TW201802180A - Polyester composition and method for producing same - Google Patents

Abstract

Provided are: a polyester composition which has good thermal stability, also has a good color and good transparency, and can exhibit a scratch-suppressing effect when formed into a molded article; and a method for producing the polyester composition. A polyester composition characterized by comprising: particles each of which contains a metal element having a standard oxidation-reduction potential of -1.70 V or more and has a size of 50 nm to 1.5 [mu]m inclusive; and an alkali metal element and/or an alkali earth metal element.

Description

Polyester composition and manufacturing method thereof

The present invention relates to a polyester composition which has good thermal stability, and further has good color tone, transparency, and scratch-suppressing effect when forming a molded article, and a method for producing the same.

Polyester is one of the resins used in a large number of applications such as films, fibers, bottles, sheets, and containers because of its excellent mechanical strength, chemical stability, transparency, and low cost.

Conventionally, in molding processes such as melt extrusion, polyester has problems such as generation of foreign matter due to gelation, increase in dirt at the nozzle of the molding machine, and clogging of filters in the manufacturing process.

Moreover, when it is used as a molded product such as a film, scratches may occur during film formation or processing, and especially in optical films or release films, quality degradation due to scratches is a problem.

These subjects have been examined as shown in the following documents.

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 is improved by adding a copper salt or a halide.

Patent Document 2 describes that heat is generated by containing a metal halide. Improved stability.

Patent Document 3 describes suppressing scratches caused by containing fine agglomerated particles.

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2010-265459

Patent Document 2: Japanese Patent Application Laid-Open No. 2015-67661

Patent Document 3: Japanese Patent Laid-Open No. 2001-171061

However, in such conventional technologies, only copper salts or metal halides are contained, and the color tone and transparency are lowered. In addition, since fine aggregated particles have no effect of improving thermal stability, there is a problem of so-called insufficient thermal stability.

An object of the present invention is to provide a polyester composition which has good thermal stability, and further has good color tone, transparency, and scratch-suppressing effect when forming a molded article, and a method for producing the same.

As a result of intensive research in order to solve the above-mentioned problems, it was found that a polyester composition having good thermal stability, further having good color tone, transparency, and scratch-suppressing effect when forming a molded article and a method for producing the same are achieved. .

The object of the present invention is achieved by the following means.

(1) A polyester composition comprising: Particles of a metal element having a reduction potential of -1.70 V or more, 50 nm to 1.5 µm, and alkali metal elements and / or alkaline earth metal elements.

(2) The polyester composition according to (1), wherein the metal element is selected from the group consisting of Cu, Pd, Pt, Au, Fe, and Zn.

(3) The polyester composition according to (1) or (2), wherein the content of the metal element is 0.01 mol / t or more and 30 mol / t or less with respect to the polyester composition.

(4) The polyester composition according to any one of (1) to (3), wherein the metal element is Cu.

(5) The polyester composition according to any one of (1) to (4), characterized in that the content of metal elements M ₁ (mol / t) and the content of alkali metal elements and / or alkaline earth metal elements The ratio of M ₂ (mol / t) satisfies the formula (I).

M₂/M₁

30 (I) 0.01

M ₂ / M ₁

30 (I)

(6) The polyester composition according to any one of (1) to (5), characterized in that the amount of COOH terminal groups is 20 eq / t or less.

(7) The polyester composition according to any one of (1) to (6), wherein the polyester is polyethylene terephthalate.

(8) A method for producing a polyester composition, characterized in that when a dicarboxylic acid or a dicarboxylic acid ester and a diol are subjected to an esterification reaction or a transesterification reaction, followed by a polycondensation reaction to produce a polyester composition Before the end of the polycondensation reaction, a metal compound containing a metal element having a standard redox potential of -1.70 V or more, and a compound containing an alkali metal element and / or an alkaline earth metal element are added.

(9) The method for producing a polyester composition according to (8), wherein the compound containing an alkali metal element and / or an alkaline earth metal element is made alkaline 组合。 The compound.

(10) The method for producing a polyester composition according to (8) or (9), wherein the compound containing an alkali metal element and / or an alkaline earth metal element is an alkali metal and / or an alkaline earth metal hydroxide.

(11) The method for producing a polyester composition according to any one of (8) to (10), wherein the metal element having a standard redox potential of -1.70 V or more is selected from Cu, Pd, and Pt , Au, Fe, Zn, and the addition amount of the metal element is 0.01 mol / t or more and 30 mol / t or less with respect to the polyester composition.

