JP2016079341A - Polyester composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester composition that has both high transparency and good thermal stability during melt molding and additionally has good mold processability with reduced process contamination during mold processing and to provide a method for producing the polyester composition.SOLUTION: A polyester resin composition contains 0.01 to 15 mol/t of an iodine element, 0.02 to 2 mol/t of a titanium element with an antimony element content of 0.10 mol/t or less, based on the polyester resin composition. Preferably, it contains 0.1 to 20 mol/t of an alkali metal element and 0.1 to 20 mol/t of an alkali earth metal element, a magnesium element or a manganese element and more preferably, it contains 0.1 to 10 mol/t of a phosphorus element and has a molar ratio of the content M1 of an alkali metal element, the content M2 of an alkali earth metal element, a magnesium element or a manganese element and a phosphorus element content P satisfying the relationship of formula (I): 0.3≤M/P≤4.5, M=(M2+M1/2)SELECTED DRAWING: None

Description

  The present invention relates to a polyester composition that has both high transparency and good thermal stability, and further suppresses base stains and film-forming stains, and a method for producing the same.

Polyester is a resin that is widely used as a film, fiber, bottle, sheet, container, and the like because it is excellent in mechanical strength, chemical stability, transparency, and inexpensive.
Polyester is usually remelted after being chipped and then processed by molding. At this time, if a thermal history of 250 ° C or higher is received, foreign matter due to gelation will cause an increase in the contamination of the die of the molding machine. There is a problem that undesirable phenomena such as filter clogging occur.
In addition, antimony compounds that are generally used commercially for polyester polymerization are partially vaporized and dissipated during the polymer melting step. Therefore, in the polyester polymerized using an antimony compound, the residue is deposited around the die and the roll around the molding process, thread breakage occurs in spinning, surface defects are induced in film formation, and film breakage occurs in some cases. Cause.

In consideration of these problems, studies as shown in the following documents have been made.
Patent Document 1 discloses a biaxially stretched polyester film having at least one of a copper salt and a halide, and describes that the thermal stability of the polyester film is improved by adding a copper salt or iodide. However, when a copper salt is contained, the solution haze increases, and there is a concern that the film moldability is insufficient during film formation, and there is a need for improvement. Moreover, since antimony is used as a catalyst, there is a concern about the die during film formation and film formation roll contamination.

  In Patent Document 2, the transparency and color tone of polyester are improved by using iodine and / or an iodine compound, but the thermal stability at the time of molding is not improved.

  Patent Document 3 discloses a method for obtaining a polyester resin having excellent transparency by using a titanium compound instead of an antimony compound. However, in this catalyst system, there is a risk of thermal degradation during molding.

JP 2010-265459 A Japanese Patent Laid-Open No. 58-2323 JP 2010-209358 A

  An object of the present invention is to provide a polyester composition that has both high transparency and good thermal stability, and has good moldability capable of suppressing the stain on the die and the film, and a method for producing the same. .

As a result of intensive studies to solve the above problems, the present inventors have found a polyester composition having high transparency and good thermal stability, and further having molding processability, and a method for producing the same, and reached the present invention.
The object of the present invention is achieved by the following means.
(1) The polyester resin composition contains iodine element 0.01 mol / t or more and 15 mol / t or less, titanium element 0.02 mol / t or more and 2 mol / t or less, and antimony element content is 0.10 mol / t. The polyester resin composition characterized by the following.
(2) The polyester resin according to claim 1, which contains an alkali metal element of 0.1 mol / t or more and 20 mol / t or less, and an alkaline earth metal element, magnesium element or manganese element of 0.1 mol / t or more and 20 mol / t or less. Composition.
(3) Phosphorus element containing 0.1 mol / t or more and 10 mol / t or less, content of alkali metal element M1, alkaline earth metal element, magnesium element or manganese element M2 and phosphorus element content P The polyester resin composition according to claim 1 or 2, wherein the molar ratio satisfies the relationship represented by the formula (I).
0.3 ≦ M / P ≦ 4.5 (I)
M = (M2 + M1 / 2)
(4) The polyester resin composition according to any one of claims 1 to 3, wherein the titanium element is a complex compound.
(5) The polyester resin composition according to any one of claims 2 to 4, wherein the alkali metal element is a potassium element.
(6) The polyester resin composition according to any one of claims 1 to 5, wherein the gelation ratio measured in an atmosphere of 1% oxygen and 99% nitrogen is 10% or less.
(7) Solution polyester haze is 10% or less, The polyester resin composition of any one of Claims 1-6.
(8) In the method for producing a polyester composition in which dicarboxylic acid or dicarboxylic acid ester and diol are esterified or transesterified, and then polycondensed, an iodine compound is added after the esterification or transesterification. The manufacturing method of the polyester resin composition in any one of Claims 1-7.

According to the present invention, it is possible to provide a polyester composition that has both high transparency and good thermal stability during melting, and has excellent moldability, and a method for producing the same.

The present invention is described in detail below.
The polyester constituting the polyester composition of the present invention comprises a dicarboxylic acid component and a diol component. Among them, terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, or esters thereof, ethylene glycol as the diol component Polyethylene terephthalate is preferable in that it can be obtained using the above-mentioned and sufficiently exhibits the effects of the present invention.

