JP2016044185A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition having excellent oxidation degradation resistance.SOLUTION: A polyester resin composition contains a transition metal element and a phosphorus element, where a diol-derived component with not more than 15 carbon atoms having carbon-carbon multiple bond sites is contained by 0.02 mol% or more based on the total acid components.SELECTED DRAWING: None

Description

The present invention relates to a polyester composition having excellent resistance to oxidative degradation.

Polyester is excellent in mechanical properties, thermal properties, chemical resistance, electrical properties, and moldability, and is used in various applications.

  Therefore, polyester film is used for solar battery back sheets, water heater motors, car air conditioner motors and drive motors, as well as magnetic insulation materials, capacitor materials, packaging materials, building materials, photographs, etc. It is used as various industrial materials such as applications, graphic applications, and thermal transfer applications.

  Among these applications, electrical insulating materials are often used in harsh environments for a long period of time. Polyesters are mechanically brittle due to a decrease in molecular weight and an increase in crystallinity due to oxidative degradation and hydrolysis. The physical properties are reduced. For this reason, when used in a harsh environment for a long period of time, resistance to oxidation and hydrolysis is required.

  As a method for avoiding problems due to oxidation, Patent Documents 1 and 2 exemplify methods in which a resin having a carbon-carbon double bond, which is a resin having an oxygen absorbing ability, is mixed with a polyester resin together with a transition metal. However, these methods imply that the mechanical properties inherent to polyester are impaired by adding a rubber-like resin, and that a resin suitable for film use requiring durability cannot be obtained due to a decrease in Tg. There is a problem, and further, there is a problem that the effect of being able to sufficiently suppress the oxidative degradation of the polyester resin composition is not obtained although it has oxygen absorption ability. Further, Patent Document 3 discloses a polyester resin having an oxygen absorbing ability even when there is no transition metal by copolymerizing a dicarboxylic acid having a double bond. However, there was a problem that a resin suitable for film use could not be obtained and an effect of improving the oxidative degradability of polyester was not obtained.

JP 2013-71968 A JP 2011-157411 A JP 2008-7739 A

  The object of the present invention is to solve the above-mentioned problems and to provide a polyester resin excellent in oxidation and decomposition resistance without impairing the mechanical properties of the polyester resin.

In order to solve the above problems, the present invention has the following configuration. That is,
(1) A polyester containing a transition metal element and containing 0.02 mol% or more of a diol-derived component having a carbon-carbon multiple bond site and having 15 or less carbon atoms, based on the total acid component Resin composition.
(2) The polyester resin composition as described in (1), which contains a phosphorus element.
(3) The polyester according to (1) or (2), wherein M / P, which is the ratio of the molar amount M of the transition metal element and the molar amount P of the phosphorus element, is 0.1 to 3.0. Resin composition.
(4) The polyester resin composition according to any one of (1) to (3), wherein the transition metal element includes at least one selected from Cr, Mn, Fe, Co, Ni, and Zn. object.
(5) The polyester resin composition according to any one of (1) to (4), wherein the carbon-carbon multiple bond site is a double bond.

  According to the present invention, a polyester resin excellent in resistance to oxidation and decomposition can be obtained without impairing the mechanical properties of polyester.

The present invention is described in detail below.
The present invention is characterized by containing 0.02 mol% or more of a diol-derived component having a carbon-carbon multiple bond site and containing a transition metal element and having a carbon-carbon multiple bond site. It is a polyester resin composition. With this configuration, since the Tg does not decrease, a polyester resin composition having excellent oxidative degradation resistance can be obtained without impairing the mechanical strength of the polyester.

The polyester used in the present invention refers to a polyester obtained by polycondensation of a dicarboxylic acid component and a diol component.
As the dicarboxylic acid component in the present invention, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, etc. Aliphatic dicarboxylic acids, adamantane dicarboxylic acid, norbornene dicarboxylic acid, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, and other alicyclic dicarboxylic acids, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5 -Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylendandicarboxylic acid Ant Senjikarubon acid, phenanthrene carboxylic acid, 9,9'-bis (4-carboxyphenyl) dicarboxylic acids such as fluorene acids and aromatic dicarboxylic acids, or include an ester derivative thereof. Among these, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are used from the viewpoint of oxidation resistance and heat resistance of the polyester resin composition, heat and humidity resistance, and mechanical strength when the composition is formed into a film. It is preferable to use it.

