JP2018021136A - Method for producing polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyester resin composition excellent in hydrolysis resistance.SOLUTION: Provided is a method for producing a polyester resin composition characterized in that, when a polyester resin obtained by using dicarboxylic acid or its ester formative derivative and diol as the main ingredients is produced, the one obtained by melting polyester resin in a polycondensation reaction step or after the polycondensation reaction is blended with a copper-containing compound and a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure, and the blend is discharged within 60 min from the point of the time of the blending.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polyester resin composition.

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

  The polyester resin has a problem that the acidic carboxyl group at the end serves as a catalyst and promotes hydrolysis of the ester bond. As a means for improving the hydrolysis resistance of the polyester resin, for example, addition of a copper compound that exhibits an acid value reduction effect by decarboxylation can be mentioned.

  In patent document 1, the polyester film formed by mix | blending a copper compound is disclosed, and it is described that an acid value can be reduced and hydrolysis resistance improves.

  Patent Document 2 discloses a polyester film formed by blending a copper compound and an alkali metal halide, and describes that the acid value can be reduced and the hydrolysis resistance is improved.

  Furthermore, Patent Document 3 describes that the acid value can be reduced and the hydrolysis resistance is improved by blending a nitrogen compound containing a copper compound and a tertiary amine structure.

JP 2010-202837 A U.S. Pat. No. 3,446,766 International Publication No. 2016/067618

  In patent document 1, patent document 2, and patent document 3, the acid value reduction effect of polyester is insufficient, and the improvement of hydrolysis resistance by expressing the acid value reduction effect more efficiently has been desired.

  As a result of intensive studies to solve the above problems, a compound containing copper and a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure are blended into the molten polyester resin, and within 60 minutes from the blending point. It has been found that a polyester resin composition having excellent hydrolysis resistance can be obtained by discharging the resin into the water, and the present invention has been achieved.

That is, the present invention is as follows.
(1) A polyester comprising a dicarboxylic acid or an ester-forming derivative thereof, a diol as a main raw material and a polyester resin, a compound containing copper, and a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure A method for producing a resin composition, comprising a polyester resin having a polycondensation reaction step or a polyester resin after polycondensation reaction melted, containing a compound containing copper and a nitrogen-containing heterocyclic structure or a tertiary amine structure. A method for producing a polyester resin composition, wherein a nitrogen chelate ligand is blended and discharged within 60 minutes from the blending time.
(2) The method for producing a polyester resin composition according to (1), wherein the compound is discharged within 30 minutes from the compounding point of the compound containing copper and the nitrogen-containing chelate ligand.
(3) The method for producing a polyester resin composition according to (2), wherein the compound containing copper and the nitrogen-containing chelate ligand are discharged within 15 minutes from the blending time point.
(4) The manufacturing method of the polyester resin composition in any one of (1)-(3) which mix | blends 0.001-10 mmol of compounds containing copper per 100 g of polyester resins on a copper atom basis.
(5) The manufacturing method of the polyester resin composition as described in (4) which mix | blends 0.001-0.1 mmol of compounds containing copper per 100 g of polyester resins on a copper atom basis.
(6) The manufacturing method of the polyester resin composition in any one of (1)-(5) which mix | blends said nitrogen-containing chelate ligand 0.001-10 mmol per 100 g of polyester resins.
(7) The manufacturing method of the polyester resin composition as described in (6) which mix | blends said nitrogen-containing chelate ligand 0.001-0.1 mmol per 100 g of polyester resins.
(8) The nitrogen-containing chelate ligand is blended at a molar ratio of 0.001 to 4 (nitrogen-containing chelate ligand / copper atom of the compound containing copper) with respect to the copper atom of the compound containing copper. (1) The manufacturing method of the polyester resin composition in any one of (7).
(9) The compound containing copper is at least one selected from organic copper salts, inorganic copper salts, copper halides, copper oxides, and copper hydroxides, according to any one of (1) to (8) A method for producing a polyester resin composition.
(10) The method for producing a polyester resin composition according to (9), wherein the compound containing copper is at least one selected from an organic copper salt and an inorganic copper salt.
(11) The nitrogen-containing chelate ligand is a compound having a partial structure of 2,2′-bipyridyl, a compound having a partial structure of 1,10-phenanthroline, and N, N, N ′, N′-tetramethyl. The method for producing a polyester resin composition according to any one of (1) to (10), which is any one selected from compounds having a partial structure of ethylenediamine.
(12) The method for producing a polyester resin composition according to (11), wherein the nitrogen-containing chelate ligand is 2,2′-bipyridyl or 1,10-phenanthroline.
(13) The method for producing a polyester resin composition according to any one of (1) to (12), wherein the polyester resin is at least one selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
(14) The polyester resin composition according to any one of (1) to (13), wherein the temperature of the polyester resin when blending the compound containing copper and the nitrogen-containing chelate ligand is 280 ° C to 300 ° C. Production method.
(15) The method for producing a polyester resin composition according to any one of (1) to (14), wherein the number average molecular weight of the polyester resin in the obtained polyester resin composition is 5,000 to 100,000.
(16) The method for producing a polyester resin composition according to any one of (1) to (15), wherein the polyester resin in the resulting polyester resin composition has an acid value of 5 eq / t or less.