(12) The method for producing a polyester composition according to any one of (8) to (11), characterized in that the additive amount of the metal element contained in the metal compound M ₃ (mol / t) and the alkali metal The ratio of the addition amount M ₄ (mol / t) of the element and / or the alkaline earth metal element satisfies the formula (II).

M₄/M₃

30 (II) 0.01

M ₄ / M ₃

30 (II)

(13) The method for producing a polyester composition according to any one of (8) to (12), characterized in that a metal is added between the end of the esterification reaction or the transesterification reaction and the end of the polycondensation reaction. Compounds and compounds containing alkali metal elements and / or alkaline earth metal elements.

(14) The method for producing a polyester composition according to any one of (8) to (13), wherein a compound containing an alkali metal element and / or an alkaline earth metal element is prepared as a solution dissolved in a solvent, Add to.

(15) The method for producing a polyester composition according to any one of (8) to (14), wherein a metal compound is mixed with a compound solution containing an alkali metal element and / or an alkaline earth metal element and added .

According to the present invention, it is possible to provide a polyester composition which has good thermal stability, and further has good color tone, transparency, and scratch-suppressing effect when forming a molded article, and a method for producing the same.

[Form of Implementing Invention]

The present invention is explained in detail below.

The polyester composition of the present invention refers to a polyester composition containing particles containing metal elements with a standard redox potential of -1.70 V or more and 50 nm to 1.5 µm, and alkali metal elements and / or alkaline earth metal elements.

In addition, in the present invention, the so-called containing: particles containing a metal element with a standard redox potential of -1.70 V or more and 50 nm to 1.5 µm and an alkali metal element and / or alkaline earth metal element means that the polyester composition contains Etc., regardless of the chemical form of each metal element in the particles and the polymer.

In order to achieve the effect of the present invention, the polyester composition of the present invention must also contain particles containing 50 nm to 1.5 μm of metal elements with a standard redox potential of -1.70 V or more, and alkali metal elements and / or alkaline earth metal elements. . In the case of containing a metal element, although the thermal stability of the polyester composition is improved, there is a possibility that a scratch suppressing effect when forming a molded article cannot be exhibited, and there is a possibility of coloring due to metal ions and the like. If the metal element is present in the polyester in the form of metal particles, especially in the form of non-ionized metal particles, it will exhibit a good color tone. Polyester composition with scratch suppression effect. By containing the metal element and the alkali metal element and / or the alkaline earth metal element at the same time, the metal element is micronized. When the particles are microdispersed, the cross-sectional area of scratches formed when a load is applied becomes small, and a scratch-suppressing effect can be provided. By containing particles containing a metal element with a standard redox potential of -1.70 V or more, and alkali metal elements and / or alkaline earth metal elements, the coloration caused by metal ions and the like can be suppressed, and thermal stability is achieved. Properties, color tone, and transparency can further provide a scratch suppression effect when forming a molded product.

The polyester composition of the present invention contains particles having a standard redox potential of -1.70 V or more and a metal element of 50 nm to 1.5 μm, but the particle diameter refers to the longest diameter of the particles. By containing such particles having finely dispersed metal elements, the hardness of a film made using this polyester composition can be improved. When the hardness of the film becomes high, the occurrence of scratches during film formation can be suppressed, and a film having high hardness can be provided.

The polyester composition of the present invention must contain an alkali metal element and / or an alkaline earth metal element. More preferably, it contains an alkali metal element and / or an alkaline earth metal element derived from a basic compound. By containing an alkali metal element and / or an alkaline earth metal element, since the metal element is made into particles, it is also possible to make the particles into finer particles, which can suppress the coloration caused by metal ions and the like, and provide excellent color tone, A polyester composition having transparency and exhibiting a scratch-suppressing effect when forming a molded article. From the viewpoint of transparency, particularly preferred is an alkali metal element.

The standard redox potential of the present invention is the value described in the 6th edition of the Electrochemical Fact Sheet at 25 ° C. Examples of metal elements having a standard redox potential of -1.70 V or more include Al, Ti, Zr, Mn, Ta, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, Sb, Bi, Cu, Hg, Ag, Pd, Ir, Pt, Au, etc., but from the viewpoint of transparency, Cu, Pd, Pt are preferred , Au, Fe, Zn. Among them, Cu is particularly preferred because of its excellent thermal stability and scratch-suppressing effect of the molded product. Metal ions containing these metal elements can easily interact with alkali metal elements and / or alkaline earth metal elements, and thus can have both color tone and transparency. In particular, a polyester composition containing Cu is excellent in thermal stability, but when it contains only Cu, there is a problem that the so-called lowering of color tone and lowering of transparency and the effect of preventing scratches are not exhibited. In the polyester composition of the present invention, by coexisting an alkali metal element and / or an alkaline earth metal element with these metal elements, problems such as improvement in coloration, reduction in transparency, and failure to exhibit scratch prevention effects are eliminated.