  Various diols can be used as the diol component in the present invention. For example, aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentylglycol, and alicyclic diols Is cyclohexanedimethanol, cyclohexanediethanol, decahydronaphthalene diethanol, decahydronaphthalene diethanol, norbornane dimethanol, norbornane dimethanol, tricyclodecane dimethanol, tricyclodecane ethanol, tetracyclododecane dimethanol, tetracyclododecane diethanol, decalin di Saturated alicyclic primary diols such as methanol and decalin diethanol, 2,6-dihydroxy-9-oxabicyclo [3,3,1] nonane, 3,9-bis 2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (spiroglycol), 5-methylol-5-ethyl-2- (1,1-dimethyl) 2-hydroxyethyl) -1,3-dioxane, saturated heterocyclic primary diols containing cyclic ethers such as isosorbide, other cyclohexanediols, bicyclohexyl-4,4′-diols, 2,2-bis (4-hydroxys) (Cyclohexylpropane), 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiol, 4-cyclopentene-1,3-diol, adamantyldiol Various alicyclic diols such as paraxylene glycol, bisphenol A, bis Phenol S, styrene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9'-aromatic cyclic diols such as bis (4-hydroxyphenyl) fluorene can be exemplified. In addition to the diol, polyfunctional alcohols such as trimethylolpropane and pentaerythritol can also be used as long as they do not gel.

  Among these, a diol having a boiling point of 230 ° C. or lower is preferable, and an aliphatic diol is preferable. Among them, for example, ethylene glycol is particularly preferable from the viewpoint of mechanical properties such as elongation and flexibility when the composition is formed into a film.

  In addition, other dicarboxylic acid and diol may be copolymerized to such an extent that the range of the effect of the present invention is not impaired.

  In the polyester resin composition of the present invention, in order to impart good oxidative degradation resistance, it is important that a component derived from a diol having a carbon-carbon multiple bond site and having 15 or less carbon atoms is contained. In addition, the carbon-carbon multiple bond site | part said here does not include the carbon-carbon multiple bond site | part applicable to an aromatic carbon-carbon double bond site like a benzene ring or a pyridine ring. By having a carbon-carbon multiple bond, even if oxidized, the multiple bond is oxidized, so that the main chain can be prevented from being broken. In addition, by setting the number of carbon atoms to 15 or less, the probability of oxidative decomposition due to hydrogen abstraction of oxygen radicals can be suppressed, so that more efficient oxidative decomposition can be suppressed.

Examples of the diol having a carbon-carbon multiple bond include 2-butene-1,4-diol, 2-pentene-1,5-diol, 3-hexene-1,6-diol, and 3-heptene-1,7. -Diol, 4-octene-1,8-diol, 4-nonene-1,9-diol, 5-decene-1,10-diol, 5-undecene-1,11-diol, 6-dodecene-1,12 Straight chain diols having double bonds such as diol, 6-tridecene-1,13-diol, 7-tetradecene-1,14-diol, 7-pentadecene-1,15-diol, and their positional isomers, cyclohexa Cyclic diols having a double bond such as -4-ene-1,2-diyldimethanol and their positional isomers, 2-butyne-1,4-diol, 2-pentyne-1,5 All, 3-hexyne-1,6-diol, 3-heptin-1,7-diol, 4-octyne-1,8-diol, 4-nonine-1,9-diol, 5-decyne-1,10- Diol, 5-undecin-1,11-diol, 6-dodecin-1,12-diol, 6-tridecine-1,13-diol, 7-tetradecin-1,14-diol, 7-pentadecine-1,15- Examples include, but are not limited to, diols having triple bonds such as diols and positional isomers thereof.
Among them, a linear diol having 14 or less carbon atoms is preferable from the viewpoint of improving the oxidative degradation resistance, more preferably a linear diol having 8 or less carbon atoms, and still more preferably a linear diol having 5 or less carbon atoms. . In addition, when a double bond and a triple bond are compared, it is more preferable to use a diol having a double bond from the viewpoint of resistance to oxidative degradation. The stereochemistry of the double bond may be either E or Z, or a mixture of E and Z forms. In addition to the diols exemplified above, a diol having a plurality of multiple bonds may be used, or two or more kinds of diols may be used.

