or after polymerization, or at the time of molding of the polyester hollow molded body. Which stage is suitable depends on the characteristics of the compound and the polyester hollow molded body. It depends on the required performance.

  The polyester resin composition of the present invention is blended with an antioxidant to suppress thermal degradation of the polyester resin during processing (to prevent the resin from being colored or sag due to thermal degradation). Is desirable. As the antioxidant, for example, a phenol-based antioxidant, an organic phosphite-based compound and the like are suitable.

  Specific examples of the phenolic antioxidant used in the present invention include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,6-di-tert. -Butyl 4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 3-methyl-4-isopropyl Phenol, 2,6-di-tert-butyl-4-hydroxymethylphenol, 2,2-bis (4-hydroxydiphenyl) propane, bis (5-tert-butyl-4-hydroxy-2-methylphenyl) sulfide, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 1,1- (3-tert-butyl-4-hydroxy-5-methylphenyl) butane, bis (3-tert-butyl-2-hydroxy-5-methylphenyl) methane, 2,6-bis (2-hydroxy-3- tert-butyl-5-methylbenzyl) -4-methylphenol, bis (3-tert-butyl-4-hydroxy-5-methylbenzyl) sulfide, bis (3-tert-butyl-5-ethyl-2-hydroxydiphenyl) Methane, bis (3,5-di-tert-butyl 4-hydroxydiphenyl) methane, bis (3-tert-butyl-2-hydroxy-5-methylphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) Cyclohexane, ethylenebis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate Bis [2- (2-hydroxy-3-tert-butyl5-methylbenzyl) -4-methyl-6-tert-butylphenyl] terephthalate, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) ) -2-Methylpropane, 4-methoxyphenol, cyclohexylphenol, p-phenylphenol, catechol, hydroquinone, 4-tert-butylpyrocatechol, ethyl gallate, propyl gallate, octyl gallate, lauryl gallate, cetyl gallate, β-naphthol 2,4,5-trihydroxybutyrophenone, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanate, 1,3,5-trimethyl-2,4,6-tris (3,5- Di-tert-butyl-4-hydroxydibenzyl) , 1,6-bis [2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] hexane, tetrakis [3- (3,5-di-tert-butyl-4-hydroxydiphenyl) ) Propionyloxymethyl] methane, bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] sulfide, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [3- (3,5-di-tert-butyl-4-hydroxydiphenyl) propionylamino] hexane, 2, 6-bis (3-tert-butyl-2-hydroxy-5-methylphenyl) -4-methyl Enol, bis [S- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)] thioterephthalate, tris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy Ethyl] isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, etc. Is mentioned. These compounds may be used alone or in combination of two or more.

  The blending amount of the phenolic antioxidant is preferably 1.0 parts by mass or less, particularly preferably 0.8 parts by mass or less, while the preferable lower limit is 0.01 parts by mass, when the total resin composition is 100 parts by mass. Part or more, particularly preferably 0.02 part by weight or more. If the blending amount is less than 0.01 parts by mass, it is difficult to obtain the effect of suppressing thermal degradation during processing, and if it exceeds 1.0 part by mass, the effect of suppressing thermal degradation is saturated and not economical.