In the polyester composition of the present invention, the content of the metal element having a standard redox potential of -1.70 V or more is preferably 0.01 mol / t or more and 30 mol / t or less. The lower limit of the content is more preferably 0.35 mol / t or more. The upper limit of the content is more preferably 10 mol / t or less, and even more preferably 2.5 mol / t or less. By satisfying the above range, it is possible to provide excellent thermal stability without causing degradation in color tone and transparency, and less gelled foreign matter during melt molding, and exhibit scratch suppression when forming a molded product. Effective polyester composition.

In the present invention, the content of the alkali metal element and / or the alkaline earth metal element is not particularly specified, but the content of the metal element M ₁ (mol / t) with a standard redox potential of -1.70 V or more and the alkali metal element are preferred. And / or the ratio of the content M ₂ (mol / t) of the alkaline earth metal element satisfies the relationship represented by the formula (I).

M₂/M₁

30 (I) 0.01

M ₂ / M ₁

30 (I)

By setting M ₂ / M ₁ within the above-mentioned numerical range, the hue and transparency of the obtained composition, and the effect of suppressing scratches when forming a molded article become better. This is a special effect due to the coexistence of metal elements with a standard redox potential of -1.70 V or more, and alkali metal elements and / or alkaline earth metal elements at a specific ratio. If M ₂ / M ₁ is 0.01 or more, the improvement effect of color tone, transparency, and scratch resistance when forming a molded article becomes remarkable. When M ₂ / M ₁ is 30 or less, an excessive alkali metal does not occur. And / or alkaline earth metal elements. The lower limit of M ₂ / M ₁ is more preferably 0.3 or more. The upper limit of M ₂ / M ₁ is more preferably 10 or less.

The polyester composition of the present invention preferably has a COOH terminal group content of 20 eq / t or less. More preferably, it is 10 eq / t or less. By setting it as the said range, a polyester composition excellent in heat resistance and hydrolysis resistance can be provided.

The polyester constituting the polyester composition of the present invention is preferably polyethylene terephthalate from the viewpoint that the effects of the present invention are fully exhibited. Moreover, a copolymerization component may be contained in the range which does not impair the effect of this invention.

The thermal stability of the polyester composition of the present invention was evaluated by a gelation rate of the polyester composition under heat treatment at 300 ° C. for 6 hours under a nitrogen gas atmosphere having an oxygen concentration of 1%. In the step of melt-forming the polyester composition, nitrogen flushing is generally performed in order to suppress thermal degradation during melting, but a small amount of oxygen is mixed. The measurement conditions of the gelation rate of the present invention are assumed to be the conditions of the molding step, and the smaller the gelation rate is, the better the thermal stability is.

The gelation rate when the polyester composition of the present invention is treated under the above conditions is preferably 15% or less, and more preferably 2% or less. By setting as above Within the range, a polyester composition suitable for film applications requiring high thermal stability can be provided.

The color tone of the polyester composition of the present invention is evaluated by a value when measured with a color difference meter. When the value of a is large, the red color of the polyester composition is significant, and when the value of a is small, the green color of the polyester composition is significant. In order to make the polyester composition of the present invention into a polyester composition with a good hue, the value of a is preferably in the range of -4 to 10. The lower limit is more preferably -3.5 or more, and even more preferably -2.5 or more. The upper limit is more preferably 3 or less, and even more preferably -1 or less.

In the present invention, a metal element having a standard reduction potential of -1.70 V or more is used in order to impart thermal stability. However, when the metal element is ionized in the polyester composition, the color tone is reduced. In the present invention, the metal element is ionized to suppress the ionization of the metal element, thereby achieving a good color tone.

The transparency of the polyester composition of the present invention is evaluated by the haze of the solution of the polyester composition. The smaller the haze of the solution, the better is the polyester composition with better transparency. In the present invention, since the metal-derived particles are finely dispersed in the polyester composition, transparency is obtained.