  According to the present invention, a polyester resin composition having excellent hydrolysis resistance can be obtained.

  In the embodiment of the present invention, a polyester resin obtained using a dicarboxylic acid or an ester-forming derivative thereof and a diol as a main raw material, a compound containing copper, and a nitrogen-containing chelate compound having a nitrogen-containing heterocyclic structure or a tertiary amine structure are used. The present invention relates to a polyester resin composition containing a ligand.

(1) Polyester resin The polyester resin obtained in the embodiment of the present invention is a polyester resin obtained by polycondensation using a dicarboxylic acid or an ester-forming derivative thereof and a diol as main raw materials. Here, the main raw material indicates that the constituent units of the dicarboxylic acid, the ester-forming derivative thereof, and the diol in the polymer are 80 mol% or more in total. The total of the structural units is more preferably 90 mol% or more, further preferably 95 mol% or more, and most preferably 100 mol%.

  Although dicarboxylic acid or its ester-forming derivative is not particularly limited, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, diphenylthioether Aromatic dicarboxylic acids such as -4,4'-dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid And aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, undecanedioic acid and dodecanedioic acid, or ester-forming derivatives thereof.

  The ester-forming derivatives mentioned here are the above-mentioned lower alkyl esters of dicarboxylic acids, acid anhydrides, acid halides, and the like. As the lower alkyl ester of dicarboxylic acid, methyl ester, ethyl ester, hydroxyethyl ester, hydroxybutyl ester and the like are preferably used. As the acid anhydride of dicarboxylic acid, an anhydride between dicarboxylic acids, an anhydride of dicarboxylic acid and acetic acid, and the like are preferably used. As halides of dicarboxylic acids, acid chlorides, acid bromides, acid iodides and the like are preferably used.

  As the dicarboxylic acid or the ester-forming derivative thereof used in the embodiment of the present invention, an aromatic dicarboxylic acid or an ester-forming derivative thereof is preferable in that the obtained polyester resin is excellent in heat resistance. As the aromatic dicarboxylic acid or its ester-forming derivative, terephthalic acid, 2,6-naphthalenedicarboxylic acid, or dimethyl ester thereof is more preferable.

  Examples of the diol used in the embodiment of the present invention include ethylene glycol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and decamethylene. 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 these, ethylene glycol, 1,3-propanediol, and 1,4-butanediol are more preferable because the obtained polyester resin is excellent in heat resistance.

  Further, dicarboxylic acid, ester-forming derivative of dicarboxylic acid, and diol may be used alone, or two or more kinds may be used in combination. 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, polycyclohexane dimethylene isophthalate, polyethylene naphthalate. Phthalate, polypropylene naphthalate, polybutylene naphthalate, polycyclohexanedimethylene terephthalate / polyethylene terephthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate Naphthalate, polybutylene terephthalate / naphthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfoisophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, and the like. Here, “/” represents a copolymer. Among these, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, and polyethylene naphthalate are preferable, and polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate are more preferable in terms of excellent heat resistance.

  About the polyester resin obtained by embodiment of this invention, it is preferable that a number average molecular weight is 5000-100000. The number average molecular weight is more preferably 7000-80000, and still more preferably 9000-50000. When the number average molecular weight is greater than 5000, the mechanical strength tends to be large. On the other hand, when the number average molecular weight is 100,000 or less, melt processing tends to be easy. The number average molecular weight can be determined by gel permeation chromatography.

(2) Compound containing copper In the embodiment of the present invention, it is considered that the compound containing copper exhibits the effect of the present invention by forming a copper complex together with a nitrogen-containing chelate ligand described later.

  In the embodiment of the present invention, the valence of copper contained in the compound containing copper to be blended with the polyester resin may be zero, monovalent or divalent. It is more preferable that the valence of copper is monovalent or divalent in that the dispersibility in the polyester resin and the acid value reduction effect are high.