  Specific examples of the organic phosphite compound used in the present invention include, for example, triphenyl phosphite, tris (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris (2-ethylhexyl). Phosphite, Tris (nonylphenyl) phosphite, Tris (octylphenyl) phosphite, Tris [decylpoly (oxyethylene) phosphite, Tris (cyclohexylphenyl) phosphite, Tricyclohexylphosphite, Tri (decyl) thiophosphite , Triisodecyl thiophosphite, phenyl bis (2-ethylhexyl) phosphite, phenyl diisodecyl phosphite, tetradecyl poly (oxyethylene) bis (ethylphenyl) phosphato, phenyl Dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di (tridecyl) phosphite, diphenyl cyclohexyl phosphite, diphenyl isooctyl phosphite, diphenyl 2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl・ Cyclohexylphenyl phosphite, diphenyl (tridecyl) thiophosphite, nonylphenyl ditridecyl phosphite, phenyl p-tert-butylphenyl dodecyl phosphite, diisopropyl phosphite, bis [otadecyl poly (oxyethylene)] phosphite , Octyl poly (oxypropylene) tridecyl poly (oxypropylene) phosphite, monoisopropyl phosphite, diisode Ruphosphite, diisooctyl phosphite, monoisooctyl phosphite, didodecyl phosphite, monododecyl phosphite, dicyclohexyl phosphite, monocyclohexyl phosphite, monododecyl poly (oxyethylene) phosphite, bis (cyclohexylphenyl) phosphite Monocyclohexyl phenyl phosphite, bis (p-tert-butylphenyl) phosphite, tetratridecyl 4,4′-isopropylidene diphenyl diphosphite, tetratridecyl 4,4′-butylidene bis (2-tert -Butyl-5-methylphenyl) diphosphite, tetraisooctyl-4,4′-thiobis (2-tert-butyl-5-methylphenyl) diphosphite, tetrakis (nonylphenyl) Poly (propyleneoxy) isopropyl diphosphite, tetratridecyl propyleneoxypropyl diphosphite, tetratridecyl 4,4'-isopropylidene dicyclohexyl diphosphite, pentakis (nonylphenyl) bis [poly (propylene Oxy) isopropyl] triphosphite, heptakis (nonylphenyl) tetrakis [poly (propyleneoxy) isopropyl] pentaphosphite, heptakis (nonylphenyl) tetrakis (4,4′-isopropylidenediphenyl) pentaphosphite, decachys (nonyl) Phenyl) ・ heptakis (propyleneoxyisopropyl) octaphosphite, decaphenyl heptakis (propyleneoxyisopropyl) octaphosphite, bis (butoxycal) Ethyl) · 2,2-dimethylene-trimethylenedithiophosphite, bis (isooctoxycarbomethyl) · 2,2-dimethylenetrimethylenedithiophosphite, tetradodecyl · ethylenedithiophosphite, tetradodecyl · hexamethylenedithio Phosphite, tetradodecyl 2,2'-oxydiethylenedithiophosphite, pentadodecyl di (hexamethylene) trithiophosphite, diphenyl phosphite, 4,4'-isopropylidene-dicyclohexyl phosphite, 4,4'- Isopropylidene diphenyl alkyl (C12-C15) phosphite, 2-tert-butyl-4- [1- (3-tert-butyl-4-hydroxydiphenyl) isopropyl] phenyldi (p-nonylphenyl) phosphite, di Ridecyl 4,4'-butylidenebis (3-methyl-6-tert-butylphenyl) phosphite, dioctadecyl 2,2-dimethylene trimethylene diphosphite, tris (cyclohexylphenyl) phosphite, hexatridecyl 4,4 ′, 4 ″ -1,1,3-butanetriyl-tris (2-tert-butyl-5-methylphenyl) triphosphite, tridodecylthiophosphite, decaphenyl heptakis (propyleneoxyisopropyl) octabosphite Dibutyl pentakis (2,2-dimethylenetrimethylene) diphosphite, dioctylpentakis (2,2-dimethylenetrimethylene) diphosphite, didecyl-2,2-dimethylenetrimethylenediphosphite and their lithium and sodium , Potassium, magnesium, caldium, barium, zinc and aluminum metal salts. These compounds may be used alone or in combination of two or more.

  The compounding amount of the organic phosphite compound is preferably 3.0 parts by mass or less, particularly preferably 2.0 parts by mass or less, and a preferred lower limit when the total resin composition is 100 parts by mass. It is 0.01 mass part or more, Most preferably, it is 0.02 mass part or more. If the blending amount is less than 0.01 parts by mass, it is difficult to obtain the effect of suppressing thermal degradation during processing, and if it exceeds 3.0 parts by mass, the effect of suppressing thermal degradation is saturated and not economical.

  In addition, it is preferable to use a phenolic antioxidant and an organic phosphite compound in combination since the effect of suppressing thermal deterioration is further improved.

  In the present invention, in order to further improve the heat resistance, impact resistance, dimensional stability, surface smoothness, rigidity, other mechanical properties, etc. of the polyester resin composition, the following characteristics are not changed. Such a resin can be added. For example, polyolefin resin such as polyethylene, polypropylene, ethylene-ethyl acrylate copolymer (EEA), or elastomer, polybutadiene, polyisoprene, butadiene-polyisoprene copolymer, acrylonitrile-isoprene copolymer, acrylate ester-butadiene Conjugated diene polymers such as copolymers, acrylate-butadiene-styrene copolymers, acrylate-isoprene copolymers; hydrogenated conjugated diene polymers; ethylene-propylene copolymers, etc. Olefin rubbers; Acrylic rubbers such as polyacrylates; Polyorganosiloxanes; Thermoplastic elastomers; Thermoplastic elastomers having epoxy groups, carboxyl groups, isocyanate groups, etc .; Ethylene ionomers Coalescence and the like, which are used alone or two or more. Among them, an acrylic rubber, a conjugated diene copolymer, or a hydrogenated product of a conjugated diene copolymer is preferable. Further, ethylene-vinyl acetate copolymer, ethylene-butene-1 copolymer, ethylene-propylene-ethyldennorbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-1,4 hexadiene Copolymer, ethylene-butene-1-dicyclopentadiene copolymer, ethylene-butene-1-1,4 hexadiene copolymer, acrylonitrile-chloroprene copolymer (NCR), styrene-chloroprene copolymer (SCR) , Butadiene-styrene copolymer (BS), ethylene-propylene ethylidene copolymer, styrene-isoprene rubber, styrene-ethylene copolymer, poly (α-methylstyrene) -polybutadiene-poly (α-methylstyrene) copolymer Coalescence (α-MES-B-α-MES), poly (α Resins or elastomers such as -methylstyrene) -polyisoprene-poly (α-methylstyrene) copolymer can also be added to the polyester resin composition.