In addition, it is important that these diol-derived components are contained in an amount of 0.02 mol% or more based on the total acid components. By containing 0.02 mol% or more, the target oxidative degradation inhibiting effect can be obtained. More preferably, it is 0.05 mol% or more, More preferably, it is 0.15 mol% or more. The upper limit of the content is not particularly provided, but when the amount of the diol-derived component is more than 2.0 mol%, the amount of COOH end groups of the polyester resin composition is increased, and the hydrolysis resistance may be deteriorated. Preferably it is 2.0 mol% or less, More preferably, it is 1.5 mol% or less. The content was determined using ¹ H-NMR. In the case of a diol having a double bond, the content was determined from the integral ratio of the double bond, and in the case of a diol having a triple bond, the content was determined from the integral ratio of the alkyl chain portion. When the content is 0.2 mol% or less, it is difficult to define the content by NMR, so the content was determined using a calibration curve created by measuring the GC of the sample whose content was determined by NMR. .

  In the polyester resin composition of the present invention, it is necessary to contain a transition metal element in order to impart oxidation resistance. The presence of a transition metal can selectively oxidize multiple bonds. As a result, the effect of inhibiting oxidative degradation is exhibited by preventing the main chain from being broken by oxidation of other alkyl chain portions. The type is not particularly limited as long as it is a transition metal that becomes an oxidation catalyst, but Cr, Mn, Fe, Co, Ni, and Zn are preferable, and among these metals, Mn is more preferable.

  Specific examples of the chromium compound include, but are not limited to, potassium potassium sulfate, chromium chloride, chromium sulfate, chromium acetate, chromium acetylacetonate, and the like.

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

  Specific examples of the iron compound include, but are not limited to, iron chloride, iron sulfate, iron nitrate, iron carbonate, iron acetate, iron acetylacetonate, and iron benzoate.

  Specific examples of the cobalt compound include cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt acetate, cobalt acetylacetonate, and cobalt benzoate.

  Specific examples of the nickel compound include nickel chloride, nickel carbonate, nickel nitrate, nickel sulfate, nickel acetate, nickel benzoate, nickel sulfamate, nickel acetylacetonate, and the like.

  Specific examples of the zinc compound include zinc chloride, zinc ammonium chloride, zinc cyanide, zinc nitrate, zinc carbonate, zinc sulfate, zinc sulfide, zinc acetate, zinc benzoate, and zinc alkoxide.

  The polyester resin composition of the present invention preferably contains a phosphorus element. The reason is that the oxidative degradation resistance is further improved by the synergistic effect of the heat resistance imparted by the phosphorus element content and the oxidative degradation resistance imparted by the above. The phosphorus compound to be used is not particularly limited, and examples thereof include phosphite compounds, phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinic acid compounds, and phosphine compounds. It is done.

  Specific examples of the phosphite compound include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4 -Di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butyl) Phenyl) octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 0-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), 4, 4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite), 4,4'-isopropylidene-bis (diphenylmonoalkyl (C12-C15) phosphite), 1,1,3- Tris (2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl) butane, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite, cyclic Neopentanetetrayl bis (octadecyl phosphite), cyclic neopentane tetrayl bis (isodecyl phosphite) Cyclic neopentanetetrayl bis (nonylphenyl phosphite), cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl phosphite), cyclic neopentanetetrayl bis (2,4-dimethylphenyl) Phosphite), cyclic neopentanetetraylbis (2,6-di-t-butylphenylphosphite), 2,2′-bis (2,6-di-t-butyl-4-methylphenoxy) -5 , 5'-spirobi [1,3,2-dioxaphosphorinane].

  Phosphate compounds include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate , Tripotassium phosphate, lithium dihydrogen phosphate, dilithium hydrogen phosphate, and trilithium phosphate.