  Although the compound containing copper at the time of mix | blending with a polyester resin is not specifically limited, For example, a copper salt is preferable. The copper salt is not particularly limited, but copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper undecylate, lauric acid Copper oxide, 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 serotate, copper montanate, copper melicinate, copper benzoate, copper oxalate, copper malonate, copper succinate, copper terephthalate, copper isophthalate, copper phthalate, copper salicylate, copper citrate, copper tartrate Organic copper salts such as copper sulfate, copper sulfate, copper carbonate, copper nitrate, etc., copper iodides, copper halides such as copper bromide, copper chloride, copper hydroxides such as copper hydroxide, copper oxide, etc. Copper oxides. The copper valence of these copper salts may be monovalent or divalent, and two or more copper salts may be used in combination. These copper salts may be hydrates. A copper halide is preferable and copper iodide is particularly preferable in that the acid value reducing effect is high. Moreover, copper sulfate is preferable at the point which can make transparency of a polyester resin composition high.

  In the embodiment of the present invention, it is preferable to add 0.001 mmol or more of a compound containing copper on a copper atom basis per 100 g of the polyester resin. By making the compound containing copper 0.001 mmol or more on a copper atom basis per 100 g of the polyester resin, the acid value reduction effect is increased. More preferably, the compound containing copper is 0.005 mmol or more, more preferably 0.01 mmol or more, based on a copper atom per 100 g of the polyester resin. Moreover, it is preferable to mix | blend the compound containing copper 10 mmol or less on a copper atom basis per 100 g of polyester resins. It is preferable to set the compound containing copper to 10 mmol or less based on the copper atom per 100 g of the polyester resin, since a decrease in transparency and a deterioration in color tone can be suppressed. The compound containing copper is more preferably 0.5 mmol or less on a copper atom basis per 100 g of the polyester resin, more preferably 0.03 mmol or less, and most preferably 0.01 mmol or less. Here, in the case of compounding a compound containing copper at the time of polycondensation of the polyester resin, the compounding amount of the compound containing copper can be calculated on the basis of the theoretical polymer amount when it is assumed that all the raw materials are polycondensed. it can.

  When a compound containing copper is blended in a molten polyester resin, components other than copper atoms of the compound containing copper may volatilize. However, since copper atoms do not volatilize, the content of copper atoms in the polyester resin composition containing a compound containing copper basically matches the amount. The copper atom content can be quantified by atomic absorption analysis, fluorescent X-ray analysis, or the like.

(3) Nitrogen-containing chelate ligand having nitrogen-containing heterocyclic structure or tertiary amine structure By blending the compound containing copper, it can be expected that the acid value reduction effect and hydrolysis resistance improvement effect of the polyester resin can be expected. Although it is known, decarboxylation activity is low only by compounding a compound containing copper, and even if the compounding amount is increased, a sufficient acid value reduction effect and hydrolysis resistance improvement effect may not be obtained. In the present invention, by adding a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure capable of coordinating to copper to form a copper complex, decarboxylation activity and dispersion in a polyester resin are achieved. It has been found that the properties are improved. As a result, the inventors succeeded in obtaining a polyester resin excellent in hydrolysis resistance and transparency by lowering the acid value of the polyester resin.

  The nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure is not particularly limited. Examples of the chelate ligand having a nitrogen-containing heterocyclic structure include N-methylazolidine, N-methylpiperidine, pyridine, pyrazine, quinoline, derivatives having a partial structure of isoquinoline, 2,2′-bipyridyl, terpyridine, Examples include 1,10-phenanthroline, 1,8-naphthyridine, nicotinic acid, isonicotinic acid, or derivatives having these partial structures. Examples of the compound having a tertiary amine structure include N-methylazolidine, derivatives having a partial structure of N-methylpiperidine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, or a derivative having a partial structure thereof. These nitrogen-containing chelate ligands having a nitrogen-containing heterocyclic structure or a tertiary amine structure may be hydrates. The nitrogen-containing chelate ligand may be a compound in which the nitrogen constituting the heterocyclic ring constitutes a tertiary amine. That is, the nitrogen-containing chelate ligand may have both a nitrogen-containing heterocyclic structure and a tertiary amine structure.

  Specific examples of nitrogen-containing chelate ligands that form stable copper complexes include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 2,2′-bipyridyl, terpyridine, 1,10-phenanthroline, 1,8-naphthyridine, or derivatives having these partial structures. Examples of the nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure include N, N, N ′, N′-tetramethylethylenediamine and 2,2′- Bipyridyl, 1,10-phenanthroline, 1,8-naphthyridine, or derivatives having these partial structures are more preferred, and 2,2′-bipyridyl, 1,10-phenanthroline is more preferred. Here, the nitrogen-containing chelate ligand is a compound having a plurality of coordination sites containing at least one nitrogen atom in the molecule, and the plurality of coordination sites coordinate simultaneously to one metal atom. It is a compound in a position where it can be formed. In addition, the nitrogen-containing bidentate chelate ligand is a compound having two or more coordination sites containing nitrogen atoms in the molecule, and the two coordination sites containing nitrogen atoms in the molecule are metal 1 It is a compound that can be coordinated to an atom at the same time. If one of the coordination sites is a nitrogen atom, the other coordination sites may be an oxygen atom or a sulfur atom. In the embodiment of the present invention, a nitrogen-containing bidentate chelate ligand or a nitrogen-containing tridentate chelate ligand is preferable, and a nitrogen-containing bidentate chelate ligand is particularly preferable.