The polyester of the present invention may contain a copolymer component other than the main component as long as the effects of the present invention are not impaired.
The polyester composition of the present invention contains iodine element 0.01 mol / t or more and 15 mol / t or less, titanium element 0.02 mol / t or more and 2 mol / t or less with respect to the polyester composition. A polyester composition having a content of 0.10 mol / t or less.
Since the polyester composition of the present invention has good thermal stability at the time of molding, it is important that the polyester composition contains specific amounts of iodine element and titanium element, and the antimony element content is not more than a certain amount. .
This is because the effect of suppressing the generation of the antimony at the time of molding processing and the generation of residues due to the provision of thermal stability by the iodine element and the inclusion of the antimony element in a certain amount or less can be obtained. Moreover, the polyester resin composition excellent in transparency can be obtained, without sacrificing the polymerizability at the time of superposition | polymerization by containing a fixed amount of titanium compounds.
Specifically, oxygen radicals that cause thermal degradation at the time of melting the polymer are captured by the reduction action of iodine element to prevent degradation of the polymer accompanied by a crosslinking reaction and the like, thereby improving the thermal stability of the polyester composition.
The amount of iodine element contained in the polyester composition of the present invention needs to be in the range of 0.01 mol / t to 15 mol / t. Preferably, it is 0.02 mol / t or more and 5 mol / t or less. By satisfying this range, it is possible to provide a polyester composition having good thermal stability. When the content of iodine element is less than 0.01 mol / t, the effect of improving the thermal stability is insufficient, and when it is more than 15 mol / t, there is a possibility of coloring due to deactivation of the metal species.
The amount of antimony element contained in the polyester composition of the present invention needs to be 0.10 mol / t or less. By being in this range, generation of residues derived from antimony during molding processing can be suppressed, foreign matter, thread breakage, film breakage, etc. can be suppressed, and high-quality molding processing becomes possible.

Further, the amount of titanium element contained in the polyester composition of the present invention needs to be 0.02 mol / t or more and 2 mol / t or less, and preferably 0.04 mol / t or more and 1 mol / t or less. If the content of titanium element is less than 0.02 mol / t, the color tone deteriorates due to deterioration during remelting, and sufficient stretchability cannot be obtained in the film-forming and spinning stretching process, resulting in film breakage. And thread breaks occur frequently. On the other hand, if it is higher than 2 mol / t, the polyester composition is highly colored when it is molded, causing haze and fouling of the film-forming process due to pyrolyzate.
The polyester composition of the present invention preferably contains an alkali metal element 0.1 to 20 mol / t and an alkaline earth metal element, magnesium element or manganese element 0.1 to 20 mol / t.

The polyester composition of the present invention has high transparency and good thermal stability, and also has excellent processability when used for film molding, so that specific amounts of iodine element, alkali metal element and alkaline earth are used. It preferably contains a metal element, a magnesium element or a manganese element. This is because the effect of imparting transparency and film moldability by the action of alkali metal element, alkaline earth metal element, magnesium element or manganese element can be obtained. Specifically, in order to impart film molding processability to the polymer, it is important to contain a specific metal element, and as the metal content increases, the film molding processability improves, but the transparency decreases. To do. In order to achieve both film forming processability and transparency, it is important to select a metal species and control its content. By using together an element selected from the alkali metal element group and an element selected from the alkaline earth metal element, magnesium element or manganese element group, both film molding processability and transparency can be achieved.
In addition, containing various elements as used in the field of this invention is content of each element which the polyester composition contains, and the chemical form in a polymer is not ask | required.

  The amount of the alkali metal element contained in the polyester composition of the present invention is preferably in the range of 0.1 mol / t to 20 mol / t. More preferably, they are 0.5 mol / t or more and 15 mol / t or less, More preferably, they are 1.5 mol / t or more and 10 mol / t or less. By satisfying this range, it is possible to provide a polyester composition having transparency and film molding processability. By setting the content of the alkali metal element within the above range, the film molding processability is good, the color is not colored, and the solution haze of the polyester composition is low and good.

  The total amount of alkaline earth metal element, magnesium element or manganese element contained in the polyester composition of the present invention is preferably in the range of 0.1 mol / t to 20 mol / t. More preferably, they are 1 mol / t or more and 4 mol / t or less. By satisfy | filling this range, a solution haze becomes low and it is possible to provide the polyester composition with favorable transparency and film molding processability.

In order to achieve both transparency and film molding processability of the polyester composition, selection of the metal species and control of the content thereof are important. Rather than using an alkali metal element, an alkaline earth metal element, a magnesium element or a manganese element alone, it is possible to achieve both film forming processability and transparency.
The transparency of the polyester composition of the present invention is evaluated by the solution haze of the polyester composition. The smaller the solution haze, the better the transparent polymer.

