JP2017008286A - Polyester resin composition and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition excellent in melting retention stability and small in haze.SOLUTION: There is provided a polyester resin composition which is manufactured by blending at least one kind of a copper compounds of the formulae (i) to (v) of 1 to 30 ppm in terms of a copper atom and contains dicarboxylic acid or ester thereof and diol as main raw materials. CuX(i), where X is I, Br or Cl, n=1, 2. Cu(OOC-R)(ii), where R is H, C1 to 30 saturated aliphatic acid hydrocarbon or aromatic hydrocarbon, m1 or 2. Cu(OOC-R'-COO)(iii), where R' is C1, C2 saturated aliphatic hydrocarbon or aromatic hydrocarbon, l=1 or 2 and k=1. CuY(iv), where Y is a sulfate ion, a carbonate ion, a nitrate ion or a hydroxide ion, j=1 or 2 and i=1 or 2. CuO (v), where h=1 or 2.SELECTED DRAWING: None

Description

  The present invention relates to a polyester resin composition having excellent melt residence stability and low haze, and a method for producing the same.

  Polyester is one of the most commonly used synthetic resins in the world as fibers, bottles, films, sheets, containers and the like because it is excellent in mechanical strength, chemical stability and transparency and is inexpensive.

  Normally, polyester is chipped after polymerization and then melt processed, but if it is retained in a molten state, a gelled product is generated via thermal decomposition, clogging the filter in the processing step, and the pressure increases. Therefore, there was a problem that could not be stably processed.

  As a means for improving the melt residence stability of polyester, for example, addition of a metal compound can be mentioned.

  Patent Document 1 discloses a polyester film containing copper (I) iodide, and describes that thermal stability is improved by containing copper (I) iodide.

  Patent Document 2 discloses a polyester in which a copper salt of an organic carboxylic acid and an alkali metal salt are blended, and describes that hydrolysis resistance is improved.

  Patent Document 3 discloses a biaxially stretched polyester film having at least one of a copper salt and a halide, and describes that it is excellent in hydrolysis resistance and electrical insulation. Moreover, in patent document 4, the biaxially-oriented polyester film containing a copper compound is disclosed and it describes that it is excellent in hydrolysis resistance.

JP-A-62-177057 Japanese Examined Patent Publication No. 43-9560 JP 2010-265459 A JP 2010-202837 A

  In patent document 1, when there is much content of copper (I) iodide, the melt residence stability in air | atmosphere deteriorated and the subject that haze increased occurred.

  In Patent Document 2, when a copper salt of an unsaturated aliphatic organic carboxylic acid is blended, there is a problem that the melt residence stability in an air atmosphere deteriorates.

  Moreover, in patent document 3 and 4, when there was much content of a copper compound, there existed a subject which haze increased.

  An object of the present invention is to provide a polyester resin composition having excellent melt residence stability and low haze, and a method for producing the same.

  The present inventors have found that the above problem can be solved by blending a specific amount of a specific copper compound, and have reached the present invention.