The solution haze of the polyester composition is preferably 10% or less. It is more preferably 3% or less, and even more preferably 1% or less. By satisfying the above range, a polyester composition suitable for a film or the like which requires high transparency can be provided.

The scratch suppression effect of the polyester composition of the present invention was evaluated by applying a cross-sectional area of a scratch formed when a load of 20 mN was applied to a film made of the polyester composition at a 5 μm terminal. The cross-sectional area is preferably 130 μm ² or less, and more preferably 120 μm ² or less. The lower limit of the cross-sectional area is preferably 0 μm ² . When the cross-sectional area is 0 μm ² , even if a load of 20 mN is applied, it is in a state without scratches. By satisfying the above range, the occurrence of scratches during film formation can be suppressed, and a film having high hardness can be further provided.

Next, the manufacturing method of the polyester composition of this invention is described.

The manufacturing method of the polyester composition of this invention uses a dicarboxylic acid component or its ester and a diol component as a main raw material, and includes the following 2 steps. That is, the step including the first stage of the (A) esterification reaction or (B) the transesterification reaction, and the subsequent step including the second stage of the (C) polycondensation reaction.

As a raw material for producing the polyester composition of the present invention, a dicarboxylic acid or a dicarboxylic acid ester and a diol may be used, or two or more kinds may be used in combination.

Examples of the dicarboxylic acid of the present invention include terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, biphenyl 4,4'-dicarboxylic acid, and 5-sulfonic acid. Sodium isophthalic acid (5-sodium sulfoisophthalic acid), oxalic acid, succinic acid, adipic acid, sebacic acid, malonic acid, dimer acid, and the like. The dicarboxylic acid ester refers to a lower alkyl ester, acid anhydride, fluorenyl chloride, or the like of the dicarboxylic acid, and methyl ester, ethyl ester, hydroxyethyl ester, or the like is preferably used. As the dicarboxylic acid or dicarboxylic acid ester of the present invention, a polyester composition having a high melting point and being easily processed into a film, a fiber, or the like can be obtained. A more preferred embodiment is terephthalic acid and 2,6-naphthalenedicarboxylic acid. Formic acid, isophthalic acid, or these alkyl esters.

烷、異山梨醇(isosorbide)等的包含環狀醚之飽和雜環1級二醇，其他環己二醇、雙環己基-4,4’-二醇、2,2-雙(4-羥基環己基丙烷)、2,2-雙(4-(2-羥基乙氧基)環己基)丙烷、環戊二醇、3-甲基-1,2-環戊二醇、4-環戊烯-1,3-二醇、金剛烷二醇等的各種脂環式二醇，或對二甲苯二醇(p-xylene glycol)、雙酚A、雙酚S、苯乙二醇、9,9-雙(4-(2-羥基乙氧基)苯基)茀、9,9’-雙(4-羥苯基)茀等的芳香環式二醇。又，於二醇以外，在不損及本發明的效果之範圍內，亦可使用三羥甲基丙烷、新戊四醇等的多官能醇。以可充分達到本發明的效果之點、及可得到容易加工成薄膜或纖維等的聚酯組成物之點，較佳為乙二醇。 Examples of the diol of the present invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, and neopentyl glycol. Aliphatic diols such as cyclohexanedimethanol, cyclohexanedimethanol, decahydronaphthalene dimethanol, decahydronaphthalene dimethanol, norbornanedimethanol, norbane Diethylene glycol, tricyclodecane dimethanol, tricyclodecane ethanol, tetracyclododecane dimethanol, tetracyclododecane diethanol, decalin dimethanol, decalin dimethanol, etc. Saturated alicyclic primary diol, 2,6-dihydroxy-9-oxabicyclo [3,3,1] nonane (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 (spiro glycerol), 5-hydroxymethyl- 5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-di

Saturated heterocyclic primary diols containing cyclic ethers such as alkane and isosorbide, other cyclohexanediols, dicyclohexyl-4,4'-diols, 2,2-bis (4-hydroxy rings) Hexylpropane), 2,2-bis (4- (2-hydroxyethoxy) cyclohexyl) propane, cyclopentanediol, 3-methyl-1,2-cyclopentanediol, 4-cyclopentene- Various alicyclic diols such as 1,3-diol and adamantanediol, or p-xylene glycol, bisphenol A, bisphenol S, phenyl glycol, 9,9- Aromatic cyclic diols such as bis (4- (2-hydroxyethoxy) phenyl) fluorene and 9,9'-bis (4-hydroxyphenyl) fluorene. In addition to diols, polyfunctional alcohols such as trimethylolpropane and neopentyl alcohol may be used as long as the effects of the present invention are not impaired. Ethylene glycol is preferred because the effects of the present invention can be fully achieved and a polyester composition that can be easily processed into a film or fiber can be obtained.