The polyester composition of the present invention preferably has a solution haze of 10% or less. More preferably, it is 5% or less, More preferably, it is 1.5% or less. By satisfy | filling this range, it becomes possible to provide the polyester composition suitable for the film etc. in which high transparency is requested | required. If it is larger than this range, it is not preferable because the transparency is lowered, and the transmitted light amount of the molded product is lowered due to the lowered transparency.
The polyester composition of the present invention preferably contains a phosphorus element of 0.1 mol / t or more and 10 mol / t or less in order to impart good color tone and thermal stability. More preferably, they are 0.5 mol / t or more and 5 mol / t or less. By setting it within this range, a transparent composition having a good color tone can be obtained.
Further, in the present invention, the content of M ₁ alkali metal element in the polyester _composition, an alkaline earth metal element, the molar ratio of the content M ₂ and a phosphorus element content P of elemental magnesium or manganese element, formula ( It is important to satisfy the relationship represented by I).

0.3 ≦ M / P ≦ 4.5 (I)
_{M = (M 2 + M 1} /2)
By making M / P within the above numerical range, the transparency and film molding processability of the resulting composition are improved. As a minimum of M / P, it is preferred that it is 0.3 or more, and it is still more preferred that it is 1.5 or more. Moreover, as an upper limit of M / P, it is preferable that it is 4.5 or less, and it is more preferable that it is 3.0 or less. When M / P is 0.3 or more, film molding processability is sufficient. On the other hand, when M / P is 4.5 or less, there is no coloring or decomposition by a metal component, and the solution haze is low and good.

  The thermal stability of the polyester composition of the present invention is evaluated by the gelation rate when the polyester composition is heat-treated at 300 ° C. for 6 hours in an atmosphere of 1 vol% oxygen and 99 vol% nitrogen. In the molding process such as film forming and spinning for remelting the polyester composition, nitrogen purge is performed to suppress thermal degradation of the polymer during remelting. For example, the film forming kneading machine and the spinning kneading machine A small amount of oxygen enters from the shaft seal. The measurement condition of the gelation rate of the present invention is a condition assuming a film formation process under a nitrogen purge in this step, and the smaller the gelation rate, the better the film formation heat resistance.

The polyester composition of the present invention preferably has a gelation rate of 10% or less when treated under the above conditions. More preferably, it is 5% or less, More preferably, it is 3% or less. By satisfying this range, it is possible to provide a polyester composition suitable for films, yarns and the like that require high thermal stability.
The alkali metal of the present invention is preferably potassium. Potassium is preferred because it has a lower solution haze than other alkali metals such as sodium. An alkali metal having an atomic number larger than that of potassium is not preferable from the viewpoint of economy.

  The manufacturing method of the polyester composition obtained by using the dicarboxylic acid or dicarboxylic acid ester and diol of the present invention as main raw materials comprises the following two steps. That is, it is a first stage process comprising (A) esterification reaction or (B) transesterification reaction, followed by a second stage process comprising (C) polymerization reaction.

  The raw material for producing the polyester composition of the present invention can be obtained using dicarboxylic acid or dicarboxylic acid ester and diol, and each of dicarboxylic acid or dicarboxylic acid ester and diol may be used alone, or two or more kinds may be used. It is also possible to use in combination. Among these, terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, or esters thereof are preferable, particularly polyester obtained by using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the diol component, and particularly preferably polyethylene terephthalate. .

  Examples of the dicarboxylic acid or dicarboxylic acid ester of the present invention include terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyl 4,4′-dicarboxylic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, and adipic acid. , Sebacic acid, malonic acid, dimer acid, stearic acid, cyclohexanedicarboxylic acid or alkyl esters thereof. The dicarboxylic acid ester referred to in the present invention is the above-mentioned lower alkyl ester, acid anhydride, acyl chloride or the like of dicarboxylic acid, and methyl ester, ethyl ester, hydroxyethyl ester, etc. are preferably used. A more preferred embodiment of the dicarboxylic acid or dicarboxylic acid ester of the present invention is that terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid can be obtained because it has a high melting point and can be easily processed into a film or fiber. Acids, or esters thereof.

  Examples of the diol of the present invention include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, and neopentylglycol. As cycloaliphatic diols, cyclohexanedimethanol, cyclohexanediethanol, decahydronaphthalene diethanol, decahydronaphthalene diethanol, norbornane dimethanol, norbornane diethanol, tricyclodecane dimethanol, tricyclodecane ethanol, tetracyclododecane dimethanol, tetra Saturated alicyclic primary diols such as cyclododecane diethanol, decalin dimethanol, decalin diethanol, 2,6-dihydroxy-9-oxabicyclo [3,3,1] Nan, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (spiroglycol), 5-methylol-5-ethyl- Saturated heterocyclic primary diols containing cyclic ethers such as 2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane and isosorbide, other cyclohexanediols, bicyclohexyl-4,4′-diols, 2 , 2-bis (4-hydroxycyclohexylpropane), 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiol, 4-cyclopentene- Various alicyclic diols such as 1,3-diol and adamant diol, para-xylene glycol, Phenol A, bisphenol 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 diols, polyfunctional alcohols such as trimethylolpropane and pentaerythritol can be used as long as the effects of the present invention are not impaired. Among these, ethylene glycol is preferable in that a polyester composition that can be easily processed into a film or fiber can be obtained.