That is, the present invention is as follows.
(1) A polyester resin mainly composed of dicarboxylic acid or its ester-forming derivative and diol is blended with at least one of the copper compounds represented by any of the following formulas (i) to (v): It is a polyester resin composition, Comprising: The polyester resin composition whose copper compound content with respect to polyester resin is 1-30 ppm on a copper atom basis.
CuX _n (i)
(Here, X is at least one selected from iodine, bromine and chlorine, and n = 1 or 2.)
Cu (OOC-R) _m (ii)
(Here, R is at least one selected from hydrogen, saturated aliphatic hydrocarbons having 1 to 30 carbon atoms, and aromatic hydrocarbons, and m = 1 or 2.)
Cu _l (OOC—R′—COO) _k (iii)
(Here, R ′ is at least one selected from saturated aliphatic hydrocarbons having 1 or 2 carbon atoms and aromatic hydrocarbons, where l = 1 or 2, and k = 1.)
Cu _j Y _i (iv)
(Here, Y is at least one selected from sulfate ion, carbonate ion, nitrate ion, and hydroxide ion, and j = 1 or 2, i = 1 or 2.)
Cu _h O (v)
(Where h = 1 or 2)
(2) The copper compound is copper iodide (I), copper bromide (I), copper bromide (II), copper chloride (I), copper chloride (II), copper acetate (I), copper acetate (II) ), Copper (II) stearate, copper (II) terephthalate, copper (II) sulfate, copper (II) carbonate, copper (I) oxide, and copper (II) polyester resin composition according to (1) object.
(3) The polyester resin composition as described in (1) or (2) whose copper compound content with respect to a polyester resin is 1-17 ppm on a copper atom basis.
(4) The dicarboxylic acid or its ester-forming derivative is at least one selected from terephthalic acid, terephthalic acid diester, 2,6-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid diester (1) to (3 ) The polyester resin composition according to any one of
(5) The polyester resin composition according to any one of (1) to (4), wherein the diol is at least one selected from ethylene glycol, propylene glycol, and butylene glycol.
(6) 2 g of polyester resin composition was dissolved in 20 ml of phenol / 1,1,2,2-tetrachloroethane 3/2 (volume ratio) mixed solution, and the solution haze measured using a cell having an optical path length of 20 mm was obtained. The polyester resin composition according to any one of (1) to (5), which is 5% or less.
(7) The polyester resin composition according to any one of (1) to (6), wherein the gelation rate after heat treatment at 300 ° C. for 6 hours in an oxygen 1% atmosphere is 10% or less.
(8) The polyester resin composition according to any one of (1) to (7), wherein the gelation ratio after heat treatment at 300 ° C. for 6 hours in an air atmosphere is 28% or less.
(9) In the polyester resin production method in which a dicarboxylic acid or an ester-forming derivative thereof and a diol are esterified or transesterified, and then polymerized, in any of the esterification, transesterification, and polymerization The polyester resin which adds at least 1 sort (s) among the copper compounds represented by either of the following (i)-(v) formula so that it may become 1-30 ppm on the basis of a copper atom with respect to the weight of the polyester resin obtained. A method for producing the composition.
CuX _n (i)
(Here, X is at least one selected from iodine, bromine and chlorine, and n = 1 or 2.)
Cu (OOC-R) _m (ii)
(Here, R is at least one selected from hydrogen, saturated aliphatic hydrocarbons having 1 to 30 carbon atoms, and aromatic hydrocarbons, and m = 1 or 2.)
Cu _l (OOC—R′—COO) _k (iii)
(Here, R ′ is at least one selected from saturated aliphatic hydrocarbons having 1 or 2 carbon atoms and aromatic hydrocarbons, where l = 1 or 2, and k = 1.)
Cu _j Y _i (iv)
(Here, Y is at least one selected from sulfate ion, carbonate ion, nitrate ion, and hydroxide ion, and j = 1 or 2, i = 1 or 2.)
Cu _h O (v)
(Where h = 1 or 2)
(10) The method for producing a polyester resin composition according to (9), wherein the polyester resin composition is added so as to be 1 to 17 ppm on a copper atom basis with respect to the weight of the obtained polyester resin.

  According to the present invention, a polyester resin composition having excellent melt residence stability and low haze can be obtained efficiently.

  The polyester resin used in the present invention is obtained using a dicarboxylic acid or an ester-forming derivative and a diol as main raw materials. Here, the main raw material comprises 80% by weight or more of the raw material monomer constituting the polyester, which consists of a dicarboxylic acid, an ester-forming derivative, and a diol. More preferably, it is 90 weight% or more, More preferably, it is 95 weight% or more, Most preferably, it is 100 weight%.

  Examples of the dicarboxylic acid or ester-forming derivative thereof used as a polyester resin raw material in the present invention include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, and 5-tetrabutylphosphonium. Dicarboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, dimer acid, or lower alkyl esters of these dicarboxylic acids , Acid anhydrides, acyl chlorides and the like are preferably used. A more preferred embodiment of the dicarboxylic acid or ester-forming derivative of the present invention is terephthalic acid, 2,6-naphthalenedicarboxylic acid, or dimethyl ester thereof in that a high melting point and high strength polyester resin can be obtained.

  Examples of the diol which is a polyester resin raw material used in the present invention include ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, deca Methylene glycol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cyclohexanedimethanol, xylylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A-ethylene oxide adduct, etc. Among them, ethylene glycol, propylene glycol, and butylene glycol are preferable because a polyester resin having a high melting point and high strength can be obtained.