  In the present invention, a lubricant may be blended for the purpose of improving moldability. The lubricant to be used is not particularly limited. For example, polyolefin wax, organophosphate metal salt, organophosphate ester, ester compound of adipic acid or azelaic acid and higher aliphatic alcohol, ethylenebisstearic acid amide, methylene Aliphatic amides such as bis-stearic acid amide, ethylene bis-oleic acid amide, glycerin higher fatty acid ester compounds, higher aliphatic alcohols, higher fatty acids, paraffins, waxes derived from petroleum or coal, natural or synthetic polymer ester waxes And metal soaps with higher fatty acids. These may be used alone or in combination of two or more.

  In the polyester resin composition of the present invention, saturated fatty acid monoamide, unsaturated fatty acid monoamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, etc. can be used simultaneously in order to improve mold releasability during molding processing. is there.

  Examples of saturated fatty acid monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide. Examples of unsaturated fatty acid monoamides include oleic acid amide, erucic acid amide, ricinoleic acid amide and the like. Examples of saturated fatty acid bisamides include methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bis behenic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid Examples include amides.

Examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide and hexamethylene bisoleic acid amide. Preferred amide compounds are saturated fatty acid bisamides, unsaturated fatty acid bisamides, and the like. The compounding amount of such an amide compound is in the range of 10 ppb to 1 × 10 ⁵ ppm.

  Similarly, in the polyester resin composition of the present invention, an aliphatic monocarboxylic acid metal salt compound having 8 to 33 carbon atoms such as naphthenic acid, caprylic acid, Lithium, potassium, magnesium, calcium and cobalt salts of saturated and unsaturated fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, melicic acid, oleic acid, linoleic acid It is also possible to use these simultaneously. The compounding amount of these compounds is in the range of 10 ppb to 300 ppm.

  When melt-molding the polyester resin composition of the present invention, the following reactive compounds can be added. Reactive compounds are used to expand the processing condition management range for expressing the “melt strength enhancement effect” that depends on the increase in molecular weight due to the reaction with the polyester resin, and to control the melt strength so that it can be adjusted. The weight average molecular weight is preferably 200 or more and 500,000 or less in order to satisfy the resistance to bending whitening and the suppression of bleed out of the unreacted product to the product surface layer. The preferred lower limit is 500 or more, more preferably 700 or more, most preferably 1000 or more, while the preferred upper limit is 300,000 or less, more preferably 100,000 or less, and most preferably 50,000 or less. When the weight average molecular weight of the reactive compound is less than 200, the unreacted reactive compound bleeds out to the surface of the product, which may cause a decrease in product adhesion and surface contamination. On the other hand, when the molecular weight exceeds 500,000, even if it is folded, voids are generated because the compatibility between the reactive compound and the amorphous polyester is poor, and the possibility of whitening is increased.

  The reactive compound used in the present invention preferably has two or more functional groups capable of reacting with the hydroxyl group or carboxyl group of the polyester per molecule in terms of partially introducing crosslinking into the entire resin. Due to the effect of the reactive compound, when a reaction product of the hydroxyl group or carboxyl group of the polyester and the reactive compound is produced during the melt extrusion, an effect of improving the melt strength can be obtained by partially forming a crosslinked product. .

  Specific examples of the functional group possessed by the reactive compound include a glycidyl group or an isocyanate group depending on the speed of the reaction. In addition to these, functional groups such as carboxyl groups, carboxylic acid metal salts, ester groups, hydroxyl groups, amino groups, carbodiimide groups, glycidyl groups and the like, and lactones, lactides, lactams, and other polyester end-opening addition functions. It may contain a group.