The method for producing a polyester composition of the present invention is characterized in that a compound containing iodine element, titanium element and antimony element is added, more preferably alkali metal element, alkaline earth metal element / magnesium element / manganese element It is also preferable to add a compound containing phosphorus element.
In the method for producing a polyester composition of the present invention, the compound containing iodine element, titanium element, antimony element, alkali metal element, alkaline earth metal element / magnesium element / manganese element and phosphorus element is the above-mentioned (A) or (B) You may add in any step of a process and the subsequent (C) process. Among them, the compound containing iodine element is preferably added after the completion of the step (A) or the step (B) in terms of producing a polyester composition having excellent thermal stability. Thereby, volatilization of the iodine compound in the polymerization step can be suppressed.

  The additive providing the element of iodine of the present invention may be added in any form, form, or form in the polymer. Either an inorganic iodine compound or an organic iodine compound may be used. For example, potassium iodide, sodium iodide, lithium iodide, copper iodide, manganese iodide, magnesium iodide, calcium iodide, ammonium iodide, hydrogen iodide, iodic acid, ammonium iodate, potassium iodate, iodine Examples thereof include sodium acid, calcium iodate, iodomethane, ethyl iodide, isopropyl iodide, ethyl iodoacetate, iodocyclohexane, iodobenzene, iodobenzoic acid and the like, and these can be used in combination of two or more. Of these, the use of potassium iodide and manganese iodide is particularly preferred. When iodine alone or hydrogen iodide is used, its boiling point is low, so that it is necessary to add a large amount in order to maintain the iodine content in the polyester composition, which is not preferable.

  The additive providing the alkali metal element of the present invention may be added in any form, in any form, and in the polymer, but it is not preferable to use an alkali metal alone for safety. Alkali metal compounds include halides such as iodide, bromide and chloride, aliphatic carboxylates such as acetates, iodine oxides and propionates, aromatic carboxylates such as benzoates, and hydroxides. , Alcoholates such as methylate, ethylate, ethylene glycolate, etc., specifically potassium iodide, sodium iodide, lithium iodide, potassium bromide, sodium bromide, lithium bromide, potassium chloride, sodium chloride , Lithium chloride, potassium acetate, sodium acetate, lithium acetate, potassium iodate, sodium iodate, potassium propionate, sodium proprate, lithium propionate, potassium benzoate, sodium benzoate, lithium benzoate, potassium hydroxide, water Sodium oxide, lithium hydroxide, Potassium methylate, potassium glycolate, and the like butyl potassium. Of these, the use of alkali metal halides and alkali metal acetates is preferred. In addition, in this invention, the compound containing an alkali metal may be 1 type, However, 2 or more types can also be used together.

  The additive that provides the alkaline earth metal element, magnesium element or manganese element of the present invention is not limited in its addition mode, form and form in the polymer, but in terms of excellent film molding processability, the alkaline earth metal, Magnesium and manganese metal compounds are preferred. For example, halides such as iodide, bromide and chloride, aliphatic carboxylates such as acetate and propionate, aromatic carboxylates such as benzoate, hydroxide, methylate, ethylate, ethylene glycolate Specific examples include alcoholates such as magnesium iodide, manganese iodide, calcium iodide, magnesium bromide, manganese bromide, calcium bromide, magnesium chloride, manganese chloride, calcium chloride, magnesium acetate, and acetic acid. Manganese, calcium acetate, magnesium propionate, manganese propionate, calcium propionate, magnesium benzoate, manganese benzoate, calcium benzoate, magnesium hydroxide, manganese hydroxide, calcium hydroxide, magnesium glycolate, etc. That. Two or more of these may be used in combination.

  The additive for providing the phosphorus element of the present invention is not limited in its addition mode, form and form in the polymer, but the use of a phosphorus compound is preferred, and phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphine oxide, It is selected from the group consisting of phosphonous acid, phosphinic acid, phosphine, phosphate, phosphite, phosphonate and phosphinate. One type of additive containing phosphorus element may be used, but two or more types may be used in combination.

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

  In the method for producing a polyester composition in the present invention, when an esterification reaction product is obtained from a dicarboxylic acid and a diol, from the viewpoint of esterification reactivity and heat resistance, the molar ratio of the dicarboxylic acid component to the diol component before the start of the esterification reaction (Diol component / dicarboxylic acid component) is preferably in the range of 1.05 to 1.40. More preferably, they are 1.05 or more and 1.30 or less, More preferably, they are 1.05 or more and 1.20 or less. By making the molar ratio 1.05 or more and 1.40 or less, the esterification reaction can be efficiently advanced, and the by-production of the dimer of the diol component can be suppressed, and as a result, obtained. The heat resistance of the polyester composition can be improved. If the molar ratio is less than 1.05, since the esterification reaction does not proceed efficiently, the time cycle may be long. On the other hand, when the molar ratio exceeds 1.40, the heat resistance may be lowered by the dimer of the diol component by-produced.

  In the method for producing a polyester composition in the present invention, when an esterified product is obtained from a dicarboxylic acid alkyl ester and a diol via an ester exchange reaction (B), from the viewpoint of esterification reactivity and heat resistance, before the esterification reaction starts. The molar ratio of the dicarboxylic acid alkyl ester to the diol (diol / dicarboxylic acid alkyl ester) is preferably in the range of 1.7 to 2.3. By setting the molar ratio of the diol to 1.7 to 2.3, the esterification reaction can efficiently proceed, and the by-product of the dimer of the diol component can be suppressed. As a result, The heat resistance of the obtained polyester composition can be improved. When the molar ratio is less than 1.7, the esterification reaction does not proceed efficiently, so that the time cycle may be long. On the other hand, if the molar ratio exceeds 2.3, the heat resistance may be reduced by the dimer of the diol component by-produced.