  The polyester resin used in the present invention may be a polyester resin that can be obtained using a dicarboxylic acid or an ester-forming derivative thereof, and a diol, and the dicarboxylic acid or an ester-forming derivative thereof and a diol may be used alone. It is also possible to use two or more types in combination. Specific examples of the polyester resin used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polycyclohexanedimethylene isophthalate, polyethylene naphthalate. Phthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polyethylene terephthalate Talate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfoisophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene Terephthalate / polytetramethylene glycol, polypropylene terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polyethylene terephthalate / isophthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, poly Tylene terephthalate / isophthalate / polytetramethylene glycol, polyethylene terephthalate / succinate, polypropylene terephthalate / succinate, polybutylene terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sebacate, polypropylene terephthalate / Sebacate, Polybutylene terephthalate / Sebacate, Polyethylene oxalate, Polypropylene oxalate, Polybutylene oxalate, Polyethylene succinate, Polypropylene succinate, Polybutylene succinate, Polyethylene adipate, Polypropylene adipate, Polybutylene azide Examples include pete, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, polybutylene succinate / adipate. Here, “/” represents a copolymer. Among these, terephthalic acid or its dimethyl ester, polyethylene terephthalate obtained using ethylene glycol as the diol component, 2,6-naphthalenedicarboxylic acid or its dimethyl ester, and polyethylene naphthalate obtained using ethylene glycol as the diol component are preferred.

The polyester resin composition of this invention mix | blends at least 1 sort (s) among the copper compounds chosen from the following (i)-(v) formula to the said polyester resin.
CuX _n (i)
(Here, X is at least one selected from iodine, bromine and chlorine, and n = 1 or 2.)
Cu (OOC-R) _m (ii)
(Here, R is at least one selected from hydrogen, saturated aliphatic hydrocarbons having 1 to 30 carbon atoms, and aromatic hydrocarbons, and m = 1 or 2.)
Cu _l (OOC—R′—COO) _k (iii)
(Here, R ′ is at least one selected from saturated aliphatic hydrocarbons having 1 or 2 carbon atoms and aromatic hydrocarbons, where l = 1 or 2, and k = 1.)
Cu _j Y _i (iv)
(Here, Y is at least one selected from sulfate ion, carbonate ion, nitrate ion, and hydroxide ion, and j = 1 or 2, i = 1 or 2.)
Cu _h O (v)
(Where h = 1 or 2)

  Specific examples of the copper compound represented by the formula (i) include copper (I) iodide, copper (II) iodide, copper (I) bromide, copper (II) bromide, copper (I) chloride, Examples thereof include copper (II) chloride.

  (Ii) Specific examples of the copper compound represented by the formula include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, caprin Copper acid, copper undecylate, copper laurate, copper tridecylate, copper myristate, copper pentadecylate, copper palmitate, copper margarate, copper stearate, copper nonadecylate, copper arachidate, copper heicosylate, copper behenate , Copper tricosylate, copper lignocerate, copper serotic acid, copper montanate, copper melicinate, copper salts with isomers of these aliphatic carboxylic acids, copper benzoate, and the like.

  Specific examples of the copper compound represented by the formula (iii) include copper terephthalate, copper oxalate, copper malonate, copper succinate, copper isophthalate, copper phthalate and the like.

  Specific examples of the copper compound represented by the formula (iv) include copper (II) sulfate, copper (II) carbonate, copper (II) nitrate, and copper (II) hydroxide.

  Specific examples of the copper compound represented by the formula (v) include copper (I) oxide and copper (II) oxide.

  The copper compound may be monovalent or divalent, and the copper compound may be a hydrate. Two or more of the above copper compounds may be used in combination.

  Among the above-mentioned copper compounds, copper (I) iodide, copper bromide (I), copper bromide (II), copper chloride (I), copper chloride (II), copper acetate ( I), copper acetate (II), copper stearate (II), copper (II) terephthalate, copper (II) sulfate, copper (II) carbonate, copper oxide (I) and copper oxide (II) are preferred.

  When the above copper compound is blended in the polyester resin, the valence of the copper cation may change due to the oxidation-reduction reaction, or the counter anion may be exchanged with a carboxyl group of the polyester resin. Although the structure of a copper compound may change, in this invention, the effect of invention is expressed by mix | blending the said copper compound with a polyester resin.

  In the present invention, since it is intended to obtain a polyester resin composition having improved melt residence stability, it is not preferable to blend a copper compound having a reactive unsaturated group. When a copper compound having a reactive unsaturated group is used, the melt residence stability in an air atmosphere is deteriorated.

  In the polyester resin composition of the present invention, the content of the copper compound with respect to the polyester resin needs to be 1 to 30 ppm based on the copper atom. Preferably it is 2 ppm or more, More preferably, it is 3 ppm or more. By setting it to 1 ppm or more, the melt residence stability in an oxygen 1% atmosphere can be improved.

  Further, the copper compound content is preferably 25 ppm or less, more preferably 17 ppm or less, and further preferably 15 ppm or less, based on the copper atom. By setting the copper compound content to 30 ppm or less based on the copper atom, it is possible to suppress deterioration of melt residence stability in an air atmosphere and obtain a polyester resin composition having a low haze.

