JP6816431B2 - Ionic salt, thermoplastic resin composition containing it, and method for producing the same - Google Patents

Description

The present invention relates to an ionic salt, a thermoplastic resin composition containing the ion salt, and a method for producing the same.

Conventionally, it has been known that by adding an ionic salt to a thermoplastic resin, it is possible to impart functionality typified by antistatic properties to the thermoplastic resin.
In addition, polyester, which is one of the thermoplastic resins, has excellent mechanical properties, thermal properties, chemical resistance, electrical properties, and moldability, and is used for various purposes. Among polyesters, polyethylene terephthalate (PET) is widely used in applications requiring high quality such as optical films because of its excellent transparency and processability. However, surface stains may occur due to the linear oligomers produced by the decomposition of the polymer adhering to or precipitating on the surface during molding. In addition, the scattering of the linear oligomer may cause process stains, which causes a problem of deterioration of the quality of the molded product due to surface stains and process stains. In recent years, the demand for quality of optical films and the like has been increasing more and more, and a resin composition that suppresses the scattering of linear oligomers that cause surface stains and process stains as described above is desired.

Patent Document 1 discloses a technique capable of imparting weather resistance to a thermoplastic resin by using an ion-bonding salt having a specific structure. However, this technique has not improved the effect of suppressing the scattering of linear oligomers in the obtained resin composition.

Patent Document 2 discloses an antistatic composition obtained by blending an ionic salt in which the conjugate acid of a weakly coordinated fluorine-containing organic anion is a super acid and a thermoplastic polymer. However, this technique has not improved the effect of suppressing the scattering of linear oligomers in the obtained resin composition. Further, when the conjugate acid of the anion of the ionic salt is a super acid and a strong acid such as a super acid is used, the generally obtained resin is easily hydrolyzed, so that the obtained resin composition There was also a problem with durability.

International Publication No. 2013/12489 Japanese Unexamined Patent Publication No. 2013-253254

The present invention solves the above-mentioned conventional problems, does not impair the transparency and durability of the thermoplastic resin composition, and is particularly suitable for suppressing the scattering of linear oligomers, and the thermoplastic resin containing the ion salt. It is an object of the present invention to provide a composition and a method for producing the same.

As a result of studies to solve the above problems, an ionic salt particularly suitable for suppressing the scattering of linear oligomers without impairing the transparency and durability of the thermoplastic resin composition was found.

That is, the object of the present invention is achieved by the following means.
(1) An ionic salt characterized by being composed of an anion having a structure in which an organic cation and an organic acid are deprotonated.

According to the present invention, an ionic salt particularly suitable for suppressing scattering of linear oligomers without impairing the transparency and durability of the thermoplastic resin composition, a thermoplastic resin composition containing the ionic salt, and a method for producing the same. Can be provided.

The present invention will be described in detail below.
The ionic salt of the present invention refers to an ionic salt composed of an anion having a deprotonated structure of an organic cation and an organic acid, and has a structure represented by the general formula [Q ⁺ ] [A ⁻ ].

The organic cation in the present invention refers to a cation characterized by having a structure containing at least one carbon atom without containing a metal element.

Examples of the cation include those having nitrogen as the ion center, those having phosphorus as the ion center, those having sulfur as the ion center, and those having nitrogen and sulfur as the ion center, but are limited to these. is not.

Examples of cations having a structure obtained by protonating a nitrogen-containing compound include imidazolium cation, ammonium cation, pyridinium cation, quinolinium cation, pyrrolidinium cation, piperazinium cation, piperazinium cation, morpholinium cation, and pyrida. Dinium cation, pyridinium cation, pyrazinium cation, pyrazolium cation, thiazolium cation, oxazolium cation, triazolium cation, guanidium cation, 4-aza-1-azonia-bicyclo- [ 2,2,2] Octanium cations and the like, but are not limited thereto. Further, these cations may have a substituent typified by an alkyl group at an arbitrary position, and the number of substituents may be plural. In addition, oxygen, nitrogen and the like may be contained in the substituent.

In the ionic salt of the present invention, the structure of the organic cation is preferably a protonated nitrogen-containing compound. A more preferable organic cation structure is a protonated nitrogen-containing compound having a boiling point of 260 ° C. or higher.

By converting the nitrogen-containing compound into a protonated structure, it is possible to efficiently suppress the scattering of linear oligomers without impairing the transparency and durability of the thermoplastic resin composition. Further, by converting a nitrogen-containing compound having a boiling point of 260 ° C. or higher into a cation having a protonated structure, the heat resistance of the ionic salt can be improved, so that the thermoplastic resin composition is decomposed during the polymerization process or molding process. In addition to the transparency and durability of the thermoplastic resin composition, the effect of suppressing the scattering of linear oligomers can be further enhanced without impairing the color tone. The boiling point of the nitrogen-containing compound is more preferably 280 ° C. or higher. The boiling point of the nitrogen-containing compound in the present invention refers to the boiling point at 1 atm.

Specific examples of preferred cations include dialkylammonium ions such as dioctylammonium ion and bis (2-ethylhexyl) ammonium ion, trioctylammonium ion, dimethylmyristylammonium ion, dimethylpalmitylammonium ion, dimethylstearylammonium ion and dimethylbehenylammonium. Examples thereof include, but are not limited to, trialkylammonium ions such as ions and dilaurylmethylammonium ions, and diarylammonium and triarylammonium ions such as dibenzylammonium ions and tribenzylammonium ions.

Further, as the structure of the organic cation, it is preferable that the structure is obtained by protonating a tertiary amine among the nitrogen-containing compounds from the viewpoint of the heat resistance of the ionic salt and the color tone of the obtained thermoplastic resin composition. By forming the structure in which the tertiary amine is protonated, the molecular weight increases and decomposition becomes difficult. Therefore, even when it is added to the thermoplastic resin, discoloration is less likely to occur, and it is possible to prevent an increase in the b value and a decrease in the L value, which are indicators of color tone.

In the ionic salt of the present invention, the anion needs to be an anion having a structure in which an organic acid is deprotonated. An anion having a deprotonated structure of an organic acid is an organic acid anion, and an organic acid is an acidic compound having at least one carbon. Taking the case where the organic acid is a carboxylic acid as an example, it is an anion having a structure represented by the general formula (RCOO ⁻ : R is an arbitrary substituent).