  In the embodiment of the present invention, the nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure is preferably blended in an amount of 0.001 mmol or more per 100 g of the polyester resin. By setting the nitrogen-containing chelate ligand to 0.001 mmol or more per 100 g of the polyester resin, the effect of reducing the acid value of the polyester resin is increased, and the effect of improving the transparency of the polyester resin is also exhibited. The nitrogen-containing chelate ligand is more preferably 0.005 mmol or more, more preferably 0.01 mmol or more per 100 g of the polyester resin. Moreover, it is preferable to mix | blend the said nitrogen-containing chelate ligand 10 mmol or less per 100 g of polyester resins, and it is more preferable to mix | blend 0.1 mmol or less. The nitrogen-containing chelate ligand is preferably 10 mmol or less per 100 g of the polyester resin because hydrolysis is not promoted. The nitrogen-containing chelate ligand is more preferably 0.1 mmol or less per 100 g of the polyester resin. The content of the compound having a nitrogen-containing heterocyclic structure or a tertiary amine structure can be determined by extracting the nitrogen-containing chelate ligand from the decomposition product after NMR or PET hydrolysis, and quantifying it by HPLC or GC. it can.

  In the present invention, a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure is used in combination with a compound containing copper, so that the acid value can be reduced even if the compounding amount of the compound containing copper is small. It can be sufficiently reduced. This is also advantageous in terms of ensuring the transparency of the polyester resin.

  Here, when the polyester resin composition of the present invention is obtained by compounding a compound having a nitrogen-containing heterocyclic structure or a tertiary amine structure during the polycondensation of the polyester resin, it is assumed that all the raw materials are polycondensed The compounding amount of the compound having a nitrogen-containing heterocyclic structure or a tertiary amine structure can be calculated on the basis of the theoretical polymer amount.

(4) Mixing ratio In the embodiment of the present invention, in order to efficiently reduce the acid value, a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure is used as a copper-containing compound. It is preferable to mix | blend with a polyester resin by the molar ratio (a nitrogen-containing chelate ligand / copper atom of the compound containing copper) of 0.001-4 on the basis of an atom. The molar ratio (nitrogen-containing chelate ligand / copper atom of the compound containing copper) is more preferably 0.01 or more, further preferably 0.1 or more, and most preferably 0.4 or more. The molar ratio (nitrogen-containing chelate ligand / copper atom of the compound containing copper) is more preferably 2 or less, further preferably 1 or less, and most preferably 0.4 or less. It is preferable to set the molar ratio (nitrogen-containing chelate ligand / copper atom of the compound containing copper) to 0.001 or more because an increase in haze of the polyester resin composition can be suppressed. On the other hand, when the molar ratio (nitrogen-containing chelate ligand / copper atom of the compound containing copper) is 4 or less, the nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure with respect to copper is excessive. This is preferable because the hydrolyzability of the polyester can be suppressed.

(5) Manufacturing method of polyester resin composition The manufacturing method of the polyester resin composition obtained by using dicarboxylic acid or its ester-forming derivative used in the embodiment of the present invention and a diol as a main raw material includes the following two steps. It consists of a process. Hereinafter, the case where dicarboxylic acid alkyl ester is used as the ester-forming derivative will be described. That is, a first stage process comprising (A) esterification reaction or (B) transesterification reaction, followed by a second stage process comprising (C) polycondensation 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 the reaction is carried out until a predetermined amount of water is distilled off. It is the process of obtaining. In addition, the step of (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 polycondensate. .

  The (C) polycondensation reaction, which is the second step, proceeds the dediol reaction by heating and reducing the pressure of the low polycondensate obtained by the (A) esterification reaction or (B) transesterification reaction. And obtaining a high molecular weight polyester resin. In general, the polycondensation reaction temperature at this time is preferably 230 ° C. or higher, more preferably 250 ° C. or higher, and most preferably 280 ° C. or higher. The polycondensation reaction temperature at this time is preferably 300 ° C. or lower. By setting the polycondensation reaction temperature to 230 ° C. or higher, the decarboxylation reaction rate increases, so that the acid value reduction effect tends to be high. When the polycondensation reaction temperature is lower than 300 ° C., the polyester resin obtained tends to be prevented from deteriorating. In the case of polycondensation of polyethylene terephthalate, 280 to 300 ° C is preferable and 290 ° C is more preferable. In the case of polycondensation of polybutylene terephthalate, 240 to 260 ° C is preferable, and 250 to 260 ° C is more preferable.