  The polyester resin composition of the present invention preferably has a solution haze of 5% or less. More preferably, it is 4% or less, More preferably, it is 3% or less. Solution haze is a turbidity measured by dissolving 2 g of a polyester resin composition in 20 ml of a phenol / 2,1,2,2-tetrachloroethane 3/2 (volume ratio) mixed solution and using a cell with an optical path length of 20 mm. It is a numerical value that represents the degree. By setting it as this range, while being able to suppress the filter clogging at the time of melt processing, transparency of a film can be maintained especially.

  The polyester resin composition of the present invention preferably has a gelation rate of 10% or less in an oxygen 1% atmosphere prepared by mixing air and nitrogen. More preferably, it is 5% or less, More preferably, it is 3% or less. The gelation rate in an oxygen 1% atmosphere is the weight of insoluble matter remaining when the polyester resin composition is treated in an oxygen 1% atmosphere at 300 ° C. for 6 hours and then dissolved in o-chlorophenol (OCP). Is defined as the numerical value obtained by dividing by the weight of the polyester resin before treatment and multiplying by 100. By setting it as this range, the gelation of the polyester in the melt processing step of the polyester resin composition can be suppressed.

  The polyester resin composition of the present invention preferably has a gelation rate of 28% or less in an air atmosphere. More preferably, it is 26% or less, More preferably, it is 25% or less. The gelation rate under an air atmosphere is determined by the weight of insoluble matter remaining when the polyester resin composition is treated in an air atmosphere at 300 ° C. for 6 hours and then dissolved in o-chlorophenol (OCP). It is defined as a value obtained by dividing by the weight of the polyester resin and multiplying by 100. By setting it as this range, even when the molten resin discharged from the die touches air in the melt processing step of the polyester resin composition, gelation can be suppressed.

  The method for producing a polyester resin obtained by using dicarboxylic acid or its ester-forming derivative and diol as main raw materials used in the present invention comprises the following two steps. That is, it is a first stage process comprising (A) esterification reaction or (B) transesterification reaction, followed by a second stage process comprising (C) polymerization reaction.

  Among the steps of the first step, (A) the esterification reaction step is an esterification reaction of dicarboxylic acid and diol at a predetermined temperature, and a reaction is performed until a predetermined amount of water is distilled off to obtain a low polymer. It is a process. The step (B) transesterification reaction is a step in which a dicarboxylic acid alkyl ester and a diol are transesterified at a predetermined temperature, and a reaction is performed until a predetermined amount of alcohol is distilled to obtain a low polymer.

  The (C) polymerization reaction as the second step is a dediol reaction by reducing the pressure in the reactor to which the low polymer obtained by (A) esterification reaction or (B) transesterification reaction is added. (Hereinafter referred to as “the time when the polymerization reaction is started”), and while adjusting the temperature, pressure and stirring speed in the reactor, the stirring torque reaches a predetermined value, that is, the polyester reaches the desired viscosity. This is a step of obtaining a polyester by carrying out a dediol reaction until it is carried out (hereinafter referred to as “the final point of the polymerization reaction”).

  Examples of the method for producing the polyester resin composition of the present invention include a method in which a copper compound is added at any stage of the step (A) or (B) and the subsequent step (C). From the viewpoint of improving the dispersibility of the copper compound, it is preferably added in the step (C), particularly preferably at the start of the polymerization reaction. The copper compound is preferably added in a state of being mixed with the diol at a weight ratio of 3/100 to 10/100.

  In the method for producing a polyester resin used in the present invention, the catalyst used for the esterification reaction may be a compound such as manganese, cobalt, zinc, titanium, calcium, or may be non-catalytic. Moreover, as a catalyst used for transesterification, compounds, such as magnesium, manganese, calcium, cobalt, zinc, lithium, titanium, are used. Moreover, as a catalyst used for the polymerization reaction, compounds such as antimony, titanium, aluminum, tin, and germanium are used.

  Antimony compounds include antimony oxides, antimony carboxylic acids, antimony alkoxides, and the like. Specific examples of antimony oxides include antimony trioxide and antimony pentoxide. Antimony carboxylic acids include acetic acid. Examples include antimony and antimony oxalate. Examples of the antimony alkoxide include antimony tri-n-butoxide and antimony triethoxide.