Specific examples of the organic acid anion include disianamide, bis (fluorosulfonyl) amide, bis (trifluoromethylsulfonyl) amide, bis (pentafluoroethylsulfonyl) amide, bis (nonafluorobutylsulfonyl) amide, methanesulfonate, and butylsulfonate. , Trifluoromethanesulfonate, tetrafluoroethanesulfonate, nonafluorobutane sulfonate, benzenesulfonate, p-toluenesulfonate, 2,4,6-trimethylbenzenesulfonate, styrene sulfonate, perfluorooctane sulfonate, heptadecafluorooctane sulfonate, 3-sulfo Propyl methacrylate, 3-sulfopropyl acrylate, methyl sulphate, ethyl sulphate, octyl sulphate, diethylene glycol monomethyl ether sulphate, hydrogen sulphate, hexafluorophosphate, tris (pentafluoroethyl) trifluorophosphate, dihydrogen sulphate. , Dibutyl phosphate, diethyl phosphate, dimethyl phosphate, bis (2,4,4-trimethylpentyl) phosphinate, methyl phosphonate, formate, acetate, propionate, butyrate, trifluoroacetate, hydroxyacetate, perfluorononanoate, decanoeate, mandelate, Thiosalicylate, benzoate, salicylate, 4-methylbenzoate, 4-nitrobenzoate, lactate, glycinate, alaninate, leucinate, variate, trifluoromethanesulfonyl leucinate, trifluoromethanesulfonyl valinate, phenoxide, thiocyanate, tris (trifluoromethanesulfonyl) methide , Acesulfamate, saccharinate, carbonate, methylcarbonate, carbamate and the like.

In the ionic salt of the present invention, the pKa of the organic acid, which is the conjugate acid of the anion, is preferably a positive value. When the pKa of the organic acid satisfies this range, the durability of the obtained thermoplastic resin composition can be improved, and the interaction with the linear oligomer works sufficiently, so that the excellent linear oligomer is excellent. The effect of suppressing scattering can be obtained. Regarding pKa of the conjugate acid of the anion, for example, International Journal of Quantum Chemistry, Vol 90, 1396-1403 (2002) and Chem. Commun. 1906-1917 (2006).

There is no particular upper limit on the pKa of the organic acid, but when used in a thermoplastic resin obtained from an acid as a raw material, such as acrylic resin and polyester resin, the pKa of the organic acid is higher than the pKa of the acid used as the resin raw material. Smaller is preferable. The reason is that when the pKa of the organic acid is larger than the pKa of the acid used as the resin raw material, the organic acid becomes a weaker acid, so that the anion having a deprotonated structure of the organic acid is protonated. This is because the effect of suppressing the scattering of linear oligomers may be reduced.

In the ionic salt of the present invention, the anion is preferably selected from carboxylic acid ion, organic phosphate ion, and sulfonic acid ion, and from the viewpoint of durability of the obtained thermoplastic resin composition and effect of suppressing linear oligomer scattering. , Particularly aromatic carboxylic acid ions are preferred. These anions are likely to interact with the linear oligomers and can effectively suppress the scattering of the linear oligomers.

Specific examples of preferable carboxylic acid ions include formate, acetate, propionate, butyrate and the like, and aromatic carboxylic acid ions include benzoate, salicylate, p-methylbenzoate and p-nitrobenzoate as organic phosphate ions. , Dibutyl phosphate, diethyl phosphate, dimethyl phosphate and the like, and specific examples of the sulfonic acid ion include, but are not limited to, methanesulfonate, p-toluenesulfonate and the like.

Most preferably, the ion salt of the present invention has a structure in which a cation is a protonated nitrogen-containing compound having a boiling point of 260 ° C. or higher, and an anion is a structure in which an aromatic carboxylic acid is deprotonated. Due to the synergistic effect of the optimum combination of cations and anions, an even more excellent linear oligomer scattering inhibitory effect can be obtained.

Specific examples of ionic salts include quaternary ammonium benzoate, quaternary ammonium = 4-methylbenzoate, quaternary ammonium = 4-nitrobenzoate, dioctylammonium salicylate, bis (2-ethylhexyl) ammonium benzoate, and bis (2-ethylhexyl) ammonium. = 4-Methylbenzoate, bis (2-ethylhexyl) ammonium = 4-nitrobenzoate, bis (2-ethylhexyl) ammonium salicylate, trioctylammonium benzoate, trioctylammonium = 4-methylbenzoate, trioctylammonium = 4- Nitrobenzoate, trioctylammonium salicylate, dimethylmyristylammonium benzoate, dimethylmyristylammonium = 4-methylbenzoate, dimethylmyristylammonium = 4-nitrobenzoate, dimethylmyristylsalicylate, dimethylpalmitylammonium benzoate, dimethylpalmitylammonium = 4-Methylbenzoate, dimethylpalmitylammonium = 4-nitrobenzoate, dimethylpalmityl salicylate, dimethylstearylammonium benzoate, dimethylstearylammonium = 4-methylbenzoate, dimethylstearylammonium = 4-nitrobenzoate, dimethylstearylsalicylate , Dimethylbehenylammonium benzoate, dimethylbehenylammonium = 4-methylbenzoate, dimethylbehenylammonium = 4-nitrobenzoate, dimethylbehenylsalicylate, dilaurylmethylammonium benzoate, dilaurylmethylammonium = 4-methylbenzoate, dilaurylmethylammonium Ammonium = 4-nitrobenzoate, dilaurylmethylammonium salicylate, dibenzylammonium benzoate, dibenzylammonium = 4-methylbenzoate, dibenzylammonium = 4-nitrobenzoate, dibenzylammonium salicylate, tribenzylammonium benzoate, Examples thereof include, but are not limited to, tribenzylammonium = 4-methylbenzoate, tribenzylammonium = 4-nitrobenzoate, and tribenzylammonium salicylate.

The ionic salt of the present invention can be synthesized by adopting a general ionic salt synthesis method. To give an example of an ammonium salt, an ammonium salt obtained by reacting an amine with an alkyl halide compound or the like is subjected to anion exchange using a metal salt and purified to obtain the desired ammonium salt. There are, but are not limited to, a method (anion exchange method) and a method (neutralization method) in which the desired ammonium salt is obtained by directly reacting an amine with an acid to neutralize the salt.

Since the ionic salt of the present invention does not produce a by-product and can be used without purification treatment, it is preferable to synthesize it by a neutralization method. When ionic salts are synthesized by the neutralization method, the color tone of the amine as a raw material may be affected by the ionic salt and the thermoplastic resin composition containing the ionic salt, so that coloring due to oxidative deterioration occurs. It is preferable to use an amine that does not. As the reaction temperature, it is preferable to stir and mix at a temperature equal to or higher than the melting point of the raw material amine to react. This is because the reaction proceeds uniformly and sufficiently by reacting the amine in a liquid state. The molar ratio of amine to acid as a raw material is preferably 1: 1. By setting the molar ratio to 1: 1 so that no unreacted raw material remains, the subsequent purification treatment becomes unnecessary. The reaction solvent may be used as needed, but it is preferable to carry out the reaction without a solvent because it is necessary to remove the solvent after the reaction.