In the manufacturing method of the present invention, in the step of the first stage, the step of (A) an esterification reaction is to perform an esterification reaction of a dicarboxylic acid and a diol at a predetermined temperature, and the reaction is performed until a predetermined amount of water is distilled off. And a step of obtaining a low polymer. In the case where a low polymer is obtained by an esterification reaction, from the viewpoint of esterification reactivity and heat resistance, the molar ratio of the dicarboxylic acid to the diol (diol / dicarboxylic acid) before the start of the esterification reaction is preferred. The range is 1.05 or more and 1.40 or less. More preferably, it is 1.05 or more and 1.30 or less, and even more preferably 1.05 or more. 1.20 or less. By setting it as the said range, since it has favorable reactivity and can suppress generation | occurrence | production of by-products, such as a dimer of a diol, heat resistance can be made favorable.

The (B) transesterification step is a step of transesterifying an alkyl dicarboxylic acid ester with a diol and performing a reaction until a predetermined amount of alcohol is distilled off to obtain an oligomer. When a low polymer is obtained by the transesterification reaction, from the viewpoint of reactivity and heat resistance, the molar ratio of the alkyl dicarboxylic acid to the diol (diol / alkyl dicarboxylic acid ester) is preferably 1.7 or more and 2.3 The following range. By setting it as the said range, a transesterification reaction can be performed efficiently, the formation of the by-product of a dimer of a diol can be suppressed, and heat resistance can be made favorable.

In the step of the second stage, the (C) polycondensation reaction is a step of obtaining a polyester composition from the oligomer obtained by (A) the esterification reaction or (B) the transesterification reaction.

The production method of the present invention can be applied to batch polymerization, semi-continuous polymerization, and continuous polymerization.

In the method for producing a polyester composition of the present invention, the catalyst used in the (A) esterification reaction may be any compound, such as manganese, cobalt, zinc, titanium, calcium, etc. From the viewpoint of thermal decomposition or generation of foreign matter, it is preferred that the esterification reaction is carried out without a catalyst. Here, (A) the esterification reaction proceeds sufficiently by the autocatalysis of a carboxylic acid even in the absence of a catalyst. As the catalyst used in the (B) transesterification reaction, a known transesterification catalyst can be used. Examples of the transesterification catalyst include organic manganese compounds, organic magnesium compounds, organic calcium compounds, organic cobalt compounds, and organic lithium compounds. Specific examples include carbonates and ethyl esters. Acid salts, benzoates, oxides, hydroxides, and the like are not limited thereto.

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

Examples of the antimony compound include an oxide of antimony, a carboxylate of antimony, and an antimony alkoxide.

Examples of the titanium compound include a titanium chelate complex, a titanium alkoxide, and titanium oxide obtained by hydrolysis of a titanium alkoxide.

Examples of the aluminum compound include aluminum carboxylate, aluminum alkoxide, aluminum chelate compound, and basic aluminum compound.

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.

The above-mentioned metal compound may be a hydrate.

Among them, from the viewpoint of polymerization time and color tone, it is preferable to use an antimony compound as a polycondensation reaction catalyst.

In the method for producing a polyester composition of the present invention, it is necessary to add a metal compound containing a metal element having a standard redox potential of -1.70 V or more, and a compound containing an alkali metal element and / or an alkaline earth metal element.

In the method for producing a polyester composition of the present invention, a metal compound containing a metal element having a standard redox potential of -1.70 V or more, and a compound containing an alkali metal element and / or an alkaline earth metal element may be previously used. The (A) esterification reaction or (B) transesterification reaction step, followed by (C) polycondensation reaction step is added, but by adding before the end of the polycondensation reaction, the amount of COOH terminal groups can be increased The polyester composition is 20 eq / t or less, and a polyester composition having good transparency can be obtained.

Examples of the metal compound containing a metal element having a standard redox potential of -1.70 V or more include Al, Ti, Zr, Mn, Ta, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, Sb, and Bi , Cu, Hg, Ag, Pd, Ir, Pt, Au and other metal element compounds, but from the viewpoint of transparency, compounds of Cu, Pd, Pt, Au, Fe, Zn are preferred. Among them, Cu compounds are particularly preferred from the viewpoint of excellent thermal stability and scratch-suppressing effect when forming molded articles.