  Among the processes of the second stage, (C) polymerization reaction is carried out by reducing the pressure in the reactor to which the low polymer obtained by (A) esterification reaction or (B) transesterification reaction is added. Start, adjust the temperature, pressure and stirring speed in the reactor to conduct the polymerization reaction, and perform polymerization until the stirring torque reaches a predetermined value, i.e., until the polyester reaches the desired viscosity. This is a step of obtaining a molecular weight polyester composition.

  In the method for producing a polyester composition of the present invention, (A) the catalyst used in the esterification reaction may be a compound such as manganese, cobalt, zinc, titanium, calcium, etc., but heat in the polycondensation reaction stage. From the viewpoint of decomposition and generation of foreign matter, the esterification reaction is preferably carried out without a catalyst. Here, the (A) esterification reaction proceeds sufficiently by autocatalysis by the COOH end group even without a catalyst. (B) The catalyst used for the transesterification reaction includes a transesterification catalyst which is a known transesterification catalyst and a co-catalyst such as an organic manganese compound, an organic magnesium compound, an organic calcium compound, an organic cobalt compound, and an organic lithium compound. Etc. are preferably used. Specific examples include carbonates, acetates, benzoates, oxides and hydroxides, but are not limited thereto.

  Moreover, a known polycondensation catalyst can be used for the catalyst used for (C) polymerization reaction. Examples thereof include compounds such as antimony, titanium, aluminum, tin, and germanium.

Examples of the antimony compound include antimony oxide, antimony carboxylic acid, antimony alkoxide, and the like.
Examples of the titanium compound include titanium alkoxide, titanium phenoxide, titanium oxide obtained by hydrolysis thereof, titanium acylate, titanium chelate complex, and the like.
Examples of the titanium alkoxide include titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, tetra-2-ethylhexoxide, titanium octoxide, and the like. Examples of titanium phenoxide include titanium phenoxide and titanium acylate. Examples include titanium lactate and titanium stearate. The titanium chelate complexes include β-diketone chelates such as acetylacetone, hydroxy polyvalent carboxylic acid chelates such as lactic acid, malic acid, tartaric acid, salicylic acid and citric acid, and ketoester chelates such as methyl acetoacetate and ethyl acetoacetate. , Phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or anhydrous Polycarboxylic acid-based chelates such as ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid, triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid , Hi B carboxymethyl ethyl imino diacetic acid, hydroxyethyliminodiacetic propionate, methoxyethyl imino diacetic acid, nitrogen-containing carboxylic acid chelating such ammonium lactate, aniline, phenylamine, diphenylamine, include amine chelates such as triethanolamine. In addition, diisopropoxybisacetylacetone or triethanolamate isopropoxide containing two kinds of these substituents, and these alkoxides, phenoxides, and acylate chelate complexes may contain two or more kinds of substituents. .
Among these titanium compounds, it is preferable to use a titanium chelate complex from the viewpoints of reactivity, haze suppression, and color tone. A single titanium chelate complex may be used, and it is also preferable to use in combination with other titanium compounds such as titanium alkoxide.

Examples of the aluminum compound include aluminum carboxylate, aluminum alkoxide, aluminum chelate compound, basic aluminum compound and the like.
Examples of the tin compound include a tin compound having an alkyl group and a tin compound having a hydroxyl group.
Examples of the germanium compound include germanium oxide and germanium alkoxide.

In the present invention, an antimony compound is not used or a small amount is added to achieve excellent molding processability. However, it is necessary to use the polycondensation catalyst to ensure polycondensation reaction activity. In view of transparency, reaction activity, and cost, it is necessary to use a titanium compound. Within the scope of this object, it is also preferable to use other compounds in addition to the titanium compound.
The various polycondensation catalysts such as iodine compounds, alkali metal compounds, alkaline earth metal compounds, magnesium compounds, manganese compounds, and titanium compounds may be hydrates.
It is also preferable to add the polycondensation catalyst exemplified in (C) in advance in (A) and (B).
Furthermore, a stabilizer, a color tone adjusting agent, an antioxidant, an ultraviolet absorber, a flame retardant, a fluorescent whitening agent, a matting agent, an antifoaming agent, or other additives may be blended as necessary.

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

The polyester composition of the present invention can be produced by batch polymerization, semi-continuous polymerization, or continuous polymerization.
The polyester composition obtained in the present invention can be molded by a known molding method, and can be processed into various products such as films, fibers, bolts, and injection molded products.

  When processing the polyester composition of the present invention into each product, various additives, for example, colorants, pigments, dyes, antistatic agents, flame retardants, ultraviolet absorbers, as long as the effects of the present invention are not impaired. One or more additives such as an antibacterial agent, a nucleating agent, a plasticizer, and a release agent may be added.