Next, the thermoplastic resin composition of the present invention will be described.
The thermoplastic resin used in the thermoplastic resin composition of the present invention includes chain polyolefins such as polyethylene, polypropylene, poly (4-methylpentene-1) and polyacetal, ring-open metathesis polymerization of norbornenes, addition polymerization, and others. Biorecyclable polymers such as alicyclic polyolefins, polylactic acid, and polybutylsuccinate, which are addition copolymers with olefins, polyamides such as nylon 6, nylon 11, nylon 12, and nylon 66, aramid, and polymethylmethacrylate, Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl butyral, ethylene vinyl acetate copolymer, polyacetal, polyglucolic acid, polystyrene, styrene acrylonitrile copolymer, styrene copolymer polymethylmethacrylate, polycarbonate, polypropylene terephthalate, polyethylene terephthalate, poly Polyesters such as butylene terephthalate, polyethylene-2,6-naphthalate, polyether sulfone, polyether ether ketone, modified polyphenylene ether, polyphenylene sulfide, polyetherimide, polyimide, polyarylate, tetrafluoroethylene resin, trifluoride ethylene Resins such as ethylene trifluoride resin, ethylene tetrafluoride-6 propylene fluoride copolymer, and polyvinylidene fluoride can be used. Among these, it is more preferable to use a polyester resin from the viewpoint of durability, transparency and versatility. These may be homopolymers, copolymerized polymers, or even mixtures.
The polyester resin refers to a polyester resin obtained by polycondensing a dicarboxylic acid component and a diol component.

Examples of the dicarboxylic acid component in the polyester resin of the present invention include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecandioic acid, eicosandionic acid, pimeric acid, azelaic acid, methylmalonic acid, and ethyl. Alicyclic dicarboxylic acids such as aliphatic dicarboxylic acids such as malonic acid, adamantandicarboxylic acid, norbornene dicarboxylic acid, cyclohexanedicarboxylic acid, decalindicarboxylic acid, 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'-diphenyletherdicarboxylic acid, 5-sodium sulfoisophthalic acid, phenyl Examples thereof include dicarboxylic acids such as endandicarboxylic acids, anthracendicarboxylic acids, phenanthrangecarboxylic acids, and aromatic dicarboxylic acids such as 9,9'-bis (4-carboxyphenyl) fluoric acid, or ester derivatives thereof. Among these, aromatic dicarboxylic acids are preferably used from the viewpoints of oxidative decomposition resistance, heat resistance, and hydrolysis resistance of the polyester resin composition and mechanical strength when the composition is made into a film, and among them, terephthalic acid. Is more preferable.

Various diols can be used as the diol component in the present invention. For example, as an aliphatic diol such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentyl glycol, or an alicyclic diol. Cyclohexanedimethanol, cyclohexanediethanol, decahydronaphthalenediethanol, decahydronaphthalenediethanol, norbornandimethanol, norbornandiethanol, tricyclodecanedimethanol, tricyclodecaneethanol, tetracyclododecanedimethanol, tetracyclododecanediethanol, decalindi 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- Saturated heterocyclic primary diol containing cyclic ether such as dioxane and isosorbide, other cyclohexanediol, bicyclohexyl-4,4'-diol, 2,2-bis (4-hydroxycyclohexylpropane), 2,2-bis (4) Various alicyclic diols such as-(2-hydroxyethoxy) cyclohexyl) propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiol, 4-cyclopentene-1,3-diol, and adamandiol, and paraxylene. Examples thereof include aromatic ring diols such as glycol, bisphenol A, bisphenol S, styrene glycol, 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, and 9,9'-bis (4-hydroxyphenyl) fluorene. it can. In addition to diols, 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, ethylene glycol is particularly preferable from the viewpoint of mechanical properties such as elongation and flexibility when the composition is made into a film.

In addition, other dicarboxylic acids, hydroxycarboxylic acid derivatives, and diols may be copolymerized to the extent that the scope of the effect of the present invention is not impaired.
The thermoplastic resin composition of the present invention preferably has a solution haze of 5% or less. More preferably, it is 3% or less. Within this range, a molded product having excellent transparency can be obtained. Therefore, it is suitable for optical films and the like.

The thermoplastic resin composition of the present invention preferably has a COOH terminal group increase amount (ΔCOOH) of 80 eq / t or less before and after the treatment when treated at 155 ° C. and 100% RH for 4 hours. More preferably, it is 65 eq / t or less. Within this range, it becomes possible to provide a thermoplastic resin composition that is less deteriorated by hydrolysis during long-term use.

From the viewpoint of durability, the thermoplastic resin composition of the present invention preferably has a COOH terminal group amount of 35 eq / t or less. Within this range, thermal decomposition and hydrolysis due to the COOH terminal group are less likely to occur, and a thermoplastic resin composition having excellent durability can be obtained.

In the thermoplastic resin composition of the present invention, the amount of DEG (diethylene glycol) contained in the resin composition is preferably 1.5 wt% or less. By setting the amount of DEG in this range, a resin composition having excellent durability and molding processability can be obtained.

In the thermoplastic resin composition of the present invention, the content of an ionic salt composed of an anion having a deprotonated structure of an organic cation and an organic acid is contained in an amount of 0.01 wt% or more based on the weight of the thermoplastic resin. Is preferable. More preferably, it is 0.05 wt% or more. Within this range, a thermoplastic resin composition with less scattering of linear oligomers can be obtained. The upper limit of the content of the ionic salt is not particularly set, but it is preferably 5 wt% or less because the color tone of the thermoplastic resin composition may deteriorate.

The linear oligomer in the present invention refers to a monomer constituting the oligomer of the thermoplastic resin composition or a linear oligomer obtained by reacting the monomer, and having a degree of polymerization of 10 or less. However, in the present invention, in the case of the polyester resin composition, the diol as a raw material is not considered as a linear oligomer.

Taking PET (polyethylene terephthalate), which is one of the thermoplastic resins, as an example, MHET (monohydroxyethyl terephthalate) and BHET (monohydroxyethyl terephthalate) and BHET (monohydroxyethyl terephthalate), which are a reaction product of terephthalic acid as a raw material and carboxylic acid of terephthalic acid and ethylene glycol Bishydroxyethyl terephthalate) and other reaction products with a degree of polymerization of 10 or less, which are produced by the reaction of terminal groups with each other.

In the present invention, the effect of suppressing the scattering of linear oligomers of an ionic salt composed of an anions having a deprotonated structure of an organic cation and an organic acid is obtained by melting a thermoplastic resin composition containing an ionic salt and then quenching the sample to re-cool the sample. It is evaluated by measuring the amount of linear oligomers scattered when heated.