  Specific examples of titanium compounds include titanium alkoxides such as tetra-i-propyl titanate, tetra-n-butyl titanate, and tetra-n-butyl titanate tetramer, titanium oxides obtained by hydrolysis of titanium alkoxide, and titanium acetyl. Examples thereof include titanium complexes using acetonate, polycarboxylic acid and / or hydroxycarboxylic acid and / or polyhydric alcohol as a chelating agent. As the chelating agent for the titanium compound, lactic acid, citric acid, mannitol, tripentaerythritol and the like are preferable from the viewpoint of the thermal stability of the polymer, the color tone, and the small amount of deposits around the mouthpiece. In particular, a titanium mannitol chelate complex obtained by the method described in Japanese Patent Application Laid-Open No. 2010-100806 is preferable because generation of foreign particles of the polymer can be suppressed.

  Specific examples of the aluminum compound include aluminum acetate, aluminum hydroxide, aluminum carbonate, aluminum ethoxide, aluminum isopropoxide, aluminum acetylacetonate, and basic aluminum acetate.

  Specific examples of tin compounds include monobutyltin oxide, dibutyltin oxide, methylphenyltin oxide, tetraethyltin oxide, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, monobutyltin trichloride, and dibutyltin sulfide. Etc.

  Examples of germanium compounds include germanium oxides and germanium alkoxides, and specific examples of germanium oxides include germanium dioxide, germanium tetroxide, and germanium alkoxides such as germanium tetraethoxide and germanium tetrabutoxide. It is done.

  Specific examples of the magnesium compound include magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, and magnesium carbonate.

  Specific examples of the manganese compound include manganese chloride, manganese bromide, manganese nitrate, manganese carbonate, manganese acetylacetonate, and manganese acetate.

  Specific examples of the calcium compound include calcium oxide, calcium hydroxide, calcium alkoxide, calcium acetate, and calcium carbonate.

  Specific examples of the cobalt compound include cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt acetylacetonate, cobalt naphthenate, and cobalt acetate tetrahydrate.

  Specific examples of the zinc compound include zinc oxide, zinc alkoxide, and zinc acetate.

  These metal compounds may be hydrates.

  It is preferable that a phosphorus compound is added as a stabilizer to the polyester resin used in the present invention. Specifically, phosphoric acid, trimethyl phosphate, ethyl diethylphosphonoacetate and the like are preferable, and 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10. -Tetraoxa-3,9-diphosphaspiro [5,5] undecane (PEP-36: manufactured by Asahi Denka) or tetrakis (2,4-di-t-butyl-5-methylphenyl) [1,1-biphenyl]- Trivalent phosphorus compounds such as 4,4′-diylbisphosphonite (GSY-P101: manufactured by Osaki Kogyo Co., Ltd.) are more preferred from the viewpoints of color tone and thermal stability improvement.

  Moreover, the dye used for resin etc. as a color tone regulator may be added as needed. In particular, COLOR INDEX GENERIC NAME gives blue color tone adjusters such as SOLVENT BLUE 104 and SOLVENT BLUE 45, and purple color adjusters such as SOLVENT VIOLET 36, which do not contain halogens that are likely to cause device corrosion. The heat resistance at high temperatures is relatively good and the color developability is excellent, which is preferable. These may be used alone or in combination of two or more.

  Furthermore, you may mix | blend antioxidant, a ultraviolet absorber, a flame retardant, a fluorescent whitening agent, a matting agent, a plasticizer or an antifoamer, or another additive as needed.

  In the present invention, a polyester resin composition having a higher molecular weight can be obtained by solid-phase polymerization of a polyester resin composition obtained by blending a copper compound and melt polymerization. The solid-state polymerization is not particularly limited in apparatus and method, but is carried out by heat treatment under an inert gas atmosphere or under reduced pressure. Any inert gas may be used as long as it is inert to the polyester, and examples thereof include nitrogen, helium, carbon dioxide, etc. Nitrogen is preferably used from the viewpoint of economy. Further, as the reduced pressure, it is advantageous to use a reduced pressure condition because the time required for the solid phase polymerization reaction can be shortened, but it is preferable to maintain 110 Pa or more.

  Moreover, the polyester resin composition obtained by this invention can also be recycled. Specifically, when the polyester resin component is polyethylene terephthalate, the waste is used as a raw material, and a depolymerization reaction is performed with a glycol component to obtain bis (hydroxyethyl) terephthalate. This may be polymerized again, but is preferably further transesterified with methanol or ethanol to give dimethyl terephthalate or diethyl terephthalate. These terephthalic acid dialkyl esters are preferred because they can be purified to high purity by distillation. The terephthalic acid dialkyl ester thus obtained can be used for polymerization again.