  Phosphonic acid compounds include methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid Anthrylphosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2,5 -Dicarboxyphenylphosphonic acid, 2,6-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid, 2 , 3, 5 Tricarboxyphenylphosphonic acid, 2,3,6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, methylphosphonic acid dimethyl ester, methylphosphonic acid diethyl Ester, ethylphosphonic acid dimethyl ester, ethylphosphonic acid diethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, benzylphosphonic acid dimethyl ester, benzylphosphonic acid diethyl ester, benzylphosphonic acid diphenyl ester, Lithium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), sodium (3,5-di-tert-butyl-4-hydroxy) Ethyl benzylphosphonate), magnesium bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate), calcium bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate), Examples include diethylphosphonoacetic acid, methyl diethylphosphonoacetate, and ethyl diethylphosphonoacetate.

  Phosphinic acid compounds include hypophosphorous acid, sodium hypophosphite, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid, xylylphosphinic acid , Biphenylylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, ditolylphosphinic acid, dixylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid Anthrylphosphinic acid, 2-carboxyphenylphosphinic acid, 3-carboxyphenylphosphinic acid, 4-carboxyphenylphosphinic acid, 2,3-dicarboxyphenylphosphine Acid, 2,4-dicarboxyphenylphosphinic acid, 2,5-dicarboxyphenylphosphinic acid, 2,6-dicarboxyphenylphosphinic acid, 3,4-dicarboxyphenylphosphinic acid, 3,5-dicarboxyphenyl Phosphinic acid, 2,3,4-tricarboxyphenylphosphinic acid, 2,3,5-tricarboxyphenylphosphinic acid, 2,3,6-tricarboxyphenylphosphinic acid, 2,4,5-tricarboxyphenylphosphinic acid 2,4,6-tricarboxyphenylphosphinic acid, bis (2-carboxyphenyl) phosphinic acid, bis (3-carboxyphenyl) phosphinic acid, bis (4-carboxyphenyl) phosphinic acid, bis (2,3-di Carboxyphenyl) phosphinic acid, bis (2,4-dicarboxy) Enyl) phosphinic acid, bis (2,5-dicarboxyphenyl) phosphinic acid, bis (2,6-dicarboxyphenyl) phosphinic acid, bis (3,4-dicarboxyphenyl) phosphinic acid, bis (3,5- Dicarboxyphenyl) phosphinic acid, bis (2,3,4-tricarboxyphenyl) phosphinic acid, bis (2,3,5-tricarboxyphenyl) phosphinic acid, bis (2,3,6-tricarboxyphenyl) phosphine Acid, bis (2,4,5-tricarboxyphenyl) phosphinic acid, and bis (2,4,6-tricarboxyphenyl) phosphinic acid, methylphosphinic acid methyl ester, dimethylphosphinic acid methyl ester, methylphosphinic acid ethyl ester Dimethyl phosphinic acid ethyl ester, ethyl phosphinic acid Chill ester, diethylphosphinic acid methyl ester, ethylphosphinic acid ethyl ester, diethylphosphinic acid ethyl ester, phenylphosphinic acid methyl ester, phenylphosphinic acid ethyl ester, phenylphosphinic acid phenyl ester, diphenylphosphinic acid methyl ester, diphenylphosphinic acid ethyl ester, Examples thereof include diphenylphosphinic acid phenyl ester, benzylphosphinic acid methyl ester, benzylphosphinic acid ethyl ester, benzylphosphinic acid phenyl ester, bisbenzylphosphinic acid methyl ester, bisbenzylphosphinic acid ethyl ester, and bisbenzylphosphinic acid phenyl ester.

  Examples of the phosphine oxide compound include trimethylphosphine oxide, triethylphosphine oxide, tripropylphosphine oxide, triisopropylphosphine oxide, tributylphosphine oxide, triphenylphosphine oxide, and the like.

  Examples of the phosphonous acid compound include methylphosphonous acid, ethylphosphonous acid, propylphosphonous acid, isopropylphosphonous acid, butylphosphonous acid, and phenylphosphonous acid.

  Phosphinic acid compounds include methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid. Examples include phosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, diphenylphosphinic acid, and the like.