As a specific example, an evaluation method when a polyester resin composition, which is one of the thermoplastic resin compositions, is used will be described. The sample obtained by melting the polyester resin composition at 300 ° C. for 60 minutes in a nitrogen atmosphere is rapidly cooled, and then heat-treated at 220 ° C. for 8 hours to attach the scattered matter to the collection plate. A solution for measurement is prepared by dissolving the deposits on the collection plate in a certain amount of organic solvent. The prepared measurement solution is measured for absorbance at a specific wavelength using a spectrophotometer. From the obtained absorbance, the amount of linear oligomer scattered is calculated using a calibration curve prepared separately. Detailed conditions will be described in the measurement method (7) in the examples described later.

Here, the main component of the scattered matter adhering to the collection plate is, taking PET as an example, linear oligomers such as terephthalic acid, MHET, and BHET. That is, the fact that the amount of scattered matter adhering to the collection plate is small means that the amount of scattered linear oligomer is small. The amount of the linear oligomer scattered is preferably 45 ppm or less in the case of the polyester resin composition. It is more preferably 42 ppm, still more preferably 39 ppm or less. By setting the amount of the linear oligomer scattered in this range, it is possible to provide a resin composition that realizes reduction of process stains and surface stains caused by the linear oligomer, which is a problem during molding.

Next, a method for producing the thermoplastic resin composition of the present invention will be shown.
The thermoplastic resin composition of the present invention can be produced, for example, by the following methods (1) and (2), but is not limited thereto. The device and technical process for producing the thermoplastic resin composition may be any device and process as long as it is a commonly used device.

(1) A method for obtaining a thermoplastic resin composition containing an ionic salt by adding the ionic salt of the present invention arbitrarily until the completion of the polymerization reaction.

(2) A method for obtaining a thermoplastic resin composition containing an ionic liquid by kneading a thermoplastic resin prepared by using a known method such as polycondensation and an ionic salt of the present invention using a kneader. ..

Among these methods, in the thermoplastic resin composition having a COOH terminal group such as a polyester resin composition, the amount of the COOH terminal group of the obtained resin composition is reduced, and the amount of the linear oligomer scattered is small. In order to obtain the resin, the production method in which the ion salt of the present invention is added at an arbitrary stage until the completion of the polymerization reaction of (1) is preferable.

In the polyester resin composition, it is more preferable to add the ionic salt of the present invention between the end of the transesterification reaction or the esterification reaction and the end of the polymerization reaction. When the addition is carried out at the above time, the dispersibility of the ionic salt is good, and it is not necessary to carry out an additional step such as a kneading step.
Specific examples of producing a polyester resin composition (particularly PET composition), which is one of the thermoplastic resin compositions, by the method (1) are shown below, but the present invention is not limited thereto.

A slurry of terephthalic acid and ethylene glycol (1.15 times mol with respect to terephthalic acid) is gradually added to an esterification reactor charged with bishydroxyethyl terephthalate dissolved at 255 ° C. using a snake pump to esterify. Proceed with the reaction. The temperature in the reaction system is controlled to be 245 to 255 ° C., and the esterification reaction is terminated when the reaction rate reaches 95%.

A polycondensation catalyst, a phosphorus compound, and an ionic salt are added to the esterification reaction product at 255 ° C. thus obtained. During these operations, it is preferable to keep the temperature in the system at 240 to 255 ° C. so that the esterified product does not solidify.

Then, while gradually raising the temperature in the polymerization apparatus to 290 ° C., the pressure in the polymerization apparatus is gradually reduced from normal pressure to 133 Pa or less to distill out ethylene glycol. At this time, if it is desired to lower the amount of COOH terminal groups in the polyester composition, it is preferable to set the polymerization temperature low. The reaction is terminated when a predetermined stirring torque is reached, the inside of the reaction system is made normal pressure with nitrogen gas, and the molten polymer is discharged into cold water in a strand shape and cut to obtain a pellet-shaped polyester resin composition. ..

As the catalyst used for producing the polyester composition of the present invention, known transesterification catalysts, polycondensation catalysts, and co-catalysts can be used. For example, examples of the polymerization catalyst include, but are not limited to, antimony compounds, germanium compounds, titanium compounds, and aluminum compounds.
Examples of the ester exchange catalyst and the co-catalyst include, but are not limited to, an organic manganese compound, an organic magnesium compound, an organic calcium compound, an organic cobalt compound, and an organic lithium compound.

In the production of the polyester resin composition of the present invention, a phosphorus compound may be added in order to impart thermal stability to the obtained resin composition. However, the phosphorus compound referred to here does not contain a salt containing phosphorus such as a phosphonium-based ion salt. By containing the phosphorus element, the thermal stability of the resin composition can be improved, so that an increase in the amount of COOH terminal groups after polymerization can be suppressed. As a result, the amount of the linear oligomer scattered can be reduced.

The phosphorus compound used is not particularly limited, but phosphite-based compounds, phosphite-based compounds, phosphonic acid-based compounds, phosphinic acid-based compounds, phosphine oxide-based compounds, phosphonic acid-based compounds, phosphinic acid-based compounds, phosphine-based compounds, etc. are used. Can be mentioned. Specific examples thereof include phosphoric acid, trimethylphosphonoacetate, triethylphosphonoacetate, dimethylphenylphosphonate, trimethylphosphate, triethyl phosphate, triphenyl phosphate and the like.

The amount of the phosphorus compound added is not particularly limited, but the lower limit of the amount of the phosphorus compound added is preferably 5 ppm or more as the amount of the phosphorus element with respect to the polyester resin composition. It is more preferably 10 ppm or more, still more preferably 20 ppm or more. The upper limit of the addition amount is preferably 600 ppm or less as the amount of phosphorus element. Within this range, the thermal stability of the resin composition can be improved without causing a delay in polymerization.

In the method for producing a thermoplastic resin composition of the present invention, solid-phase polymerization may be carried out in order to obtain a resin composition having a higher molecular weight. By carrying out solid-phase polymerization, it is possible to reduce cyclic trimers and linear oligomers in the polyester resin composition. The conditions for solid-phase polymerization are not particularly limited, but the polyester resin composition is preferably carried out in a temperature range of -30 ° C or lower to -60 ° C or higher, and the degree of vacuum is 0.3 Torr or lower. preferable. The solid-phase polymerization time is appropriately set depending on the desired melt viscosity, but is preferably 3 hours or more and 20 hours or less from the viewpoint of the production time cycle.