  The polyester resin composition of the present invention can be produced by batch polymerization, semi-continuous polymerization, or continuous polymerization.

  The polyester resin composition of the present invention can be molded by a known processing method, and can be processed into various products such as fibers, films, bottles, and injection molded products.

  For example, a normal melt spinning-drawing process can be applied to a method of processing a polyester resin composition into fibers. Specifically, after the polyester resin composition is heated to the melting point of the polyester resin or higher and melted, it is discharged from the pores, cooled and solidified with cooling air, applied with an oil agent, taken up by a take-up roller, and taken up. Undrawn yarn can be collected by winding with a winding device disposed after the roller.

  The undrawn yarn wound in this way becomes a fiber to which physical properties such as mechanical properties according to the application are given by drawing with a pair of heated rollers or more and finally applying tension or relaxation heat treatment. In addition, in this extending process, it can carry out continuously, without winding once after taking up in the above-mentioned melt spinning process, and it is preferable to set it as continuous extending | stretching from industrial viewpoints, such as productivity. Here, in performing this stretching-heat treatment, the draw ratio, the stretching temperature, and the heat treatment conditions can be appropriately selected depending on the target fiber fineness, strength, elongation, shrinkage rate, and the like.

  When the polyester resin composition of the present invention is processed into various products, various additives such as colorants, pigments, dyes, lubricants, antistatic agents, flame retardants, ultraviolet rays, and the like, as long as the effects of the present invention are not impaired. One or more additives such as an absorbent, an antibacterial agent, a nucleating agent, a plasticizer, and a release agent can be added.

  Since the polyester resin composition of the present invention is excellent in melt residence stability and transparency, it can be used as various products such as fibers, films, bottles and injection molded products. These products are used for agricultural materials and horticulture. It is useful for materials, fishery materials, civil engineering / architectural materials, stationery, medical supplies, automotive parts, electrical / electronic components or other applications.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured by the method described below.

(1) Intrinsic viscosity ([η], unit: dl / g)
The polyester resin composition was dissolved in an o-chlorophenol (OCP) solvent to prepare solutions having concentrations of 0.5 g / dL, 0.2 g / dL, and 0.1 g / dL. Then, the relative viscosity (ηr) at 25 ° C. of the obtained solution having the concentration C was measured with an Ubero-De viscosity tube, and (ηr−1) / C was plotted against C. And the intrinsic viscosity was calculated | required by extrapolating the obtained result to the density | concentration of 0.

(2) Copper compound content based on copper atom relative to polyester resin (unit: ppm)
Measurement was performed by atomic spectrum analysis using a flame atomic absorption spectrometer (AAnalyst200 manufactured by Perkin Elmer).

(3) Solution haze (unit:%)
2 g of the polyester resin composition was dissolved in 20 ml of a phenol / 2,1,2,2-tetrachloroethane 3/2 (volume ratio) mixed solution, and a haze meter (manufactured by Suga Test Instruments Co., Ltd.) was used using a cell having an optical path length of 20 mm. HZ-1) was analyzed by integrating sphere photoelectric photometry.

(4) Gelation rate (unit:%)
1 g of the polyester resin composition was pulverized with a freeze pulverizer (Splex CertiPerp, 6750-115) to form a powder having a diameter of 300 μm or less, and then a vacuum dryer (Tokyo Rika Kikai Co., Ltd., VOS-451SD) was used. And vacuum-dried at 150 ° C. for 12 hours. Then, what was heat-treated in an oven (manufactured by Yamato Scientific Co., Ltd., DN410I) in an oxygen 1% atmosphere or an air atmosphere at 300 ° C. for 6 hours was dissolved in 50 ml of OCP at 150 ° C. for 0.5 hours. Then, it filtered with the Buchner type | mold glass filter (The magnitude | size of the largest pore 20-30 micrometers), and wash | cleaned and vacuum-dried. The weight of the OCP insoluble matter remaining on the filter is calculated from the increase in the weight of the filter before and after filtration, and the weight fraction of the OCP insoluble matter relative to the weight (1 g) of the polyester resin composition before the treatment is obtained. (%).

Example 1
After 105 parts by weight of (bishydroxyethyl) terephthalate was melted at 255 ° C., a slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol was gradually added thereto to carry out an esterification reaction. The temperature in the reaction system was controlled to be 245 ° C. to 255 ° C., and the esterification reaction was completed when the reaction rate reached 95%.