Examples of the phosphine compound include methylphosphine, dimethylphosphine, trimethylphosphine, melephosphine, diethylphosphine, triethylphosphine, phenylphosphine, diphenylphosphine, and triphenylphosphine.
Among them, it is preferable to use phosphoric acid and phosphoric acid metal salt in combination so that hydrolysis resistance can be imparted while maintaining oxidative degradation resistance, and this combination is preferable. Among the phosphoric acid metal salts, phosphoric acid is preferable. More preferably, sodium dihydrogen or potassium dihydrogen phosphate is used.
In the polyester resin composition of the present invention, M / P, which is the ratio of the molar amount of the transition metal element to the molar amount of the phosphorus element, is preferably 0.1 to 3.0. By making M / P within this range, excellent oxidative degradation resistance can be imparted. The lower limit of M / P is preferably 0.2 or more, and more preferably 0.5 or more. As an upper limit, Preferably it is 2.5 or less, More preferably, it is 1.5 or less.

  The polyester resin composition of the present invention is an endblocker, antioxidant, ultraviolet absorber, flame retardant, fluorescent whitening agent, matting agent, plasticizer or antifoaming agent, as long as the effects of the present invention are not impaired. You may mix | blend another additive etc. as needed.

  The oxidative degradation resistance of the polyester resin is evaluated by the values of ΔIV, which is an IV decrease amount when heat-treated at 200 ° C. for 24 hours in an air atmosphere, and ΔCOOH, which is an increase amount of COOH end groups. For ΔIV, the lower limit is ΔIV = 0.26, preferably ΔIV ≦ 0.25, more preferably ΔIV ≦ 0.22, more preferably ΔIV ≦ 0.20, and even more preferably ΔIV ≦ 0.18. . Regarding ΔCOOH, the lower limit is ΔCOOH = 130, preferably ΔCOOH ≦ 100, more preferably ΔCOOH ≦ 85.0, still more preferably ΔCOOH ≦ 75.0, and even more preferably ΔCOOH ≦ 70.0.

  Although the specific example is given below about the manufacturing method of the polyester resin composition of this invention, it is not limited to this. In addition, as long as the apparatus for manufacturing polyester and a technical process are apparatuses normally used, what kind of apparatus and process may be sufficient as it.

  A reaction vessel is charged with dimethyl terephthalate, ethylene glycol, and a diol having multiple bonds so as to have a predetermined polymer composition. In this case, the reactivity is improved by adding 1.7 to 2.3 times mol of ethylene glycol with respect to all dicarboxylic acid components. After melting these at about 150 ° C., a transesterification catalyst and a polycondensation catalyst are added, and methanol is distilled off while gradually raising the temperature to 240 ° C. to carry out a transesterification reaction. After the transesterification reaction, a phosphorus compound is added to deactivate the transesterification catalyst.

  Thereafter, the reaction product was charged into the polymerization apparatus, while the temperature inside the polymerization apparatus was gradually raised to 290 ° C., while the polymerization apparatus internal pressure was gradually reduced from normal pressure to 133 Pa or less, and ethylene glycol was distilled off while allowing the polymerization reaction to proceed. The reaction is terminated at a stage where a predetermined stirring torque is reached, and the polyester resin is discharged from the polymerization apparatus into a water tank in a strand shape. The discharged polyester resin is quenched in a water tank and wound up, and then cut with a cutter to obtain a polyester chip.

  As the catalyst used for the production of the polyester composition of the present invention, known transesterification catalysts, polycondensation catalysts, and cocatalysts can be used. For example, examples of the polymerization catalyst include antimony compounds, germanium compounds, titanium compounds, and aluminum compounds. As the transesterification catalyst and co-catalyst, an organic manganese compound, an organic magnesium compound, an organic calcium compound, an organic cobalt compound, an organic lithium compound, or the like is preferably used.

  The polycondensation catalyst is preferably an antimony compound from the viewpoints of polymerization stability, production cost, and heat resistance of the composition, more preferably diantimony trioxide, diantimony pentoxide, and more preferably diantimony trioxide. The addition amount of the antimony element is preferably 80 ppm or more and 500 ppm or less with respect to the total amount of the polyester from the viewpoint of high catalytic effect and suppression of foreign matter in the polyester, and more preferably 200 ppm or more and 400 ppm or less.