  The polyester composition of the present invention can be used as various products such as films, fibers, bolts, injection-molded products, taking advantage of its excellent thermal stability and high transparency. It is preferable to be used for production.

A general method can be adopted as the film forming method. A manufacturing method such as a casting method, an inflation method, a T-die method, or a hot press method can be adopted, but a casting method is preferable.
Casting method measures molten resin with a gear pump and then discharges it from a T die die, and on a cooled drum, the electrostatic application method as an adhesion means, the air chamber method, the air knife method, the press roll method, etc. It is preferable to closely cool and solidify to the cooling medium and rapidly cool to room temperature to obtain an unstretched film. Since particularly good flatness and uniform thickness are required, the electrostatic application method can be particularly preferably employed.

Further, the film can be uniaxially stretched, biaxially stretched and / or stretched in the thickness direction. The biaxial stretching method is not particularly limited, and methods such as a sequential biaxial stretching method and a simultaneous biaxial stretching method can be employed.
These products are useful for agricultural materials, horticultural materials, fishery materials, civil engineering / architectural materials, stationery, medical supplies, automotive parts, electrical / electronic components or other uses.

The present invention will be described more specifically with reference to the following examples.
In addition, the measuring method of a physical property and the evaluation method of an effect were performed in accordance with the following method.

(1) Intrinsic viscosity of polyester (IV)
Orthochlorophenol (OCP) was used as a solvent and measured at 25 ° C.

(2) Determination of elemental iodine in polyester composition A sample is weighed according to JISZ7302, burned in a combustion tube, the generated gas is absorbed in the solution, and a part of the absorption liquid is ion chromatographed using an ultraviolet absorption detector. The analysis was performed by GRAPHICA ICA2000 (manufactured by Toa DDK).

(3) Quantitative determination of alkali metal elements in the polyester composition Quantification was performed by atomic absorption spectrometry (Hitachi, Ltd .: polarized Zeeman atomic absorption photometer 180-80, frame: acetylene-air).

(4) Quantitative determination of alkaline earth metal element, magnesium element or manganese element, phosphorus element, and titanium element in the polyester composition Measured using a fluorescent X-ray analyzer (model number: 3270) manufactured by Rigaku Corporation.

(5) Solution haze Approximately 2 g of the sample to be measured was dissolved in 20 mL of orthochlorophenol, and the haze meter (manufactured by Suga Test Instruments Co., Ltd.) HGM-2DP type was used, and the measurement was performed by an integrating sphere photoelectric photometry method.

(6) Gelation rate 1 g of the polyester composition was pulverized by a freeze pulverizer (Splex CertiPerP, 6750-115) to form a powder having a diameter of 300 μm or less, and then a vacuum dryer (Tokyo Rika Machine, VOS-). 451SD) and vacuum dried at 150 ° C. for 12 hours. Then, what was heat-treated in an oven (manufactured by Yamato Scientific Co., Ltd., DN410I) in an oxygen 1% atmosphere at 300 ° C. for 6 hours was dissolved in 50 ml of orthochlorophenol (OCP) at 150 ° C. for 0.5 hours. . Subsequently, it is filtered with a Buchner type glass filter (maximum pore size 20-30 μm), washed and vacuum dried. The weight of the OCP insoluble matter remaining on the filter was calculated based on the increase in the weight of the filter before and after filtration, and the weight fraction of the OCP insoluble matter relative to the polyester composition (1 g) was determined to obtain the gelation rate (%).

(7) Film molding processability Light is applied to the sheet surface 2.25 mm ² (1.5 mm × 1.5 mm) cast 10 minutes after the start of film formation, and the surface irregularities such as craters are observed by looking at the reflected light with a microscope. Judge by acceptance Judgment criteria are ◎ when there is no unevenness on the surface at all, ◎ when there are unevenness on the surface, but the number is 50 or less, the depth is shallower than 0.1 μm, and disappears by stretching, ○ There are irregularities, but the number is over 50 and the depth is shallow, less than 0.1 μm, and Δ is when the surface disappears by stretching, and × when the surface is uneven and does not disappear by stretching. .

(8) Cast drum and preheating roll stains Clean the cast drum, preheating roll and its surroundings thoroughly before starting film formation, and visually observe the dirt state 48 hours after the start of film formation. “◎” for clean items, “○” for those with almost no dirt at first glance, “△” for those that can be confirmed to be very thin but have no problem with continued use, and the dirt is considerably thick and cleaned. Or the thing which needs exchange was evaluated as "x".