In addition, metal compounds of metal elements with a standard redox potential of -1.70 V or more are provided, regardless of the addition state, form, and form in the polyester composition. Examples thereof include aliphatic carboxylic acid salts such as acetates and propionates of the above-mentioned metal elements, aromatic carboxylic acid salts such as benzoates, nitrates, nitrites, sulfates, sulfites, and phosphoric acids. Halides, hydroxides, oxides, methylates, ethanolates, ethyl glycolate, and the like of salts, iodides, bromides, and chlorides may be used in combination of two or more. Among them, from the viewpoint of excellent transparency, it is particularly preferable to use a metal acetate.

The addition amount of the metal element with a standard redox potential of -1.70 V or more contained in the metal compound relative to the polyester composition of the present invention is preferably 0.01 mol / t or more and 30 mol / t or less. The lower limit of the amount added is more preferably 0.35 mol / t or more. The upper limit of the amount of addition is more preferably 10 mol / t or less, and even more preferably 2.5 mol / t or less. By satisfying the above Range, it can provide a polyester composition which does not cause a decrease in color tone or a decrease in transparency, has good thermal stability and has a small amount of gelling foreign matter generated during melt molding, and has a scratch suppressing effect when forming a molded product. .

Moreover, in the manufacturing method of the polyester composition of this invention, it is necessary to add the compound containing an alkali metal element and / or an alkaline-earth metal element.

The addition state and form of the compound containing an alkali metal element and / or an alkaline earth metal element according to the present invention are optional. The compound containing an alkali metal element and / or an alkaline earth metal element is preferably a basic compound. The basic compound of the present invention means a compound satisfying the definition of a Lewis base or an Arenis base. More preferred is hydroxide, and even more preferred is alkali metal hydroxide. When an alkali metal hydroxide is used, a polyester composition having a more excellent hue can be obtained. Among them, potassium hydroxide and sodium hydroxide are particularly preferred. When potassium hydroxide and sodium hydroxide are used, a polyester composition which is particularly excellent in color tone and transparency can be obtained. These may be used in combination of two or more kinds.

The method for producing a polyester composition of the present invention was found to be applicable to a metal compound containing a metal element having a standard redox potential of -1.70 V or more, and a compound containing an alkali metal element and / or an alkaline earth metal element. The polyester composition imparts excellent thermal stability, further imparts good color tone, transparency, and a scratch-suppressing effect when formed into a molded article. By adding a specific amount of a metal compound containing a metal element having a standard redox potential of -1.70 V or more, although a good thermal stability can be imparted to the polyester composition, it cannot provide a scratch-suppressing effect when forming a molded article. In addition, the polyester composition is colored due to ions derived from the metal, and further, the transparency of the polyester composition is reduced due to aggregation of the metal compound and the like. In the present invention, by adding an alkali metal element and / or an alkali The compound of the earth metal element dehydrates a part of the diol component of the raw material of the polyester composition to generate a reducing aldehyde component. Thereby, the metal ions that cause the deterioration of the color tone are reduced, and metal particles having no coloration are formed, thereby making it possible to obtain a good color tone and high transparency. Furthermore, by forming metal fine particles in the polyester composition, a scratch-suppressing effect is exhibited during molding. When a compound containing an alkali metal element and / or an alkaline earth metal element is a basic compound, the effect is further enhanced. The formation of metal particles is affected by the standard redox potential of metal elements. That is, in order to achieve the effect of the present invention, it is particularly important to use a specific metal compound in combination with a compound containing an alkali metal element and / or an alkaline earth metal element. By using this specific metal compound in combination with a compound containing an alkali metal element and / or an alkaline earth metal element, it is possible to form a polyester composition containing a metal element having a standard redox potential of -1.70 V or higher at 50 nm to 1.5 μm. particle.

The amount of metal element M ₃ (mol / t) and the amount of alkali metal element and / or alkaline earth metal element M ₄ (mol / t) that are contained in the metal compound with a standard redox potential of -1.70 V or more are preferred. The ratio satisfies the relationship represented by the formula (II).