  In the method for producing a polyester resin used in the embodiment of 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. good. 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 a polycondensation reaction, compounds, such as antimony, titanium, aluminum, tin, germanium, etc. are used.

  Examples of the antimony compound include antimony oxide, antimony carboxylic acid, antimony alkoxide, and the like. Specifically, the antimony oxide includes antimony trioxide, antimony pentoxide and the like, the antimony carboxylic acid includes antimony acetate, antimony oxalate, potassium antimony tartrate, and the like, and the antimony alkoxide includes antimony tri- Examples include n-butoxide and antimony triethoxide.

  Titanium compounds include titanium complexes, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer and other titanium alkoxides, titanium oxides obtained by hydrolysis of titanium alkoxides, titanium acetylacetonate Etc.

  Examples of the aluminum compound include aluminum carboxylate, aluminum alkoxide, aluminum chelate compound, basic aluminum compound and the like. Specific examples of the aluminum compound include aluminum acetate, aluminum hydroxide, aluminum carbonate, aluminum ethoxide, aluminum isopropoxide, aluminum acetylacetonate, and basic aluminum acetate.

  Examples of the tin compound include monobutyltin oxide, dibutyltin oxide, methylphenyltin oxide, tetraethyltin oxide, hexaethylditin oxide, triethyltin hydroxide, monobutylhydroxytin oxide, monobutyltin trichloride, and dibutyltin sulfide.

  Examples of germanium compounds include germanium oxides and germanium alkoxides. Specifically, germanium dioxide, germanium tetroxide, germanium alkoxide as germanium oxide, germanium tetraethoxide, germanium tetrabutoxide, and the like can be given.

  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, and cobalt naphthenate.

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

  These metal compounds may be hydrates.

  A phosphorus compound may be added as a stabilizer to the polyester resin used in the embodiment of the present invention. Specifically, as a stabilizer, phosphoric acid, trimethyl phosphate, triethyl phosphate, ethyl diethylphosphonoacetate, 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2, 4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, tetrakis (2,4-di-t-butyl-5-methylphenyl) [1,1-biphenyl] -4,4′- Examples include diyl bisphosphonite.

  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 have good heat resistance at high temperatures and good color development. It is preferable because it is excellent. 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.

  As a manufacturing method of the polyester resin composition of the embodiment of the present invention, a compound containing copper, a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure may be blended in the step (C). preferable. Or it is preferable to mix | blend the nitrogen-containing chelate ligand which has a compound containing copper, a nitrogen-containing heterocyclic structure, or a tertiary amine structure with respect to what fuse | melted the polyester resin after a polycondensation reaction. In order to efficiently reduce the acid value of the polyester resin, the time from blending to discharging the polyester resin composition is set to 60 minutes or less. It is preferably from 5 minutes to 60 minutes, more preferably from 5 minutes to 30 minutes, and most preferably from 5 minutes to 15 minutes. A compound containing copper in the case where a compound containing copper, a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure, and discharging the resin composition exceeds 60 minutes In addition, since the decarboxylation activity of a copper complex composed of a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure is decreased, the carboxylic acid terminal may be increased by thermal decomposition. In addition, when the time from the blending of the compound containing copper, the nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or the tertiary amine structure to the discharge of the resin composition is within 5 minutes, the removal is performed. Since the time for the carbonation reaction to proceed is insufficient, the acid value cannot be reduced efficiently.

  In addition, polyester when blending a compound containing copper, a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure with a melted polyester resin after the step (C) or polycondensation reaction The effect of the present invention is great when the temperature of the resin is 280 to 300 ° C.

  In addition, as a blending form of a polycondensation catalyst, a compound containing copper, a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure, and other additives, each of them is blended individually. , Any of a form in which each is dissolved or dispersed in a solvent and a form in which the additives are mixed in the solvent and then blended may be used. In order to efficiently reduce the acid value of the polyester resin, a copper-containing compound and a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure are mixed in advance in a solvent to form a copper complex. It is preferable to add after the above. Specific examples of blending a polycondensation catalyst, a compound containing copper, a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure, and other additives as a solution or dispersion include diol as a solvent. It is preferable to mix them after mixing at a weight ratio of 1/100 to 20/100 with respect to the diol.