  As the transesterification catalyst and the cocatalyst, known catalysts such as an organic manganese compound, an organic calcium compound, an organic magnesium compound, and an organic cobalt compound can be used. The addition amount of the transesterification catalyst and the co-catalyst is 30 ppm or more and 200 ppm or less, preferably 100 ppm or more and 190 ppm or less as a metal element with respect to the total amount of the polyester resin composition from the viewpoint of heat resistance and reactivity.

  As a minimum of the addition amount of a phosphorus compound, it is preferable that it is 7 ppm or more as a phosphorus element amount with respect to this polyester resin composition, More preferably, it is 20 ppm or more, More preferably, it is 30 ppm or more. Moreover, as an upper limit of the addition amount of a phosphorus compound, it is preferable that it is 210 ppm or less as a phosphorus element amount with respect to this polyester resin composition, More preferably, it is 150 ppm or less, More preferably, it is 100 ppm or less.

  The polyester resin composition of the present invention may be subjected to solid phase polymerization according to the purpose. The solid phase polymerization is preferably performed at a temperature of the melting point of the polyester resin composition of −10 ° C. or lower and the melting point of −60 ° C. or higher and a vacuum degree of 0.3 Torr or lower.

  In addition, the polyester composition of the present invention is excellent in oxidation and decomposition resistance, and the film obtained by forming a film is an electrically insulating film that requires durability when exposed to air or oxygen for a long time. It is used suitably for the film for solar cell backsheets.

  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 with the following method.

(1) Phosphorous amount in polymer and amount of transition metal element Measured using a fluorescent X-ray analyzer (model number: 3270) manufactured by Rigaku Corporation.

(2) Measurement of glass transition temperature (Tg) In accordance with JIS-K7121 (No. 1987), Tm is calculated with the chart obtained at the time of the second cycle temperature rise using the following measuring machine, and the drop in melting point is calculated. confirmed.

Apparatus: Differential scanning calorimeter DSCQ100 (manufactured by TA Instruments)
Measurement conditions: Under nitrogen atmosphere Measurement range: 50-280 ° C
Sample weight: 10 mg (using TA Instruments aluminum pan)
Temperature program:
1st cycle Room temperature → Temperature rise (16 ° C / min) → Hold at 50 ° C for 2 minutes → Temperature rise (16 ° C / min) → Hold at 280 ° C for 5 minutes → Take out outside the electric furnace and quench with liquid nitrogen (cool for 2 minutes) → Raise to room temperature (Leave for 5 minutes)
2nd cycle 50 ° C. 2 minutes hold → temperature rise (16 ° C./min)→280° C. → temperature drop (16 ° C./min)→25° C.

(3) Measurement of content of diol-derived component having multiple bonds
Determined using ¹ H-NMR. In the case of a diol having a double bond, the content was determined from the integration ratio of the double bond, and in the case of a diol having a triple bond, the content was determined from the integration ratio of the alkyl chain portion. When the content is 0.2 mol% or less, it is difficult to define the content by NMR, so the content was determined using a calibration curve created by measuring the GC of the sample whose content was determined by NMR. .

(4) Intrinsic viscosity of polyester (IV)
It measured at 25 degreeC using the o-chlorophenol solvent.

(5) COOH terminal group amount of polyester Measured by the method of Malice. (Reference M. J. Malice, F. Huizinga, Anal. Chem. Acta, 22 363 (1960)).

(6) Oxidative degradation resistance A pellet-shaped polyester resin composition vacuum-dried at 150 ° C. for 12 hours is heat-treated at 200 ° C. for 24 hours in an air atmosphere, and ΔIV that is an IV decrease amount and ΔCOOH that is an increase amount of COOH end groups Was calculated by the following equation.
ΔIV = | IV (after treatment) −IV (before treatment) ｜
ΔCOOH = | COOH (after treatment) −COOH (before treatment) |
The lower the ΔCOOH and ΔIV, the better the heat resistance.