  After the obtained esterification reaction product was put into a test tube and kept in a molten state at 250 ° C., 70 ppm of antimony trioxide in terms of antimony atoms per 100 g of the obtained polymer, and 45 ppm in terms of phosphorus atoms per 100 g of the resulting polymer. Trimethyl phosphate and 17 ppm of copper (I) iodide (manufactured by Wako Pure Chemical Industries, Ltd.) in terms of copper atoms were added per 100 g of the resulting polymer. Copper iodide (I) was mixed with ethylene glycol at a weight ratio of 7/100 30 minutes before addition, and stirred at room temperature for 30 minutes, and then the mixture was added. The reaction was started after 5 minutes had passed since each compound was added. While the reactor was gradually heated from 250 ° C. to 290 ° C. over 90 minutes, the pressure was reduced from normal pressure to 130 Pa over 60 minutes, and a polymerization reaction was carried out at 290 ° C. and 130 Pa for a predetermined time. After the completion of the polymerization reaction, the melt was discharged in a strand form, cooled, and immediately cut to obtain pellets. Using the obtained pellets, intrinsic viscosity, copper atom content with respect to the polyester resin, solution haze, and gelation rate were measured. The results are shown in Table 1.

Example 2
A polyester resin composition was obtained in the same manner as in Example 1 except that the amount of copper (I) iodide was changed as shown in Table 1.

Example 3
A polyester resin composition was obtained in the same manner as in Example 1 except that copper bromide (I) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper iodide (I).

Example 4
A polyester resin composition was obtained in the same manner as in Example 1 except that copper bromide (II) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper iodide (I).

Example 5
A polyester resin composition was obtained in the same manner as in Example 1, except that copper chloride (I) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper iodide (I).

Example 6
A polyester resin composition was obtained in the same manner as in Example 1, except that copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper iodide (I).

Examples 7 and 8
Instead of copper iodide (I), copper acetate (I) (manufactured by Wako Pure Chemical Industries, Ltd.) was used, and the compounding amount was changed as shown in Table 1 in the same manner as in Example 1. A polyester resin composition was obtained.

Example 9
In the same manner as in Example 1, except that copper (II) acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper (I) iodide and the blending amount was changed as shown in Table 1. A polyester resin composition was obtained.

Example 10
Polyester in the same manner as in Example 1 except that copper (II) stearate (manufactured by Kanto Chemical Co., Inc.) was used instead of copper (I) iodide and the blending amount was changed as shown in Table 1. A resin composition was obtained.

Example 11
Example except that copper terephthalate trihydrate (II) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper iodide (I) and the blending amount was changed as shown in Table 1. 1 was used to obtain a polyester resin composition.

Example 12
Instead of copper iodide (I), copper sulfate pentahydrate (II) (manufactured by Aldrich) was used, and the blending amount was changed as shown in Table 1, and the same as in Example 1 A polyester resin composition was obtained by the method.

Example 13
Instead of copper iodide (I), basic copper carbonate (II) (manufactured by Wako Pure Chemical Industries, Ltd.) was used, and the blending amount was changed as shown in Table 1, and the same as in Example 1 A polyester resin composition was obtained by the method.

Example 14
In the same manner as in Example 1 except that copper (I) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper iodide (I), and the blending amount thereof was changed as shown in Table 1. A polyester resin composition was obtained.

Example 15
In the same manner as in Example 1, except that copper (II) oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper iodide (I), and the blending amount thereof was changed as shown in Table 1. A polyester resin composition was obtained.

Comparative Example 1
A polyester resin composition was obtained in the same manner as in Example 1 except that copper (I) iodide was not added.

Comparative Examples 2-4
A polyester resin composition was obtained in the same manner as in Example 1 except that the amount of copper (I) iodide was changed as shown in Table 1.

Comparative Example 5
A polyester resin composition was obtained in the same manner as in Example 7 except that the amount of copper (I) acetate was changed as shown in Table 1.

Comparative Example 6
A polyester resin composition was obtained in the same manner as in Example 9 except that the amount of copper (II) acetate was changed as shown in Table 1.

Comparative Example 7
Example 1 except that magnesium acetate tetrahydrate (II) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper (I) iodide, and the blending amount thereof was changed as shown in Table 1. A polyester resin composition was obtained in the same manner as above.

Comparative Example 8
A method similar to Example 1 except that copper oleate (II) (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of copper iodide (I), and the blending amount thereof was changed as shown in Table 1. A polyester resin composition was obtained.