M₄/M₃

30 (II) 0.01

M ₄ / M ₃

30 (II)

By setting M ₄ / M ₃ within the above-mentioned numerical range, the hue, transparency, and scratch-suppressing effect when forming a molded article become better. The lower limit of M ₄ / M ₃ is more preferably 0.3 or more. The upper limit of M ₄ / M ₃ is more preferably 10 or less. When M ₄ / M ₃ is 0.01 or more, the color tone, transparency, and scratch-suppressing effect when forming a molded article become remarkable. When M ₄ / M ₃ is 30 or less, an excessive amount of alkali metal elements and And / or coloration caused by alkaline earth metal elements.

Compared with the case where the above-mentioned metal compound is added to the polyester composition alone, the color tone and transparency of the polyester composition are significantly better when used in combination with a compound containing an alkali metal element and / or an alkaline earth metal element.

In the method for producing a polyester composition of the present invention, in order to fully achieve the effects of the present invention, it is preferably between (A) the esterification reaction or (B) the transesterification reaction is completed and (C) the polycondensation reaction is completed. Metal compounds and compounds containing alkali metal elements and / or alkaline earth metal elements are added. The end point of the esterification reaction or the transesterification reaction is set to a time when the reaction rate becomes 95% or more and the reaction is substantially completed. When it is added in the middle of (A) the esterification reaction or (B) the transesterification reaction, agglomeration of the metal compound or coarsening of the metal particles may occur in the (C) polycondensation reaction stage. Moreover, when it adds after (C) polycondensation reaction stage, the improvement effect of transparency may become inadequate.

In the method for producing a polyester composition of the present invention, a compound containing an alkali metal element and / or an alkaline earth metal element is preferably added as a solution dissolved in a solvent, and more preferably, it is a glycol solution of the above compound. Form added. In the presence of the above compounds, the glycol system undergoes a dehydration reaction to generate a reducing aldehyde. At this time, the metal ions that are derived from the metal compound used in combination react with the aldehyde, and the metal ions become metal fine particles, and the coloring problem caused by the metal ions is improved. By dissolving in a solvent, metal fine particles can be uniformly formed.

In the method for producing a polyester composition of the present invention, it is preferable to convert a metal compound containing a metal element having a standard redox potential of -1.70 V or more and an alkali metal element and / or an alkaline earth metal element. The solution of the compound is mixed and added. By adding and mixing, a polyester composition having a more favorable hue can be obtained.

As the solvent, water or a diol of a polyester raw material can be used. However, in terms of operability and the quality of the obtained polyester composition, it is preferably the same as the diol of the raw material. For example, if it is polyphthalic acid Ethylene glycol is preferably ethylene glycol.

When and after adding a metal compound containing a metal element having a standard redox potential of -1.70 V or more and a compound containing an alkali metal element and / or an alkaline earth metal element, the reaction system is preferably stirred. The additives can be dispersed more evenly by stirring, and the transparency can be improved.

Moreover, in the manufacturing method of the polyester composition of this invention, in order to obtain a polyester composition of a high molecular weight, solid-phase polymerization can also be performed. The apparatus and method of solid-phase polymerization are not particularly limited, and are carried out by subjecting the polyester composition to a heat treatment under an inert gas atmosphere or under reduced pressure. The inert gas may be any one that is inert with respect to the polyester composition. Examples of the inert gas include nitrogen, helium, and carbon dioxide. However, nitrogen is preferably used from the viewpoint of economic efficiency. In addition, the reduced pressure conditions are advantageous because a higher vacuum can be used, and the time required for the solid-phase polymerization reaction can be shortened. Specifically, it is preferably maintained at 110 Pa or less.

Hereinafter, specific examples of the method for producing the polyester composition in the present invention will be listed, but it is not limited thereto.

Slowly add a slurry of terephthalic acid and ethylene glycol (1.15 times moles relative to terephthalic acid) in an esterification reactor equipped with dihydroxyethyl terephthalate (hereinafter referred to as BHT) dissolved at 255 ° C. To carry out the esterification reaction. Reaction system The internal temperature is controlled to be 245 to 250 ° C, and the esterification reaction is considered to be completed when the reaction rate reaches 95%.

The thus obtained 255 ° C. esterification reaction product was transferred to a polymerization apparatus, and a phosphorus compound, a metal compound containing a metal element having a standard redox potential of −1.70 V or more, and a compound containing an alkali metal element and / or an alkaline earth metal element were added. , Polycondensation catalyst, etc. During these operations, it is preferable to keep the temperature in the system at 240-255 ° C in a manner that the ester compound is not cured.