(6) Polyester resin composition In the polyester resin composition of the embodiment of the present invention, the polyester resin contained in the polyester resin composition is blended with the compound containing copper and the nitrogen-containing chelate ligand described above. A polyester resin composition having an acid value of 5 eq / t or less can be obtained. In a more preferred embodiment, the acid value of the polyester resin can be 3 eq / t or less, and the hydrolysis resistance can be improved. The acid value of the polyester resin is most preferably 2 eq / t or less. Here, the acid value of the polyester resin is usually 0 eq / t or more. Here, when the total blending amount of the polycondensation catalyst other than the polyester resin, the compound containing copper, the nitrogen-containing chelate ligand, the additive and the like is less than 1% by weight, the polyester resin composition is used as the ortho-cresol solvent. The acid value obtained by dissolving and titrating at 25 ° C. using a 0.02 N aqueous sodium hydroxide solution is defined as the acid value of the polyester resin.

  When the total compounding amount of the polycondensation catalyst, the compound containing copper, the nitrogen-containing chelate ligand, the additive, etc. is contained in the polyester resin composition by 1% by weight or more in total, the total compounding material is less than 1% by weight The acid value is measured in a state where additives and the like are removed.

  By setting the acid value of the polyester resin to 5 eq / t or less, the polyester resin composition of the present invention is improved in the number average molecular weight retention of the polyester resin after being treated for 24 hours at 121 ° C. and 100% RH. be able to. The number average molecular weight retention is preferably 85% or more, particularly preferably 90% or more. Here, the number average molecular weight retention is usually 100% or less. The number average molecular weight can be determined by gel permeation chromatography.

  In the embodiment of the present invention, solid phase polymerization may be performed in order to obtain a higher molecular weight polyester resin composition. The apparatus and method used for the solid phase polymerization are not particularly limited, but the solid phase polymerization is carried out by heat treatment under an inert gas atmosphere or under reduced pressure. The inert gas is not particularly limited as long as it is inert to the polyester, and examples thereof include nitrogen, argon, helium, carbon dioxide gas, 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.

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

  The polyester resin composition obtained in the embodiment of the present invention can be molded by a known processing method. The polyester resin composition obtained in the embodiment of the present invention 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, the polyester resin composition is discharged from the pores and cooled and solidified with cooling air. Thereafter, an oil agent is applied to the polyester resin composition, taken up by a take-up roller, and taken up by a take-up device disposed after the take-up roller, whereby undrawn yarn can be collected.

  The undrawn yarn wound up in this way is drawn by a pair of heated rollers. Finally, the unstretched yarn is subjected to tension or relaxation heat treatment to give a fiber having physical properties such as mechanical properties according to the application. In addition, in this extending | stretching process, after taking up in the above-mentioned melt spinning process, it can carry out continuously, without winding once, and it can be set 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.

  Moreover, the method to process the polyester resin composition of this invention into a film is demonstrated concretely. Here, an example is shown in which a low-density unstretched film is prepared by quenching and then biaxially stretched successively, but is not limited to this example.

  The polyester resin composition is vacuum-dried at 180 ° C. for 3 hours or more and then supplied to a single-screw or twin-screw extruder heated to 270 to 320 ° C. under a nitrogen stream or under vacuum to plasticize the polymer. Make it. Then, an unstretched film is obtained by melt-extruding a polyester resin composition from a slit-shaped die and cooling and solidifying it on a casting roll. At this time, it is preferable to use various types of filters, for example, filters made of materials such as sintered metal, porous ceramics, sand, and wire mesh, in order to remove foreign substances and altered polymers. In addition, a gear pump may be provided as necessary to improve the quantitative supply. Subsequently, the sheet-like material molded as described above is biaxially stretched. That is, the sheet-like material formed as described above is stretched biaxially in the longitudinal direction and the width direction and heat-treated. Stretching methods include a sequential biaxial stretching method such as stretching in the width direction after stretching in the longitudinal direction, a simultaneous biaxial stretching method in which the longitudinal direction and the width direction are stretched simultaneously using a simultaneous biaxial tenter, etc. Examples include a method of combining a sequential biaxial stretching method and a simultaneous biaxial stretching method. In order to control the thermal expansion coefficient and the thermal shrinkage rate within the scope of the present invention, it is desirable that the heat treatment after the stretching process is effectively performed without causing relaxation of molecular chain orientation due to excessive heat treatment.

  When processing the polyester resin composition of the embodiment of the present invention into various products, one or more various additives may be added. Examples of the various additives include colorants including pigments and dyes, lubricants, antistatic agents, flame retardants, ultraviolet absorbers, antibacterial agents, nucleating agents, plasticizers, mold release agents, and the like.