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

  In particular, as the above-mentioned reactive compound, (X) 20 to 99% by mass of vinyl aromatic monomer, (Y) 1 to 80% by mass of hydroxyalkyl (meth) acrylate and / or glycidylalkyl (meth) acrylate, and (Z) A copolymer comprising 0 to 40% by mass of alkyl (meth) acrylate is preferred. More preferably, (X) is a resin comprising 25 to 90% by mass, (Y) is 10 to 75% by mass, and (Z) is 0 to 35% by mass, and most preferably (X) is 30 to 85% by mass. %, (Y) is 15 to 70% by mass, and (Z) is a resin composed of 0 to 30% by mass. Since these compositions affect the functional group concentration contributing to the reaction with the polyester resin system, it is necessary to appropriately control them as described above. When it deviates from the above-mentioned composition, there is a possibility that the reactivity with the polyester resin is lowered and the molding processability is lowered.

  The addition amount of the reactive compound can be selected individually depending on the molecular weight and the number of functional groups introduced, but when the total composition is 100% by mass, 0.5% by mass to 80% by mass is preferable, and the lower limit is 1% by mass. As described above, the upper limit is more preferably 70% by mass or less. If it is less than 0.5% by mass, the targeted resin sag suppressing effect may not be exhibited, and if it exceeds 80% by mass, the mechanical properties of the product may be affected.

The polyester resin composition of the present invention may contain an ultraviolet absorber. In particular, in order to impart excellent weather resistance, it is preferable to use a UV absorber and a hindered amine light stabilizer in combination. Further, the vapor pressure at 20 ° C. of the ultraviolet absorber and / or hindered amine light stabilizer added for improving the weather resistance is preferably 1 × 10 ⁻⁶ or less, more preferably 1 × 10 ⁻⁷ or less, particularly preferably. Is 1 × 10 ⁻⁸ or less. Although the lower limit of the vapor pressure is preferable, it is practically 1 × 10 ⁻¹⁵ .

  Examples of the ultraviolet absorber used in the present invention include 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H). ) -Benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) ) Oxy] -phenol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and the like. As for the compounding quantity to a polyester resin composition, 0.5 to 15 weight% is preferable. More preferably, it is 2 to 10% by weight. When the blending amount in the polyester resin composition is less than 0.5% by weight, sufficient weather resistance cannot be obtained. On the other hand, when the blending amount is more than 15% by weight, the ultraviolet absorber bleeds out and the appearance is deteriorated.

  Examples of the hindered amine light stabilizer used in the present invention include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6 A polycondensate of hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1 , 3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) ) Imino}], bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, Screw (2,2, , 6-tetramethyl-4-piperidyl) sebacate, etc. The blending amount in the polyester resin composition is preferably 0.5 to 15% by weight, more preferably 2 to 10% by weight. When the blending amount in the polyester resin composition is less than 0.5% by weight, sufficient weather resistance cannot be obtained, whereas when the blending amount is more than 15% by weight, the hindered amine light stabilizer bleeds out. , The appearance gets worse.

  As a method for blending these additives into the polyester resin composition, they can be blended using a kneader such as a heating roll, an extruder, a Banbury mixer, or can be added before molding. Moreover, when superposing | polymerizing a thermoplastic polyester resin, it can also add and mix in the raw material before transesterification reaction, or the oligomer before a polycondensation reaction.

  Polyester resin compositions include known hindered phenol-based, sulfur-based, phosphorus-based and other antioxidants, hindered amine-based, triazole-based, benzophenone-based, benzoate-based, nickel-based and salicyl-based light stabilizers. , Antistatic agents, lubricants, molecular modifiers such as peroxides, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, fluorescent brighteners, glass fibers, carbon Fibers Inorganic fibrous materials such as silica fibers and alumina fibers, carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, iron oxide , Titanium oxide, zinc oxide, metal oxides such as alumina, calcium carbonate, metal carbonates such as barium carbonate, and other various metal powders Fillers, mica, plate-like fillers such as glass flakes, various metal powders, flame retardant, flame retardant aid, and pigments of an organic or inorganic may be added one or more.

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

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

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

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

  Analysis of contained metal: Quantified by elemental analysis by fluorescent X-ray. About 10 g of the raw material was melted and smoothed in a 300 ° C. melting oven for 15 minutes using a stainless steel ring. After cooling, the ring was removed and the sample was scraped with a razor blade to obtain a measurement sample, and elemental analysis was performed. A RIGAKU ZSX100e (4.0 kW Rh tube) was used as a measuring apparatus.