The thermoplastic resin composition of the present invention is a terminal sealant, an antioxidant, an ultraviolet absorber, a flame retardant, an optical brightener, a matting agent, a plasticizer or an antifoaming agent as long as the effects of the present invention are not impaired. Alternatively, other additives and the like may be blended as needed.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition having excellent transparency and durability and a small amount of linear oligomers scattered, and is a high-quality film such as an optical film or a release film, fibers, and molded products. It can be suitably used for various purposes such as the body.

The film made of the thermoplastic resin composition of the present invention may be an unstretched film by melt extrusion, or a stretched film subjected to uniaxial stretching or biaxial stretching. It can be selected according to the intended use of the film.

The film made of the thermoplastic resin composition of the present invention may be a single film film in which the entire film is made of the same resin, or includes at least one film layer made of the thermoplastic resin composition of the present invention. It may be a laminated film. In the case of a single film, the effect of suppressing the scattering of linear oligomers is most exerted, but in the case of a laminated film, the effect of suppressing the scattering of oligomers generated from other film layers is exhibited.

In the case of a laminated film, it is preferable to have a film layer made of the thermoplastic resin composition of the present invention on at least one surface layer. Since the scattering of the linear oligomer is generated from the film surface, it is possible to suppress the scattering of the linear oligomer on at least one side surface with the above configuration. Therefore, the most preferable structure of the laminated film is a structure in which the film layers made of the thermoplastic resin composition of the present invention are arranged on both surfaces.

Hereinafter, the present invention will be described in more detail with reference to examples. The physical property values in the examples were measured by the following methods. Further, in the following, Examples 10 and 11 will be read as reference examples, respectively.

(1) Intrinsic viscosity of thermoplastic resin composition (IV)
It was measured at 25 ° C. using an o-chlorophenol solvent.

(2) The amount of COOH terminal groups in the thermoplastic resin composition was measured by the method of Maurice. (References M.J. Maulice, F. Huizinga, Anal. Chem. Acta, 22 363 (1960)).

(3) Transparency of thermoplastic resin composition (solution haze)
2 g of the thermoplastic resin composition is dissolved in 20 ml of a mixed solution of phenol / 1,1,2,2, tetrachloroethane in a 3/2 (volume ratio) mixture, and a haze meter (Suga Test Instruments Co., Ltd.) is used using a cell having an optical path length of 20 mm. The analysis was performed by the integrating sphere-type photoelectric photometry method using HZ-1) manufactured by HZ-1). When the solution haze was 5% or less, it was judged that the transparency was good.

(4) Amount of DEG (diethylene glycol) in the thermoplastic resin composition The polyester composition is dissolved using monoethanolamine as a solvent, a mixed solution of 1,6-hexanediol / methanol is added to the solution, cooled, and terephthalic acid is used. After neutralization and centrifugation, the supernatant was measured by gas chromatography (manufactured by Shimadzu Corporation, GC-14A).

(5) Color tone (L value and b value) of the thermoplastic resin composition
The color tone of the polyester resin composition was measured with a color meter (manufactured by Suga Test Instruments Co., Ltd .: SM-T45).

(6) Durability of Thermoplastic Resin Composition (ΔCOOH)
The thermoplastic resin composition was heat-treated at 155 ° C. and 100% RH for 4 hours, and the difference in the amount of COOH terminal groups before and after the treatment (COOH terminal group amount after treatment-COOH terminal group amount before treatment) was compared. When the difference in the amount of COOH terminal groups (ΔCOOH) at this time was 80 eq / t or less, it was judged to have good durability.

(7) Amount of linear oligomer generated 8 g of the thermoplastic resin composition was weighed in a test tube having a diameter of 16.5 mm and a length of 165 mm, and allowed to stand in a vacuum dryer. After reducing the pressure to 10 Torr or less, the temperature inside the dryer was raised to 150 ° C. After reaching 150 ° C., vacuum drying was performed for 3 hours, and then the temperature inside the dryer was raised to 180 ° C. After reaching 180 ° C., it was vacuum dried for 7.5 hours. Then, with the inside of the test tube in a nitrogen atmosphere, the test tube was immersed in an oil bath at 300 ° C., and the resin composition heat-treated for 60 minutes was extracted with a PTFE tube having an inner diameter of 10 mm and rapidly cooled with ice water to quench the resin column. Got A sample obtained by cutting the obtained resin column into 5 mm squares was vacuum dried at room temperature for 3 hours to prepare a sample for measurement.
1.5 g of the obtained measurement sample was spread evenly on the crucible (model number: CC-crucible, B-3, 100 mL), and the center of the glass plate whose surface was washed under the following conditions was placed in the center of the crucible. A 100 mm × 100 mm transparent glass plate (Alpha Purchase Catalog No .: 31396) was placed on the crucible.
A crucible containing a sample covered with a glass plate was placed on a hot plate heated to a surface temperature of 220 ° C. and heated for 8 hours to collect scattered substances on a transparent glass plate. A solution for measurement was prepared by dissolving the scattered matter adhering to the transparent glass plate in 5 mL of DMF. The absorbance of the obtained measurement solution at a wavelength of 286 nm was measured using a spectrophotometer (U-3010 spectrophotometer manufactured by Hitachi, Ltd.). The amount of linear oligomers scattered (ppm) was calculated by applying the obtained absorbance value to the following formula (1). When the scattered amount (ppm) of the linear oligomer was 45 ppm or less, it was judged that the scattered amount of the linear oligomer was small.

The symbols in the formula (1) are Abs: absorbance, a: slope of the calibration curve, b: solvent amount (5 mL), and c: thermoplastic resin amount (1.5 g), respectively.

<Glass plate cleaning conditions>
After washing both sides of the glass plate with water, both sides were washed with detergent by tracing with a finger. After washing with water so that no detergent remained, both sides were rinsed with ethanol. Then, it was dried in a hot air dryer at 50 ° C. until the ethanol adhering to the surface disappeared.

<Measurement conditions of spectrophotometer>
The spectrophotometer was used for measurement under the following conditions, and a quartz glass cell (T-1-UV-10) was used as the measurement cell.
-Measurement wavelength: 320 to 220 nm
・ Measurement mode: Wavelength scan ・ Data mode: Abs
・ Scan speed: Automatic ・ Sampling interval: 0.50 nm
・ Slit: 0.1 nm
・ Cell length: 10.0 nm
-Peak detection method: Rectangle
・ Peak detection sensitivity: 2
-Peak detection threshold: 0.01.

(8) ¹ H-NMR measurement of ion salt ¹ H-NMR of a solution in which an ion salt was dissolved in CDCl ₃ was measured using a 400 MHz nuclear magnetic resonance apparatus (AL-400) manufactured by JEOL Ltd.
(Boiling point of amine and pKa of organic acid)
The boiling point of amines and the pKa of organic acids are shown in Table 1.