(9) Film surface scratch A biaxially stretched film 48 hours after the start of continuous film formation was sampled with a length of 165 cm, which was laterally stretched and heat-treated with a tenter, and observed visually with transmitted light. The number of surface scratches that could be confirmed was measured. When the number of surface scratches is 10 or more and cannot be used, “x”, when it is 3 to 9, the surface is considerably deteriorated, but when usable, “△” is 1 to 2 The case where there was almost no scratch and the surface property was good was evaluated as “◯”, and the case where no scratch was observed was evaluated as “◎”.
The film forming conditions are as follows.
The polyester composition pellets were melted in a vent type twin screw extruder, and vinylbenzene-divinylbenzene copolymer particles having an average particle size of 0.3 μm were added as a lubricant to a concentration of 0.5% by weight. It was melt-extruded at a composition temperature of 280 ° C. and cut to obtain pellets of a polyethylene terephthalate resin composition containing lubricant particles.
This polyester composition was dried in a vacuum dryer and supplied to an extruder.
The polyester composition was melted at 280 ° C. with an extruder, passed through a gear pump and a filter, supplied to a T die, formed into a sheet, and then electrostatically applied with a wire electrode, while the surface temperature was 20 ° C. It was rapidly cooled and solidified on a casting drum kept at a low temperature.
The obtained cast film was heated with a roll group set at 90 ° C., stretched 3.0 times in the longitudinal direction, led to a tenter, preheated with hot air at 100 ° C., and stretched 3.3 times in the lateral direction. The stretched film was heat-treated with hot air at 200 ° C. in a tenter as it was, and after gradually cooling to room temperature, it was wound up. The thickness of the obtained film was 10 μm.

Example 1
In an esterification reactor charged with 105 parts by weight of bishydroxyethyl terephthalate dissolved at 250 ° 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) is gradually added. And the esterification reaction proceeds. The temperature in the reaction system was controlled to be 245 to 250 ° C., and the esterification reaction was terminated when the reaction rate reached 95% to obtain bis (hydroxyethyl) terephthalate (BHT).

The BHT thus obtained was put into a test tube and kept in a molten state at 255 ° C., then, 0.42 mol of titanium citrate chelate per 1 t of the obtained polymer, 2.56 mol of potassium iodide per 1 t of the obtained polymer 1.28 mol of trimethyl phosphate per 1 t of the obtained polymer and 2.56 mol of manganese (II) acetate per 1 t of the obtained polymer were added. The reaction was started after each compound was added. While gradually raising the temperature in the reactor from 255 ° C. to 290 ° C. over 90 minutes, the pressure was reduced from normal pressure to 150 Pa or less over 90 minutes, and a polymerization reaction was performed at 290 ° C. to a predetermined torque. After completion of the polymerization reaction, the melt was discharged in a strand shape, cooled, and cut to obtain a pellet-shaped polyester composition.
The polyester composition contained 0.42 mol / t titanium, 0.8 mol / t iodine, 2.5 mol / t potassium, 2.3 mol / t manganese, 1.3 mol / t phosphorus atoms. . The properties of the obtained polyester composition are shown in Table 2.
The obtained polyester composition had good transparency and thermal stability, and all of film molding processability, rolls, and film surface states were good.

(Examples 2 to 16, Comparative Examples 1 to 5)
Esterification in the same manner as in Example 1 except that the addition mode and / or addition amount of iodine element, titanium element, antimony element, alkali metal element, alkaline earth metal element, magnesium element, manganese element, and phosphorus element were changed. Next, a polycondensation reaction was performed to obtain a polyester composition.

  In Examples 2 to 4, polymerization and film formation were performed in the same manner as in Example 1 except that the amount of titanium compound added during polymerization was changed. The transparency and heat stability of the composition were good, and film molding processability, rolls, and film surface conditions were all good.

  In Examples 5 to 6, polymerization and film formation were performed in the same manner as in Example 1 except that the amount of iodine compound added during polymerization was changed. The transparency and heat stability of the composition were good, and film molding processability, rolls, and film surface conditions were all good.

  In Example 7, polymerization and film formation were performed in the same manner as in Example 1 except that 0.05 mol / t of antimony trioxide as an antimony element was added during polymerization. Although the roll and film surface conditions during film formation were slightly deteriorated, the transparency, thermal stability, and film molding processability of the composition were good.

  In Example 8, polymerization and film formation were conducted in the same manner as in Example 1 except that the amount of manganese acetate added during polymerization was increased. Although an increase in solution haze and a slight amount of roll contamination during film formation were observed, the transparency, thermal stability, and film molding processability of the composition were good.

In Example 9, polymerization and film formation were conducted in the same manner as in Example 1 except that a small amount of magnesium acetate was added instead of manganese acetate during polymerization.
Although the gelation rate slightly increased and a decrease in thermal stability and a decrease in film formability were observed, the transparency of the composition, the roll during film formation, and the surface state of the film were good.

  In Example 10, polymerization and film formation were carried out in the same manner as in Example 1 except that the amount of potassium iodide added during the polymerization was increased (7.0 mol / t). The transparency and heat stability of the composition were good, and film molding processability, rolls, and film surface conditions were all good.

  In Example 11, polymerization and film formation were conducted in the same manner as in Example 1 except that the amount of trimethyl phosphate during polymerization was increased. Although the film molding processability was slightly lowered, the transparency and thermal stability of the composition were good, and both the roll during film formation and the surface state of the film were good.

  In Example 12, polymerization and film formation were conducted in the same manner as in Example 1 except that sodium iodide was added instead of potassium iodide during polymerization. Although the transparency and thermal stability of the composition were slightly lowered, the film molding processability, the roll, and the surface state of the film were all good.

  In Example 13, polymerization and film formation were carried out in the same manner as in Example 1 except that potassium acetate and titanium acetylacetonate as a titanium compound were added instead of manganese acetate. The transparency and heat stability of the composition were good, and film molding processability, rolls, and film surface conditions were all good.