[PET resin]
The following were used as PET resin.
PET (I): Germanium-based catalyst Nippon Unipet Corporation RP553P
IV 0.85 (dl / g) (germanium content 50 ppm)
PET (II): antimony-based catalyst Eastman Chemical EASTAPAK9921
IV 0.83 (dl / g) (antimony amount 260 ppm)
Recycled PET: PET bottles were blow-molded with PET (I) and then pulverized to obtain flakes. Further, flakes were obtained in the same manner for PET (II). PET (I) and PET (II) flakes were blended at 50/50 (mass ratio) to obtain recycled PET flakes. (Germanium 25ppm, Antimony 130ppm)

[Synthesis Example of Polyester Resin (A)]
A 10 L volume esterification reaction vessel having a stirrer and a distillation condenser was charged with 2414 parts by mass of terephthalic acid (TPA), 1497 parts by mass of ethylene glycol (EG), and 515 parts by mass of neopentyl glycol (NPG) as a catalyst. Germanium dioxide as an 8 g / L aqueous solution was added to the resulting polyester as 30 ppm as germanium atoms, and cobalt acetate tetrahydrate was added as a 50 g / L ethylene glycol solution so as to contain 35 ppm as cobalt atoms relative to the resulting polymer. .

  Thereafter, the temperature in the reaction system was gradually raised until it finally reached 240 ° C., and the esterification reaction was performed at a pressure of 0.25 MPa for 180 minutes. After confirming that distillate water from the reaction system stops, the inside of the reaction system is returned to normal pressure, and trimethyl phosphate is contained as a 130 g / L ethylene glycol solution so as to contain 52 ppm as phosphorus atoms with respect to the produced polymer. Added to.

  The obtained oligomer was transferred to a polycondensation reaction tank, and the pressure was reduced while gradually raising the temperature, so that the final temperature was 280 ° C. and the pressure was 0.2 hPa. The reaction was continued until the torque value of the stirring blade corresponding to the intrinsic viscosity reached a desired value, and the polycondensation reaction was completed. The reaction time was 100 minutes. The obtained molten polyester resin was extracted in a strand form from the outlet at the bottom of the polymerization tank, cooled in a water tank, and then cut into chips to obtain a polyester resin (A).

  As a result of NMR analysis, the polyester resin (A) had a composition in which the dicarboxylic acid component was 100 mol% terephthalic acid, the diol component was 70 mol% ethylene glycol, and 30 mol% neopentyl glycol. The glass transition temperature was 78 ° C., the reduced viscosity at this time was 0.81 dl / g, and the germanium atom was 30 ppm.

[Synthesis Example of Polyester Resin (B)]
In the polyester resin (A), the polyester resin (A) was used in the same manner as the polyester resin (A) except that antimony trioxide as a catalyst was contained in an ethylene glycol solution of 12 g / L in an amount of 300 ppm as antimony atoms. B) was obtained.

  As a result of NMR analysis of the polyester resin (B), the dicarboxylic acid component had a composition of 100 mol% terephthalic acid, the diol component had 69 mol% ethylene glycol, and 31 mol% neopentyl glycol, and the antimony atom was 300 ppm. .

[Synthesis example of thermoplastic polyester elastomer (C)]
394 parts by weight of dimethyl terephthalate (DMT), 252 parts by weight of 1,4-butanediol (BD), 247 parts by weight of polytetramethylene glycol (PTMG) (number average molecular weight 1000), Irganox 1330 (manufactured by Ciba Specialty Chemicals) 1.4 parts by mass and 0.6 parts by mass of tetrabutyl titanate (TBT) were charged, the temperature was raised from room temperature to 200 ° C. over 2 hours, and then heated at 200 ° C. for 1 hour to perform a transesterification reaction. Next, the inside of the can was gradually depressurized and the temperature was raised, and an initial polymerization reaction was performed at 245 ° C. under 130 Pa over 45 minutes. Further, the polymerization reaction is carried out for 3 hours at 245 ° C. and 130 Pa or less, and the obtained molten polyester resin is extracted in a strand form from the outlet at the bottom of the polymerization tank, cooled in a water tank, cut into chips, and thermoplastic. A polyester elastomer (C) was obtained.

As a result of NMR analysis, the thermoplastic polyester elastomer (C) was found to have a dicarboxylic acid component of 100 mol% terephthalic acid component, a diol component of 87 mol% of 1,4-butanediol, and polytetramethylene glycol (number average molecular weight 1000). It had a composition of 13 mol%. The glass transition temperature was −60 ° C., the number average molecular weight was 28000, the reduced viscosity was 1.4 dl / g, and the acid value was 40 equivalents / 10 ⁶ g.