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

Hereinafter, the present invention will be described in more detail with reference to examples. The raw materials and reagents used in the examples are as follows.
Dimethyl terephthalate manufactured by SK Chemical Co., Ltd. ethylene glycol manufactured by Nippon Shokubai Co., Ltd. magnesium acetate tetrahydrate manufactured by Kanto Chemical Co., Ltd. antimony trioxide manufactured by Kanto Chemical Co., Ltd. trimethyl phosphate manufactured by Kanto Chemical Co., copper iodide manufactured by Kanto Chemical Co., Ltd.・ Aldrich 1,10-phenanthroline ・ STREM CHEMICALS copper acetate (I)
-Copper acetate (II) manufactured by Kanto Chemical Co., Inc.
・ Aldrich copper sulfate pentahydrate ・ Kanto Chemical Co., Ltd. 2,2′-bipyridyl ・ Tokyo Chemical Industry Co., Ltd. N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine

  In addition, the physical-property value in an Example was measured by the method described below.

(1) Number average molecular weight The number average molecular weight of the polyester resin contained in the polyester resin composition was calculated by gel permeation chromatography under the following conditions.

In the gel permeation chromatography, a sample concentration 1 mg / mL solution obtained by dissolving in hexafluoroisopropanol (added with 0.005N sodium trifluoroacetate) was used for measurement. The measurement conditions are shown below.
Pump: Waters 515 (manufactured by Waters)
Detector: differential refractometer Waters 410 (manufactured by Waters)
Column: Shodex HFIP-806M (2) + HFIP-LG
Solvent: hexafluoroisopropanol (added 0.005N sodium trifluoroacetate)
Flow rate: 1.0 ml / min
Sample injection volume: 0.1 ml
Temperature: 30 ° C
Molecular weight calibration: polymethylmethacrylate.

(2) Acid value (unit: eq / t)
The polyester resin composition was dissolved in ortho-cresol at a concentration of 30 mg / L, and measured with an automatic titration apparatus (Hiranuma Sangyo Co., Ltd., COM-550) at 25 ° C. using a 0.02 N aqueous sodium hydroxide solution. .

(3) Hydrolysis resistance (molecular weight retention rate under 100% humidity)
The pellets obtained by vacuum drying the polyester resin composition at 140 ° C. for 16 hours were pressed at 280 ° C. to form a plate having a thickness of 1 mm, and then, using a highly accelerated life test apparatus (EHS-411, manufactured by Espec), The temperature was maintained for 24 hours under high humidity conditions of 100% RH. The retention (%) of the number average molecular weight after treatment relative to the number average molecular weight before treatment was calculated.

Example 1
100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and 0.06 part by weight of magnesium acetate tetrahydrate were mixed. Thereafter, the mixture was melted at 150 ° C. in a nitrogen atmosphere, heated to 240 ° C. over 4 hours with stirring, methanol was distilled off, and then transesterification was performed, whereby bis (hydroxyethyl) terephthalate. Got.

  0.2 mmol of antimony trioxide, 0.1 mmol of trimethyl phosphate, 0.02 mmol of copper (I) iodide, 0.1 g of the theoretical amount of polymer obtained by polycondensation of bis (hydroxyethyl) terephthalate is 100 g. 02 mmol of 1,10-phenanthroline was weighed respectively. 15 times the amount of ethylene glycol was added to each weight of antimony trioxide and trimethyl phosphate to prepare a mixture with ethylene glycol. In addition, to a mixture in which 15 times the amount of ethylene glycol was added to the weight of copper (I) iodide, a solution in which 15 times the amount of ethylene glycol was added and dissolved relative to the weight of 1,10-phenanthroline was added. A mixture of copper (I) iodide, 1,10-phenanthroline, and ethylene glycol was prepared.

  Bis (hydroxyethyl) terephthalate was charged into a test tube and melted at 250 ° C., and then a mixture of antimony trioxide and ethylene glycol prepared as described above and an ethylene glycol solution of trimethyl phosphate were charged and reacted. While gradually raising the temperature from 250 ° C. to 290 ° C. over 60 minutes, the pressure was reduced from normal pressure to 130 Pa over 60 minutes, and a polycondensation reaction was performed at 290 ° C. and 130 Pa. After 125 minutes had elapsed from the time when the temperature was disclosed, a mixture of copper (I) iodide, 1,10-phenanthroline and ethylene glycol was added. Thereafter, after 125 minutes had elapsed from the time when the temperature was disclosed, the polycondensation reaction was stopped by using atmospheric pressure with nitrogen. Immediately after the melt was discharged in the form of a strand, it was cooled and cut to obtain a polyester resin composition pellet. The number average molecular weight, acid value, and hydrolysis resistance were measured using the obtained pellets.

  The results are shown in Tables 1 and 2.

Examples 2-16 and Comparative Examples 1-7
A polyester resin composition was obtained in the same manner as in Example 1 except that the type, compounding amount and charging time of the compound containing copper and / or the nitrogen-containing chelate ligand were changed.