(Synthesis Example 1)
3.54 g (10 mmol) of trioctylamine and 1.38 g (10 mmol) of salicylic acid were weighed and charged into a reaction vessel. The contents were stirred and mixed at room temperature for 1 hour to obtain 4.92 g of trioctyl ammonium salicylate (Chemical formula 1, colorless to pale yellow liquid).
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (1).
^{1 1} H-NMR (CDCl ₃ ) δ: 7.89 (1H, dd, J = 7.3, 1.8 Hz), 7.28 (1H, ddd, J = 8.2, 7.3, 1.8) Hz), 6.88 (1H, dd, J = 8.2,1.3Hz), 6.73 (1H, td, J = 7.3, 1.3Hz), 3.02-2.98 (6H) , M), 1.74-1.66 (6H, m), 1.36-1.21 (30H, m), 0.87 (9H, t, J = 6.8Hz).

(Synthesis Example 2)
2.98 g (10 mmol) of dimethylstearylamine and 1.38 g (10 mmol) of salicylic acid were weighed and charged into a reaction vessel. The contents were heated to 140 ° C. to dissolve them, and then heated and stirred at 140 ° C. for 1 hour. Then, by cooling to room temperature, 4.36 g of dimethylstearylammonium salicylate (chemical formula 2, white solid) was obtained.
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (2).
^{1 1} H-NMR (CDCl ₃ ) δ: 7.89 (1H, dd, J = 7.7, 1.8 Hz), 7.30 (1H, ddd, J = 8.2, 7.3, 1.8) Hz), 6.90 (1H, dd, J = 8.2,1.3Hz), 6.80 (1H, ddd, J = 7.7, 7.3, 1.3Hz), 2.98-2 .93 (2H, m), 2.78 (6H, s), 1.75 (2H, tt, J = 14.8, 7.3Hz), 1.34-1.22 (30H, m), 0 .88 (3H, t, J = 6.9Hz).

(Synthesis Example 3)
2.70 g (10 mmol) of dimethylpalmitylamine and 1.38 g (10 mmol) of salicylic acid were weighed and charged into a reaction vessel. The contents were heated to 140 ° C. to dissolve them, and then heated and stirred at 140 ° C. for 1 hour. Then, by cooling to room temperature, 4.08 g of dimethylpalmityl ammonium salicylate (chemical formula 3, white solid) was obtained.
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (3).

^{1 1} H-NMR (CDCl ₃ ) δ: 7.89 (1H, dd, J = 7.6, 1.6 Hz), 7.30 (1H, ddd, J = 8.2, 7.3, 1.6) Hz), 6.90 (1H, dd, J = 8.2,1.0Hz), 6.79 (1H, ddd, J = 7.6,7.3,1.0Hz), 2.96-2 .90 (2H, m), 2.76 (6H, s), 1.75 (2H, tt, J = 14.8, 7.3Hz), 1.42-1.18 (26H, m), 0 .88 (3H, t, J = 6.9Hz).

(Synthesis Example 4)
2.42 g (10 mmol) of dimethyl myristylamine and 1.38 g (10 mmol) of salicylic acid were weighed and charged into a reaction vessel. The contents were heated to 140 ° C. to dissolve them, and then heated and stirred at 140 ° C. for 1 hour. Then, by cooling to room temperature, 3.80 g of dimethyl myristyl ammonium salicylate (chemical formula 5, white solid) was obtained.
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (4).

^{1 1} H-NMR (CDCl ₃ ) δ: 7.89 (1H, dd, J = 7.7, 1.6Hz), 7.30 (1H, ddd, J = 8.2,7.3,1.6) Hz), 6.90 (1H, dd, J = 8.2,1.0 Hz), 6.80 (1H, ddd, J = 7.7, 7.3, 1.0 Hz), 2.98-2 .94 (2H, m), 2.78 (6H, s), 1.76 (2H, tt, J = 15.2,7.6Hz), 1.41-1.18 (22H, m), 0 .88 (3H, t, J = 6.9Hz).

(Synthesis Example 5)
3.68 g (10 mmol) of dilaurylmethylamine and 1.38 g (10 mmol) of salicylic acid were weighed and charged into a reaction vessel. The contents were stirred and mixed at room temperature for 1 hour to obtain 5.06 g of didilaurylmethylammonium salicylate (chemical formula 5, pale yellow liquid).
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (5).

^{1 1} H-NMR (CDCl ₃ ) δ: 7.89 (1H, dd, J = 7.7, 1.5Hz), 7.29 (1H, ddd, J = 8.2,7.3,1.6) Hz), 6.89 (1H, dd, J = 8.2,1.0Hz), 6.79 (1H, ddd, J = 7.7, 7.3, 1.0Hz), 2.98 (4H) , Br), 2.75 (3H, s), 1.77-1.69 (4H, m), 1.39-1.22 (36H, m), 0.88 (6H, t, J = 7) .3Hz).

(Synthesis Example 6)
2.87 g (10 mmol) of tribenzylamine and 1.38 g (10 mmol) of salicylic acid were weighed and charged into a reaction vessel. The contents were heated to 140 ° C. to dissolve them, and then heated and stirred at 140 ° C. for 1 hour. Then, by cooling to room temperature, 4.25 g of tribenzylammonium salicylate (chemical formula 6, pale yellow viscous liquid) was obtained.
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (6).
^{1 1} H-NMR (CDCl ₃ ) δ: 7.95 (1H, dt, J = 8.0, 1.6Hz), 7.49-7.41 (6H, m), 7.34 (6H, tt, J = 7.3, 1.3Hz), 7.31-7.24 (4H, m), 6.98 (1H, dd, J = 8.6, 1.0Hz), 6.90 (1H, ddd) , J = 7.8, 7.3, 1.3Hz), 3.80 (6H, s).

(Synthesis Example 7)
2.42 g (10 mmo1) of dioctylamine and 1.38 g (10 mmol) of salicylic acid were weighed and charged into a reaction vessel. The contents were stirred and mixed at room temperature for 1 hour to obtain 3.80 g of dioctyl ammonium salicylate (chemical formula 7, pale yellow liquid).
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (7).
^{1 1} H-NMR (CDCl ₃ ) δ: 7.80 (1H, dd, J = 7.7, 1.8Hz), 7.31 (1H, ddd, J = 8.2,7.3, 1.6Hz) ), 6.90 (1H, d, J = 8.2Hz), 6.79 (1H, t, J = 7.3Hz), 2.94-2.88 (4H, m), 1.76 (3H) , Tt, J = 15.5, 7.3 Hz), 1.35-1.16 (20 H, m), 0.84 (6 H, t, J = 6.6 Hz).