[Synthesis example of thermoplastic polyester elastomer (D)]
Dimethyl terephthalate (DMT) 143 parts by mass, ethylene glycol (EG) 131 parts by mass, polytetramethylene glycol (PTMG) (number average molecular weight 2000) 370 parts by mass, Irganox 1330 (manufactured by Ciba Specialty Chemicals) 1.0 mass Parts, 6 parts by mass of zinc acetate dihydrate as a catalyst, and germanium dioxide as an 8 g / L aqueous solution were charged to 300 ppm as germanium atoms with respect to the produced polyester, and the temperature was raised from room temperature to 215 ° C. over 2 hours. Thereafter, the mixture was heated at 215 ° C. for 1 hour to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and the temperature was raised, and the initial polymerization reaction was performed at 240 ° C. and 130 Pa or less over 45 minutes. Furthermore, a polymerization reaction is performed for 2 hours at 250 ° C. and 130 Pa or less, and the obtained molten polyester resin is extracted in a strand form from the outlet at the bottom of the polymerization tank, cooled in a water tank, and then cut into chips to be thermoplastic. A polyester elastomer (D) was obtained.

As a result of NMR analysis, the thermoplastic polyester elastomer (D) has a dicarboxylic acid component of 100 mol%, a diol component of 75 mol% of ethylene glycol, and 25 mol% of polytetramethylene glycol (number average molecular weight 2000). Had a composition. The glass transition temperature was -70 ° C, the number average molecular weight was 38000, the reduced viscosity was 2.4 dl / g, and the acid value was 40 equivalents / 10 ⁶ g.

[Synthesis example of thermoplastic polyester elastomer (N)]
425 parts by mass of polybutylene terephthalate (PBT) polymerized using a titanium compound as a catalyst, 192 parts by mass of ε-caprolactone (CLM; manufactured by Daicel Chemical Industries), 1.2 parts by mass of Irganox 1330 (manufactured by Ciba Specialty Chemicals) The mixture was charged at ℃, and the temperature was raised from 220 ° C to 235 ° C at normal pressure over 1 hour. Subsequently, the pressure was gradually reduced, and an initial polymerization reaction was performed at 235 ° C. and 130 Pa or less over 50 minutes. Furthermore, the polymerization reaction is carried out for 60 minutes at 235 ° C. and 130 Pa or less, and the obtained molten polyester resin is drawn out in a strand form from the outlet at the bottom of the polymerization tank, cooled in a water tank, cut into chips, and thermoplastic. A polyester elastomer (N) was obtained.

As a result of NMR analysis, the thermoplastic polyester elastomer (N) had a composition of 69% by mass of the polybutylene terephthalate (PBT) component and 31% by mass of the ε-caprolactone component. The glass transition temperature was −10 ° C., the number average molecular weight was 25000, the reduced viscosity was 1.3 dl / g, and the acid value was 45 equivalents / 10 ⁶ g. The remaining titanium atoms were 600 ppm. Their compositions and the measurement results are shown in Table 1. However, in Table 1, “31 mass%” means that the ε-caprolactone component contained as a soft segment in the polyester elastomer is 31 mass%, and the polybutylene terephthalate (PBT) component contained as a hard segment remains. Of 69% by mass.

  The polyester resins (E) to (K) were produced using germanium oxide as a polymerization catalyst in the same manner as the polyester resin (A). The remaining germanium atoms were 30 ppm. The thermoplastic polyester elastomers (L) and (M) were produced using tetrabutyl titanate (TBT) as a polymerization catalyst in the same manner as the thermoplastic polyester elastomer (C). The remaining titanium atoms were 600 ppm. Their compositions and measurement results are shown in Table 1. (Figures are mol% in resin)

[Example 1]
<Container 1>
80 parts by mass of recycled PET flakes, 5 parts by mass of polyester resin (A) and 15 parts by mass of thermoplastic polyester elastomer (C) are mixed, dried with a dryer using dehumidified nitrogen, and then resin is used with a Toshiba machine IS80 injection molding machine. A 2000 ml container 1 was molded at a temperature of 290 ° C. and a mold temperature of 20 ° C.