  In Example 14, polymerization and film formation were performed in the same manner as in Example 1 except that manganese iodide was used instead of manganese acetate, phosphoric acid was added as the phosphorus compound, and lactic acid chelate titanium was added as the titanium compound. The transparency and heat stability of the composition were good, and film molding processability, rolls, and film surface conditions were all good.

  In Example 15, polymerization and film formation were performed in the same manner as in Example 1 except that tetrabutyl titanate was added as a titanium compound. The composition had good transparency, heat stability and film molding processability, and the surface condition of the roll and film was slightly reduced, but was good.

In Example 16, polymerization was carried out by a transesterification method.
A transesterification reaction apparatus was weighed at a ratio of 86.3 parts by weight of dimethyl terephthalate, 14.8 parts by weight of dimethyl 2,6-naphthalenedicarboxylate, and 62.6 parts by weight of ethylene glycol (2 mols of dicarboxylic acid component). Was charged.
After the contents were dissolved at 180 ° C., 2.56 mol of potassium iodide was added per 1 ton of the polymer obtained based on the amount of the polyester composition obtained by the polymerization reaction, and stirred.
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, 1.43 mol of trimethyl phosphate per 1 t of the obtained polymer, 2.56 mol of manganese (II) acetate per 1 t of the obtained polymer, 0.42 mol of 1 mol of the obtained polymer Tetrabutyl titanate was added and stirred for 5 minutes to complete the transesterification reaction. Thereafter, the reaction product is charged into a polymerization apparatus, and the temperature in the reactor is gradually increased from 235 ° C. to 290 ° C. over 90 minutes, and the pressure is reduced from normal pressure to 150 Pa or less over 90 minutes, and the temperature is set at 290 ° C. The polymerization reaction was allowed to torque. After completion of the polymerization reaction, the melt was discharged in a strand shape, cooled, and cut to obtain a pellet-shaped polyester composition. The composition had good transparency, heat stability, and film molding processability. Since tetrabutyl titanate was used, the surface condition of the roll and film was slightly reduced, but it was good.

  In Comparative Example 1, polymerization and film formation were carried out in the same manner as in Example 1 except that antimony trioxide was added as a polymerization catalyst instead of the titanium compound so that the amount of antimony element was 0.15 mol per 1 t of the polymer. As a result, dirt on the roll during film formation was recognized, and film surface scratches also increased.

  In Comparative Example 2, polymerization and film formation were conducted in the same manner as in Example 1 except that the content of the titanium compound in the polymerization catalyst was 0.01 mol per 1 ton of polymer. As a result, a polymer having an intrinsic viscosity capable of forming a film could not be obtained because of insufficient activity of the polymerization catalyst, and film tearing occurred frequently during film forming stretching.

  In Comparative Example 3, polymerization and film formation were conducted in the same manner as in Example 1 except that the content of the titanium compound in the polymerization catalyst was 2.5 mol per 1 ton of polymer. As a result, dirt on the roll during film formation was recognized, and film surface scratches also increased.

  In Comparative Example 4, polymerization and film formation were carried out in the same manner as in Example 1 except that potassium acetate was added in place of potassium iodide so that the potassium content was 2.5 mol per 1 ton of polymer. As a result, the gelation rate was increased and the thermal stability was greatly reduced.

  In Comparative Example 5, polymerization and film formation were conducted in the same manner as in Example 1 except that 2.56 mol / t of iodine was added instead of potassium iodide. As a result, the gelation rate was increased and the thermal stability was greatly reduced. It seems that the boiling point of iodine is low and volatilized during the polymerization due to the iodine content in the composition.

Claims (8)

The polyester resin composition contains iodine element 0.01 mol / t or more and 15 mol / t or less, titanium element 0.02 mol / t or more and 2 mol / t or less, and antimony element content is 0.10 mol / t or less. A polyester resin composition characterized by that. The polyester resin composition according to claim 1, comprising an alkali metal element of 0.1 mol / t to 20 mol / t and an alkaline earth metal element, magnesium element or manganese element of 0.1 mol / t to 20 mol / t. The phosphorus element content is 0.1 mol / t or more and 10 mol / t or less, and the molar ratio of the alkali metal element content M1, the alkaline earth metal element, magnesium element or manganese element content M2 and the phosphorus element content P is The polyester resin composition according to claim 1, wherein the relationship represented by the formula (I) is satisfied.
0.3 ≦ M / P ≦ 4.5 (I)
M = (M2 + M1 / 2) Titanium element is a complex compound, The polyester resin composition of any one of Claims 1-3 characterized by the above-mentioned. The polyester resin composition according to any one of claims 2 to 4, wherein the alkali metal element is a potassium element. The polyester resin composition according to any one of claims 1 to 5, wherein a gelation ratio measured in an atmosphere of 1% oxygen and 99% nitrogen is 10% or less. The polyester resin composition according to any one of claims 1 to 6, wherein the solution haze is 10% or less. A method for producing a polyester composition in which dicarboxylic acid or dicarboxylic acid ester and diol are esterified or transesterified, and then polycondensed, wherein an iodine compound is added after the esterification or transesterification. The manufacturing method of the polyester resin composition in any one of claim | item 1 -7.