Example 1
100.0 parts by weight of dimethyl terephthalate, 60.7 parts by weight of ethylene glycol (1.9 times mole of dicarboxylic acid component), 6.9 parts by weight of cis / trans mixture of 2-butene-1,4-diol (dicarboxylic acid) Each was measured at a rate of 15 mol%) with respect to the acid component, and charged into the transesterification reactor. After the contents were dissolved at 150 ° C., 0.052 parts by weight of manganese acetate tetrahydrate and 0.027 parts by weight of antimony trioxide were added and stirred as catalysts.
The temperature was raised to 190 ° C. over 60 minutes, further raised to 200 ° C. over 60 minutes, and then methanol was distilled while raising the temperature to 240 ° C. over 90 minutes. After distillation of a predetermined amount of methanol, an ethylene glycol solution of 0.015 part by weight of phosphoric acid / 0.0235 part by weight of sodium dihydrogen phosphate dihydrate was added and stirred for 5 minutes to complete the transesterification reaction. did.
Thereafter, the reaction product is charged into the polymerization apparatus, and while the temperature in the polymerization apparatus is raised from 235 ° C. to 290 ° C. over 90 minutes, the pressure in the polymerization apparatus is gradually reduced from normal pressure to vacuum to distill ethylene glycol. . When the melt viscosity corresponding to an intrinsic viscosity of 0.7 is reached, the reaction is terminated, the inside of the reaction system is brought to atmospheric pressure with nitrogen gas, discharged into cold water in the form of a strand from the lower part of the polymerization apparatus, cut, and pelletized polyester A resin composition was obtained. The properties of the obtained polyester resin composition are shown in Table 1. The content derived from a diol component having a carbon-carbon multiple bond was determined by NMR.
The polyester resin composition obtained in Example 1 had sufficient oxidative degradation resistance.

(Examples 2 to 6)
A polyester resin composition as in Example 1 except that the amount of 2-butene-1,4diol added was changed so that the content of the component derived from the diol having a carbon-carbon bond would be the value shown in Table 1. I got a thing. The properties of the obtained polyester resin composition are shown in Table 1. In addition, content of the component derived from the diol which has a carbon-carbon multiple bond was determined by NMR and GC as above-mentioned.
The polyester resin compositions obtained in Examples 2 to 6 had sufficient oxidative degradation resistance.

(Comparative Example 1)
A polyester resin composition was obtained in the same manner as in Example 1 except that a cis-trans mixture of 2-butene-1,4-diol, which is a diol having a carbon-carbon multiple bond, was not added. Table 2 shows the characteristics of the obtained polyester resin composition.
Since the polyester resin composition obtained in Comparative Example 1 does not contain a component derived from a diol having a carbon-carbon multiple bond, sufficient oxidative degradation resistance was not obtained.

(Comparative Example 2)
A polyester resin composition was obtained in the same manner as in Example 1 except that the compound used as a catalyst for the transesterification reaction was replaced with Mg acetate, which is a compound not containing a transition metal, to conduct the transesterification reaction. Table 2 shows the characteristics of the obtained polyester resin composition.
Since the polyester resin composition obtained in Comparative Example 2 did not contain a transition metal, sufficient oxidative degradation resistance was not obtained.

(Comparative Examples 3 to 7)
A polyester resin composition was obtained in the same manner as in Example 1 except that the compound to be added and the content thereof were changed. Table 2 shows the characteristics of the obtained polyester resin composition.
The polyester resin composition obtained in Comparative Example 3 did not have sufficient oxidative degradation resistance because the carbon chain was too long.
Since the polyester resin composition obtained in Comparative Example 4 used a diol to be added which does not have a carbon-carbon multiple bond, sufficient oxidative degradation resistance was not obtained.
In Comparative Examples 5 and 7, a rubber-like composition was obtained, and the discharge after the completion of polymerization was impossible.
Although the polyester resin composition obtained in Comparative Example 6 uses a resin having a carbon-carbon double bond, it is C15 or more and the molecular chain is too long, so it does not have sufficient oxidative degradation resistance. It was.