Example 17
0.02 mmol of copper (I) iodide and 0.02 mmol of 1,10-phenanthroline were weighed with respect to 100 g of the theoretical amount of polymer obtained by polycondensation of bis (hydroxyethyl) terephthalate. A solution prepared by adding 15 times the amount of ethylene glycol to the weight of 1,10-phenanthroline to a mixture obtained by adding 15 times the amount of ethylene glycol to the weight of copper (I) iodide is added. A mixture of copper (I) chloride, 1,10-phenanthroline, and ethylene glycol was prepared.

  100 g of the polyester resin composition obtained in Comparative Example 1 was melted at 280 ° C. for 10 minutes in a nitrogen atmosphere. The molten polyester resin composition was charged with a mixture of copper (I) iodide, 1,10-phenanthroline and ethylene glycol, and the pressure was reduced to 130 Pa while stirring. 15 minutes after charging the mixture of copper (I) iodide, 1,10-phenanthroline and ethylene glycol, the mixture was discharged, cooled, and cut to obtain a polyester resin composition pellet.

The number average molecular weight of the obtained pellet was 14000, the acid value was 1.8 eq / t, and the number average molecular weight retention after 24 hours under the condition of 121 ° C. and 100% RH was 90.5%.
The polyethylene terephthalate resin compositions obtained in Examples 1 to 17 of the present invention exhibited a value excellent in hydrolysis resistance as compared with the polyethylene terephthalate resin compositions obtained in Comparative Examples 1 to 7.

Claims (16)

Polyester resin composition comprising a dicarboxylic acid or ester-forming derivative thereof and a diol as a main raw material and a polyester resin, a compound containing copper, and a nitrogen-containing chelate ligand having a nitrogen-containing heterocyclic structure or a tertiary amine structure A process comprising the steps of: a polyester resin polycondensation reaction step or a polyester resin after a polycondensation reaction is melted, and a compound containing copper and a nitrogen-containing chelate compound having a nitrogen-containing heterocyclic structure or a tertiary amine structure. A method for producing a polyester resin composition, wherein a ligand is blended and discharged within 60 minutes from the blending time. It discharges within 30 minutes from the compounding time of the compound containing copper and the said nitrogen-containing chelate ligand, The manufacturing method of the polyester resin composition of Claim 1 characterized by the above-mentioned. 3. The method for producing a polyester resin composition according to claim 2, wherein the compound is discharged within 15 minutes from the compounding point of the compound containing copper and the nitrogen-containing chelate ligand. The manufacturing method of the polyester resin composition in any one of Claims 1-3 which mix | blend 0.001-10 mmol of compounds containing copper with respect to 100 g of polyester resins on a copper atom basis. The manufacturing method of the polyester resin composition of Claim 4 which mix | blends the compound containing copper 0.001-0.1 mmol per 100 g of polyester resins on a copper atom basis. The manufacturing method of the polyester resin composition in any one of Claims 1-5 which mix | blends the said nitrogen-containing chelate ligand 0.001-10 mmol per 100 g of polyester resins. The manufacturing method of the polyester resin composition of Claim 6 which mix | blends the said nitrogen-containing chelate ligand 0.001-0.1 mmol per 100 g of polyester resins. The said nitrogen-containing chelate ligand is mix | blended with the molar ratio (a nitrogen-containing chelate ligand / copper atom of the compound containing copper) of 0.001-4 with respect to the copper atom of the compound containing copper. The manufacturing method of the polyester resin composition in any one of -7. The polyester resin composition according to any one of claims 1 to 8, wherein the compound containing copper is at least one selected from an organic copper salt, an inorganic copper salt, a copper halide, a copper oxide, and a copper hydroxide. Manufacturing method. The method for producing a polyester resin composition according to claim 9, wherein the compound containing copper is at least one selected from an organic copper salt and an inorganic copper salt. The nitrogen-containing chelate ligand is a compound having a 2,2′-bipyridyl partial structure, a compound having a 1,10-phenanthroline partial structure, and a N, N, N ′, N′-tetramethylethylenediamine moiety. It is either selected from the compound which has a structure, The manufacturing method of the polyester resin composition in any one of Claims 1-10. The method for producing a polyester resin composition according to claim 11, wherein the nitrogen-containing chelate ligand is 2,2'-bipyridyl or 1,10-phenanthroline. The method for producing a polyester resin composition according to claim 1, wherein the polyester resin is at least one selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. The method for producing a polyester resin composition according to any one of claims 1 to 13, wherein the temperature of the polyester resin at the time of blending the compound containing copper and the nitrogen-containing chelate ligand is 280 ° C to 300 ° C. The method for producing a polyester resin composition according to any one of claims 1 to 14, wherein the number average molecular weight of the polyester resin in the obtained polyester resin composition is 5,000 to 100,000. The method for producing a polyester resin composition according to any one of claims 1 to 15, wherein an acid value of the polyester resin in the obtained polyester resin composition is 5 eq / t or less.