  From the comparison between Examples 1 to 15 and Comparative Examples 1 and 4, the gelation rate in an oxygen 1% atmosphere can be greatly reduced by setting the copper compound content to 1 ppm or more based on the copper atom. . Moreover, from comparison of Examples 1-15 and Comparative Examples 2, 3, 5, and 6, by making the copper compound content 30 ppm or less on the basis of copper atoms, the gelation rate under a solution haze and air atmosphere is reduced. Can be reduced. In Comparative Example 8, the copper compound content is within the range of the present invention, but since the compounded copper compound contains a reactive unsaturated group (double bond), the gelation rate in an air atmosphere was high. .

Claims (10)

Polyester resin composition formed by blending at least one of copper compounds represented by any of the following formulas (i) to (v) with a polyester resin mainly composed of dicarboxylic acid or its ester-forming derivative and diol. A polyester resin composition, wherein the copper compound content relative to the polyester resin is 1 to 30 ppm on a copper atom basis.
CuX _n (i)
(Here, X is at least one selected from iodine, bromine and chlorine, and n = 1 or 2.)
Cu (OOC-R) _m (ii)
(Here, R is at least one selected from hydrogen, saturated aliphatic hydrocarbons having 1 to 30 carbon atoms, and aromatic hydrocarbons, and m = 1 or 2.)
Cu _l (OOC—R′—COO) _k (iii)
(Here, R ′ is at least one selected from saturated aliphatic hydrocarbons having 1 or 2 carbon atoms and aromatic hydrocarbons, where l = 1 or 2, and k = 1.)
Cu _j Y _i (iv)
(Here, Y is at least one selected from sulfate ion, carbonate ion, nitrate ion, and hydroxide ion, and j = 1 or 2, i = 1 or 2.)
Cu _h O (v)
(Where h = 1 or 2) The copper compound is copper iodide (I), copper bromide (I), copper bromide (II), copper chloride (I), copper chloride (II), copper acetate (I), copper acetate (II), stearin The polyester resin composition according to claim 1, which is copper (II) acid, copper (II) terephthalate, copper (II) sulfate, copper (II) carbonate, copper (I) oxide or copper (II) oxide. The polyester resin composition according to claim 1 or 2, wherein the content of the copper compound with respect to the polyester resin is 1 to 17 ppm on a copper atom basis. The dicarboxylic acid or its ester-forming derivative is at least one selected from terephthalic acid, terephthalic acid diester, 2,6-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid diester. The polyester resin composition as described. The polyester resin composition according to any one of claims 1 to 4, wherein the diol is at least one selected from ethylene glycol, propylene glycol, and butylene glycol. 2 g of the polyester resin composition was dissolved in 20 ml of a phenol / 2,1,1,2,2-tetrachloroethane 3/2 (volume ratio) mixed solution, and the solution haze measured using a cell having an optical path length of 20 mm was 5% or less. The polyester resin composition according to any one of claims 1 to 5. The polyester resin composition according to any one of claims 1 to 6, wherein the gelling ratio after heat treatment at 300 ° C for 6 hours in an oxygen 1% atmosphere is 10% or less. The polyester resin composition according to any one of claims 1 to 7, which has a gelation rate of 28% or less after heat treatment at 300 ° C for 6 hours in an air atmosphere. In the method for producing a polyester resin in which a dicarboxylic acid or an ester-forming derivative thereof and a diol are esterified or transesterified and then polymerized, any of the following (at the time of esterification, transesterification and polymerization): i) to a polyester resin composition in which at least one of the copper compounds represented by formulas (v) is added so as to be 1 to 30 ppm based on a copper atom based on the weight of the obtained polyester resin. Production method.
CuX _n (i)
(Here, X is at least one selected from iodine, bromine and chlorine, and n = 1 or 2.)
Cu (OOC-R) _m (ii)
(Here, R is at least one selected from hydrogen, saturated aliphatic hydrocarbons having 1 to 30 carbon atoms, and aromatic hydrocarbons, and m = 1 or 2.)
Cu _l (OOC—R′—COO) _k (iii)
(Here, R ′ is at least one selected from saturated aliphatic hydrocarbons having 1 or 2 carbon atoms and aromatic hydrocarbons, where l = 1 or 2, and k = 1.)
Cu _j Y _i (iv)
(Here, Y is at least one selected from sulfate ion, carbonate ion, nitrate ion, and hydroxide ion, and j = 1 or 2, i = 1 or 2.)
Cu _h O (v)
(Where h = 1 or 2) The manufacturing method of the polyester resin composition of Claim 9 added so that it may become 1-17 ppm on the basis of a copper atom with respect to the weight of the polyester resin obtained.