(Synthesis Example 8)
2.42 g (10 mmo1) of bis (2-ethylhexyl) amine and 1.38 g (10 mmol) of salicylic acid were weighed and charged into a reaction vessel. The contents were stirred and mixed at room temperature for 1 hour to obtain 3.80 g of bis (2-ethylhexyl) ammonium salicylate (chemical formula 8, pale yellow liquid).
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (8).
^{1 1} H-NMR (CDCl ₃ ) δ: 7.81 (1H, d, J = 7.6 Hz), 7.30 (1H, ddd, J = 8.2, 7.3, 1.6 Hz), 6. 89 (1H, dd, J = 8.2,1.0Hz), 6.78 (1H, ddd, J = 7.6,7.3,1.0Hz), 2.87 (4H, d, J =) 6.6 Hz), 1.82 (2H, ttt, J = 12.5, 6.3, 5.9 Hz), 1.53-1.40 (4H, m), 1.40-1.31 ( 4H, m), 1.29-1.18 (8H, m), 0.89-0.79 (12H, m).

(Synthesis Example 9)
1.87 g (10 mmo1) of 3- (2-ethylhexyloxy) propylamine and 1.38 g (10 mmol) of salicylic acid were weighed and charged into a reaction vessel. The contents were stirred and mixed at room temperature for 1 hour to obtain 3.25 g of 3- (2-ethylhexyloxy) propylammonium salicylate (chemical formula 9, orange liquid).
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (9).
¹ H-NMR (CDCl ₃ ) δ: 7.81 (1H, dd, J = 7.9, 1.6Hz), 7.32 (1H, ddd, J = 8.2,7.3,1.6) Hz), 6.90 (1H, dd, J = 8.2, 0.9Hz), 6.79 (1H, td, J = 7.3, 0.9Hz), 3.52 (2H, t, J) = 5.4Hz), 3.30-3.21 (2H, m), 3.14 (2H, t, J = 6.3Hz), 1.90 (2H, tt, J = 11.5, 5. 6Hz), 1.50-1.40 (1H, m), 1.34-1.17 (8H, m), 0.86 (3H, t, J = 6.8Hz), 0.82 (3H, t, J = 7.6 Hz).

(Synthesis Example 10)
3.54 g (10 mmol) of trioctylamine and 0.60 g (10 mmol) of acetic acid were weighed and charged into a reaction vessel. The contents were stirred and mixed at room temperature for 1 hour to obtain 4.04 g of trioctyl ammonium acetate (chemical formula 10, transparent to pale yellow liquid).
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (10).
^{1 1} H-NMR (CDCl ₃ ) δ: 2.74-2.68 (6H, m), 1.99 (3H, s), 1.60-1.50 (6H, m), 1.33-1 .23 (30H, m), 0.88 (9H, t, J = 7.3Hz).

(Synthesis Example 11)
3.54 g (10 mmol) of trioctylamine and 0.96 g (10 mmol) of methanesulfonic acid were weighed and charged into a reaction vessel. The contents were stirred and mixed at room temperature for 1 hour to obtain 4.46 g of trioctylammonium methanesulfonate (chemical formula 11, pale yellow liquid).
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (11).
^{1 1} H-NMR (CDCl ₃ ) δ: 3.04-2.96 (6H, m), 2.78 (3H, s), 1.77-1.67 (6H, m), 1.39-1 .22 (30H, m), 0.88 (9H, t, J = 6.9Hz).

(Synthesis Example 12)
3.54 g (10 mmol) of trioctylamine and 1.22 g (10 mmol) of benzoic acid were weighed and charged into a reaction vessel. The contents were stirred and mixed at room temperature for 1 hour to obtain 4.76 g of trioctyl ammonium benzoate (chemical formula 12, transparent to pale yellow liquid).
¹ The measurement results of ¹ H-NMR are as follows, and it was confirmed that the structure has the chemical formula (12).
^{1 1} H-NMR (CDCl ₃ ) δ: 8.06 (2H, dd, J = 6.9, 1.6Hz), 7.46-7.34 (3H, m), 2.91-2.83 ( 6H, m), 1.68-1.59 (6H, m), 1.35-1.20 (30H, m), 0.87 (9H, t, J = 6.9Hz).

(Example 1)
In an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C., a slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times mol with respect to terephthalic acid) was gradually added. Was added to promote the esterification reaction. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was terminated when the reaction rate reached 95%.
After transferring 105 parts by weight (equivalent to 100 parts by weight of PET) of the esterification reaction product at 255 ° C. thus obtained to a polymerization apparatus, 0.02 part by weight of trimethyl phosphate was added and the mixture was stirred for 5 minutes. Next, 0.1 part by weight of the ionic salt (trioctylammonium salicylate) of Synthesis Example 1 was added, and after stirring for 5 minutes, 0.01 part by weight of diantimony trioxide was added.

Then, while gradually raising the temperature inside the polymerization apparatus to 290 ° C., the pressure inside the polymerization apparatus was gradually reduced from normal pressure to 133 Pa or less to distill out ethylene glycol. When the melt viscosity equivalent to the intrinsic viscosity of 0.65 is reached, the reaction is terminated, the inside of the reaction system is made normal pressure with nitrogen gas, and the reaction system is discharged from the lower part of the polymerization apparatus into cold water in a strand shape, cut, and pelletized heat. A plastic resin composition was obtained. The characteristics of the obtained thermoplastic resin composition are shown in Table 2.
The thermoplastic resin composition obtained in Example 1 had good transparency, color tone, and durability, and the amount of linear oligomer scattered was small.

(Examples 2 to 6)
A thermoplastic resin composition was obtained in the same manner as in Example 1 except that the ionic salt to be added was changed to the ionic salt of Synthesis Examples 2 to 6 as shown in Table 2. The characteristics of the obtained thermoplastic resin composition are shown in Table 2. The thermoplastic resin compositions obtained in Examples 2 to 6 have good transparency, color tone, and durability, and the amount of linear oligomer scattered is also large. There were few.

(Comparative Example 1)
In an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C., a slurry consisting of 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times mol with respect to terephthalic acid) was gradually added. Was added to promote the esterification reaction. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was terminated when the reaction rate reached 95%.

After transferring 105 parts by weight (equivalent to 100 parts by weight of PET) of the esterification reaction product at 255 ° C. thus obtained to a polymerization apparatus, 0.02 parts by weight of trimethyl phosphate was added, and the mixture was stirred for 10 minutes and then diantimony trioxide. 0.01 parts by weight was added.