<Hollow molding>
80 parts by mass of recycled PET flakes, 5 parts by mass of a polyester resin (A), and 15 parts by mass of a thermoplastic polyester elastomer (C) are mixed and dried with a drier using dehumidified nitrogen. DM) A preform was molded by an injection molding machine at a resin temperature of 290 ° C. and a mold temperature of 20 ° C. This preform was biaxially stretch blow molded in a 20 ° C. mold at a blow pressure of 20 kg / cm ² using a LB-01E stretch blow molding machine manufactured by Corpoplast, and a 2000 ml hollow molded body (the body was circular). )

<Extruded blow hollow molding>
80 parts by mass of recycled PET flakes, 5 parts by mass of the polyester resin (A) and 15 parts by mass of the thermoplastic polyester elastomer (C) were mixed and dried with a drier using dehumidified nitrogen. Using a direct blow molding machine “Electric small hollow molding machine JEB-7 / P50 / WS60S” manufactured by Nippon Steel, the temperature of each part of the cylinder and the nozzle was set to about 285 ° C., and a hollow molded body having a capacity of 100 ml was extrusion blow molded.

<Large hollow molded body>
80 parts by mass of recycled PET flakes, 5 parts by mass of the polyester resin (A), and 15 parts by mass of the thermoplastic polyester elastomer (C) are mixed and dried with a dryer using dehumidified nitrogen, and an injection blow molding machine (H-3000). : Made by Aoki Solid Laboratories Co., Ltd.) at a resin temperature of 290 ° C. and a preform temperature of 60 to 100 ° C., and biaxially stretched and blown at a stretch blow station (inside the mold) to obtain a hollow molded body having a capacity of 85000 ml.

The molding processability of these molded products in the molding process was evaluated according to the following criteria.
<Container 1>
○: Injection pressure during production is constant, and resin fluidity is stable.
X: Injection pressure during production decreases, resin fluidity decreases, and filling property and dimensionality are not stable.
<Hollow molding>
○: The moldability of the preform is good and the product dimensionality after the stretch blow process is stable.
(Triangle | delta): Although a preform can be shape | molded, the product dimensionality after a stretch blow process is not stabilized.
X: The shape of the preform is not stable, and the product dimensions after the stretch blow process are not as intended.
<Extruded blow hollow molding>
○: Preform molding in a molten state is good, and product dimensionality after blowing is stable.
(Triangle | delta): The preform in a molten state draws down a little and the product dimensionality after a blow is not stabilized.
X: The preform in the molten state is drawn down and difficult to form, and blow molding cannot be performed.
<Large hollow molded body>
○: The moldability of the preform is good and the product dimensionality after the stretch blow process is stable.
(Triangle | delta): Although a preform can be shape | molded, the product dimensionality after a stretch blow process is not stabilized.
X: The shape of the preform is not stable, and the product dimensions after the stretch blow process are not as intended.

  Separately, molding was carried out with the same formulation, and surface hardness (needle puncture resistance), flexibility, and molding cycle (mold releasability) were evaluated. Evaluation criteria were as follows.

Needle puncture resistance evaluation:
A sample of 10 cm × 10 cm was cut from the body (thickness: about 0.45 mm) of the large hollow molded body having a capacity of 85000 ml, and a needle [19 G × 1 ^1/2 (diameter 1.10 mm, length) at 23 ° C. 38 mm)], and the force at the time of penetration was measured with an electronic balance.
◯: The force at the time of penetration is 1.5 kgf or more in terms of load.
X: The force at the time of penetration is less than 1.5 kgf in terms of load.

Flexibility evaluation:
A JIS standard No. 3 dumbbell sample was cut out from the body (thickness: about 0.45 mm) of the large hollow molded body having a capacity of 85000 ml, and tensile measurement was performed at a tensile speed of 500 mm / min.
◯: The tensile breaking strength in the molding flow direction is less than 60 Mpa.
X: The tensile breaking strength in the molding flow direction is 60 Mpa or more.

Mold releasability evaluation:
Using an injection molding machine (Toshiba IS-80: clamping force of 80 tons), a cylinder temperature of 250 to 295 ° C., a mold temperature of 16 ° C., and a back pressure of 20 kg / cm ² were prepared. The mold adhesion was determined according to the following criteria.
○: Resin mold separation was very smooth. ×: Resin mold adhesion increased, and it was necessary to apply a release agent to the mold.

[Examples 2 to 9, Comparative Examples 1 to 5]
Using the raw materials described in Tables 2 and 3, various evaluations were performed by injection molding, blow molding, and evaluation sample molding in the same manner as in Example 1 under the conditions described in the respective tables.