(Example 7)
A polyester resin composition was obtained in the same manner as in Example 1 except that the phosphorus compound used was a combination of potassium dihydrogen phosphate and phosphoric acid. The properties of the obtained polyester resin composition are shown in Table 1. The content derived from a diol component having a carbon-carbon multiple bond was determined by NMR.
The polyester resin composition obtained in Example 7 had sufficient oxidative degradation resistance.

(Examples 8 to 13)
A polyester resin composition was obtained in the same manner as in Examples 1 to 6, except that the diol having carbon-carbon multiple bonds used was changed to cis-2-butene-1,4-diol. Table 3 shows the properties of the obtained polyester resin composition. In addition, content of the component derived from the diol which has a carbon-carbon multiple bond was determined using NMR or GC.
Any polyester resin composition obtained in Examples 8 to 13 had sufficient oxidative degradation resistance.

(Example 14)
Polyester similar to Example 1 except that the diol having carbon-carbon multiple bonds used was changed to cis-2-butene-1,4-diol and the phosphorus compound was changed to potassium dihydrogen phosphate and phosphoric acid. A resin composition was obtained. Table 3 shows the properties of the obtained polyester resin composition. The content derived from a diol component having a carbon-carbon multiple bond was determined by NMR.
The polyester resin composition obtained in Example 14 had sufficient oxidative degradation resistance.

(Examples 15 to 20)
The diol having a carbon-carbon multiple bond to be used is changed to cis-2-butene-1,4-diol, and the amount of manganese acetate tetrahydrate or phosphorus compound is adjusted, and the value of M / P is set. A polyester resin composition was obtained in the same manner as in Example 1 except for the change. Table 4 shows the properties of the obtained polyester resin composition. The content derived from a diol component having a carbon-carbon multiple bond was determined by NMR.
The polyester resin compositions obtained in Examples 15 to 20 exhibited sufficient oxidative degradation resistance.

(Examples 21 to 23)
A polyester resin composition was obtained in the same manner as in Example 1 except that the diol having a carbon-carbon multiple bond to be used was changed. Table 5 shows the properties of the obtained polyester resin composition. The content derived from a diol component having a carbon-carbon multiple bond was determined by NMR.

The polyester resin compositions obtained in Examples 21 to 23 exhibited sufficient oxidative degradation resistance.
(Examples 24-28)
A polyester resin composition was obtained in the same manner as in Example 1 except that the diol having carbon-carbon multiple bonds used was changed to cis-2-butene-1,4-diol and the transition metal compound salt used was changed. It was. Table 5 shows the properties of the obtained polyester resin composition. The content derived from a diol component having a carbon-carbon multiple bond was determined by NMR.
The polyester resin compositions obtained in Examples 24-28 exhibited sufficient oxidative degradation resistance.

(Examples 29 to 33)
A polyester resin composition was obtained in the same manner as in Example 1 except that the diol having a carbon-carbon multiple bond to be used was changed to cis-2-butene-1,4-diol and the phosphorus compound to be used was changed. Table 6 shows the properties of the obtained polyester resin composition. The content derived from a diol component having a carbon-carbon multiple bond was determined by NMR.
The polyester resin compositions obtained in Examples 29 to 33 exhibited sufficient oxidative degradation resistance.

  The polyester resin composition of the present invention can be used for fibers and various film applications, but is suitable for electrical insulation films and solar cell backsheet films that are exposed to oxygen for a long period of time and require oxidative degradation resistance. Available to:

Claims (5)

  A polyester resin composition comprising a transition metal element and containing 0.02 mol% or more of a component derived from a diol having a carbon-carbon multiple bond site and having 15 or less carbon atoms, based on the total acid component .   The polyester resin composition according to claim 1, comprising a phosphorus element.   The polyester resin composition according to claim 1 or 2, wherein M / P, which is the ratio of the molar amount M of the transition metal element and the molar amount P of the phosphorus element, is 0.1 to 3.0.   4. The polyester resin composition according to claim 1, comprising at least one selected from Cr, Mn, Fe, Co, Ni, and Zn as a transition metal element. 5.   The polyester resin composition according to claim 1, wherein the carbon-carbon multiple bond site is a double bond.