Then, while gradually raising the temperature inside the polymerization apparatus to 290 ° C., the pressure inside the polymerization apparatus was gradually reduced from normal pressure to 133 Pa or less to distill out ethylene glycol. When the melt viscosity equivalent to the intrinsic viscosity of 0.65 is reached, the reaction is terminated, the inside of the reaction system is made normal pressure with nitrogen gas, and the reaction system is discharged from the lower part of the polymerization apparatus into cold water in a strand shape, cut, and pelletized heat. A plastic resin composition was obtained. The characteristics of the obtained thermoplastic resin composition are shown in Table 3.
Since the obtained thermoplastic resin composition does not use the ionic salt of the present invention, the result is that the amount of linear oligomers scattered is large.

(Comparative Example 2)
A thermoplastic resin composition was obtained in the same manner as in Example 1 except that tetrabutylammonium bromide was added as an ionic salt. The characteristics of the obtained thermoplastic resin composition are shown in Table 3. Since the obtained thermoplastic resin composition does not use an ionic salt having an anion having a deprotonated structure of an organic acid, it is a linear oligomer. The result was a large amount of scattering.

(Comparative Example 3)
A thermoplastic resin composition was obtained in the same manner as in Example 1 except that ammonium acetate was added as an ionic salt. The characteristics of the obtained thermoplastic resin composition are shown in Table 3.
Since the obtained thermoplastic resin composition does not use an ionic salt having an organic cation, the result is that the amount of linear oligomer scattered is large.

(Comparative Example 4)
A thermoplastic resin composition was obtained in the same manner as in Example 1 except that sodium acetate was added as an ionic salt. The characteristics of the obtained thermoplastic resin composition are shown in Table 3.
Since the obtained thermoplastic resin composition does not use an ionic salt having an organic cation, the result is that the amount of linear oligomers scattered is large, and the transparency is also poor.

(Examples 7 to 12)
A thermoplastic resin composition was obtained in the same manner as in Example 1 except that the ionic salt to be added was changed to the ionic salt of Synthesis Examples 7 to 12 as shown in Table 4. The characteristics of the obtained thermoplastic resin composition are shown in Table 4. The thermoplastic resin compositions obtained in Examples 7 to 10 and 12 had good transparency and durability, and the amount of linear oligomer was small.
The thermoplastic resin composition obtained in Example 11 had good transparency and a small amount of linear oligomers.

(Examples 13 to 17)
A thermoplastic resin composition was obtained in the same manner as in Example 1 except that the amount of the ionic salt of Synthesis Example 1 was changed as shown in Table 5. The characteristics of the obtained thermoplastic resin composition are shown in Table 5.
The thermoplastic resin compositions obtained in Examples 13 to 17 had good transparency, color tone, and durability, and the amount of linear oligomer scattered was small.

(Example 18)
(Reference Example 1) Method for synthesizing polyethylene terephthalate 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1 with respect to terephthalic acid) were placed in an esterification reactor in which 105 parts by weight of bishydroxyethyl terephthalate dissolved at 255 ° C. was charged. A slurry consisting of .15 times mol) was gradually added to allow the esterification reaction to proceed. The temperature in the reaction system was controlled to be 245 to 255 ° C., and the esterification reaction was terminated when the reaction rate reached 95%.
After transferring 105 parts by weight (equivalent to 100 parts by weight of PET) of the esterification reaction product at 255 ° C. thus obtained to a polymerization apparatus, 0.02 parts by weight of trimethyl phosphate was added, and the mixture was stirred for 10 minutes and then diantimony trioxide. 0.01 parts by weight was added.
Then, while gradually raising the temperature inside the polymerization apparatus to 290 ° C., the pressure inside the polymerization apparatus was gradually reduced from normal pressure to 133 Pa or less to distill out ethylene glycol. When the melt viscosity equivalent to the intrinsic viscosity of 0.70 is reached, the reaction is terminated, the inside of the reaction system is made normal pressure with nitrogen gas, and the reaction system is discharged from the lower part of the polymerization apparatus into cold water in a strand shape, cut, and pelletized heat. A plastic resin was obtained.
The polyethylene terephthalate resin obtained in Reference Example 1 was vacuum dried at 160 ° C. for 5 hours, and then the ionic salt of Synthesis Example 1 was added to 100 parts by weight of the polyethylene terephthalate at a blending ratio of 1.0 part by weight. It was supplied to a twin-screw extruder with a vent, and melt extrusion was performed at a temperature of 280 ° C. The discharged strand-shaped polymer was cooled in water and cut with a pelletizer to obtain a pellet-shaped thermoplastic resin composition. The characteristics of the obtained thermoplastic resin composition are shown in Table 5.
The obtained thermoplastic resin composition was excellent in transparency and the amount of linear oligomer scattered was small, but as compared with Example 17, the b value increased and the COOH terminal group of the thermoplastic resin composition increased. As a result, the durability was reduced.

Claims (11)

A polyethylene terephthalate resin composition containing an ionic salt, which comprises an organic cation obtained by protonating a nitrogen-containing compound and an aromatic carboxylic acid ion . The polyethylene terephthalate resin composition according to claim 1, wherein the pKa of the aromatic carboxylic acid has a positive value. The polyethylene terephthalate resin composition according to claim 1 or 2 , wherein the structure of the organic cation is a protonation of a nitrogen-containing compound having a boiling point of 260 ° C. or higher. The polyethylene terephthalate resin composition according to any one of claims 1 to 3, wherein the solution haze is 5% or less. The polyethylene terephthalate resin composition according to any one of claims 1 to 4 , wherein the amount of increase in COOH terminal groups (ΔCOOH) when treated at 155 ° C. and 100% RH for 4 hours is 80 eq / t or less. The polyethylene terephthalate resin composition according to any one of claims 1 to 5 , wherein the amount of DEG contained in the resin composition is 1.5 wt% or less. A method for producing a polyethylene terephthalate resin composition, which comprises mixing an ionic salt composed of an organic cation protonated with a nitrogen-containing compound and an aromatic carboxylic acid ion and a polyethylene terephthalate resin composition. Using a dicarboxylic acid component and a diol component, a process for the preparation of polyethylene Chi terephthalate, organic cation and an aromatic carboxylic where the nitrogen-containing compound was protonated during the transesterification or esterification reaction started until the end of the polycondensation reaction method for producing a polyethylene Chi terephthalate resin composition which comprises adding an ionic salt consisting of acid ion. A film comprising the polyethylene terephthalate resin composition according to any one of claims 1 to 6 . A film having at least one film layer made of the polyethylene terephthalate resin composition according to any one of claims 1 to 6 . A film having a film layer made of the polyethylene terephthalate resin composition according to any one of claims 1 to 6 on at least one surface layer.