Moreover, about the compounding ratio in a table | surface, the polyester resin composition was 100 mass parts, and the following antioxidant, the ultraviolet absorber, the light stabilizer, and the impact modifier were represented as the addition amount with respect to 100 mass parts.
Antioxidant (O): Hindered phenol antioxidant (trade name) IRGANOX 1010 manufactured by Ciba Specialty Chemicals
Ultraviolet absorber (P): Ciba Specialty Chemicals (trade name) TINUVIN 234
Light Stabilizer (Q): A hindered amine light stabilizer HALS (trade name) Sanol @ LS770 manufactured by Sankyo Lifetech

  As can be seen from Tables 2 and 3, Examples 1 to 9 use two or more kinds of polyester resins, include a thermoplastic polyester elastomer, and have a mass ratio of 10/90 to 99 / germanium atoms and antimony atoms. Since it is contained at a ratio of 1, the injection moldability and blow moldability are good, the flexibility and high surface hardness of the blow molded product are realized, the molding cycle is improved, and the productivity is good.

  On the other hand, Comparative Example 1 is outside the scope of the present invention because two or more kinds of polyester resins are not melt-mixed and a thermoplastic polyester elastomer is not included. In Comparative Example 2, the material is softened using a polyethylene resin as an impact resistance improving material, but germanium atoms and antimony atoms are out of the ratio of 10/90 to 99/1 by mass ratio. It is outside the scope of the invention. In Comparative Example 3, two or more kinds of polyester resins are not melt-mixed, the thermoplastic polyester elastomer is not included, and germanium atoms and antimony atoms are out of the mass ratio of 10/90 to 99/1. This is outside the scope of the present invention. In Comparative Example 4, two or more kinds of polyester resins are not melt-mixed, a thermoplastic polyester elastomer is not included, and germanium atoms and antimony atoms are out of a ratio of 10/90 to 99/1 by mass ratio. This is outside the scope of the present invention. Comparative Example 5 is outside the scope of the present invention because germanium atoms and antimony atoms are out of the ratio of 10/90 to 99/1 by mass ratio. It is clear that Comparative Examples 1 to 5 which are outside the scope of the present invention are considerably inferior to Examples 1 to 9 in terms of molding processability and resin evaluation items (characteristics).

  According to the present invention, it is possible to provide a polyester resin composition having a high surface hardness and particularly suitable for producing a flexible polyester resin molded product. Especially for resin compositions made mainly from recycled PET bottle flakes, it is possible to provide environment-friendly molded products that are softened by lowering the rigidity at room temperature and have high surface hardness. The contribution to is great.

Claims (9)

  In the polyester resin composition obtained by melt-mixing two or more kinds of polyester resins, the thermoplastic polyester elastomer resin is an essential component of the composition, and the mass ratio of germanium atoms / antimony atoms contained as a catalyst in the entire composition Is a polyester resin composition characterized by being 10/90 to 99/1.   In a polyester resin composition obtained by melt-mixing two or more polyester resins, a thermoplastic polyester elastomer resin is an essential component of the composition, and is contained as a catalyst in the entire composition (germanium atom + antimony atom) / A polyester resin composition having a mass ratio of titanium atoms of 10/90 to 99/1.   The thermoplastic polyester elastomer resin is polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymer, polybutylene terephthalate, polybutylene terephthalate-isophthalate copolymer, polyethylene naphthalate, polyethylene naphthalate-terephthalate copolymer, polyethylene naphthalate- Isophthalate copolymer, polyethylene naphthalate-terephthalate-isophthalate copolymer, polybutylene naphthalate, polybutylene naphthalate-terephthalate copolymer, polybutylene naphthalate-isophthalate copolymer and polybutylene naphthalate-terephthalate -One or more hard segments selected from the group consisting of isophthalate copolymers, and poly (alkylene oxide) The polyester resin composition according to claim 1 or 2 having a soft segment is a glycol and / or polycaprolactone in the molecule.   The polyester resin composition according to any one of claims 1 to 3, wherein one of the two or more polyester resins is a polyethylene terephthalate resin.   The polyester resin composition according to any one of claims 1 to 3, wherein one of the two or more polyester resins is a PET bottle recycled resin.   The polyester resin composition according to claim 5, wherein the PET bottle recycled resin contains both germanium atoms and antimony atoms as catalysts.   6. The polyester resin composition according to claim 5, wherein the PET bottle regenerated resin contains two or more of germanium atoms, antimony atoms, titanium atoms, aluminum atoms, phosphorus atoms, and zinc atoms as a catalyst.   The polyester resin composition according to any one of claims 5 to 7, wherein a polyester resin other than the PET bottle regenerated resin among the two or more kinds of polyester resins contains a titanium atom as a catalyst.   As a polyester resin other than the thermoplastic polyester elastomer resin, a copolymer polyester resin is included, and the copolymer component is isophthalic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, adipic acid, sebacic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, lactone compounds, D-lactic acid and L- The polyester resin composition according to claim 1, wherein the polyester resin composition is at least one selected from the group consisting of lactic acid.