Thereafter, the temperature in the polymerization apparatus was gradually raised to 290 ° C, and the pressure in the polymerization apparatus was gradually reduced from normal pressure to 250 Pa or less to distill off ethylene glycol. When the reaction reaches a predetermined stirring torque, the reaction is completed. The reaction system is brought to normal pressure with nitrogen, and the molten polyester is discharged into strands in cold water and cut to obtain a polyester composition.

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

When the polyester composition of the present invention is processed into various products, one or more kinds of various additives may be added as long as the effects of the present invention are not impaired, for example, a coloring agent including a pigment and a dye, a lubricant, Additives such as electrostatic agents, flame retardants, ultraviolet absorbers, antibacterial agents, nucleating agents, plasticizers, and release agents.

The polyester composition of the present invention can make use of thermal stability, high transparency, and excellent scratch-suppressing effect when it is formed into a molded article. The polyester composition is used as various products such as films, fibers, bottles, and injection molded products. Excellent thermal stability, can be used for film applications.

The molded article produced from the polyester composition of the present invention is excellent in thermal stability, color tone, and transparency, and is suitable for agricultural materials, horticultural materials, fishery materials, civil and construction materials, stationery, medical supplies, and automobiles. Useful for parts, electrical, electronic, or other purposes.

[Example]

Examples are given below to further explain the present invention.

In addition, the measurement method of a physical property and the evaluation method of an effect are performed as follows.

(1) Inherent viscosity of polyester composition (unit: dl / g)

The measurement was performed at 25 ° C using o-chlorophenol (hereinafter referred to as OCP) as a solvent.

(2) Amount of COOH terminal group of polyester composition (unit: eq / t)

The measurement was performed by the method of Maurice (document M.J. Maurice, F. Huizinga, Anal. Chem. Acta, 22, 363 (1960)).

(3) Confirmation of particles containing metal elements, measurement of their particle size, and analysis of metal elements contained in particles

A film of a polyester composition having a thickness of 0.1 μm to 0.2 μm was prepared, and the particle and particle size were confirmed using a transmission electron microscope (H-7650, manufactured by Hitachi). The particle size refers to the longest diameter of the particles. After the particles were confirmed, the thin film sample was transferred to EDX (SuperXerophyS-779XI, manufactured by Horiba, Ltd.), and measured by an energy dispersive X-ray spectrometry to confirm the metal elements.

A case where particles containing a metal element having a standard redox potential of -1.70 V or more with a particle diameter of 50 nm or more and 1.5 μm or less is ○, and a case where it is not contained is ×.

(4) Quantification of Cu, Pd, Pt, Au, Fe, Zn, Ag and alkali metal elements in polyester composition (unit: mol / t)

Atomic absorption spectrometry (Hitachi: Polarized Zeeman Atomic Absorption Spectrophotometer (Polarized Zeeman Atomic Absorption Spectrophotometer) 180-80; flame: acetylene-air) was used for quantification and conversion into the amount of 1t of the polyester composition.

(5) Quantification of Sb and Mg elements in polyester composition (unit: mol / t)

Quantification was performed using a fluorescent X-ray analyzer (model: 3270) manufactured by Rigaku Denki Co., Ltd., and the amount was converted into the amount in 1 t of the polyester composition.

(6) Gelation rate (unit:%)

The polyester composition was pulverized with a freeze pulverizer (manufactured by Sprex CertiPerp), and 0.5 g was weighed in a stainless steel beaker. After vacuum drying at 50 ° C for 2 hours using a vacuum dryer, a mixed gas of air and nitrogen was used to achieve an oxygen concentration of 1%, and the mixed gas with an oxygen concentration of 1% was passed through a pipe into a container containing a sample, and fully replaced. Then, this container was immersed in an oil bath at 300 ° C., and heat-treated for 6 hours under a nitrogen flow (flow rate: 0.5 L / min) with an oxygen concentration of 1%. This was dissolved in 20 ml of OCP at 160 ° C for 1 hour, and allowed to cool.

This solution was filtered using a glass filter (made by Shibata Scientific Corporation, 3GP40), and the glass filter was washed with dichloromethane. The glass filter was dried at 130 ° C for 2 hours, and the weight of the filter before and after the filtration was increased, The weight of the OCP insoluble matter (gel) remaining in the filter was calculated, and the weight fraction of the OCP insoluble matter with respect to the weight of the polyester (0.5 g) was calculated as the gelation rate (%).

(7) Hue (a value)

=50mm，高度20mm)，使用色差計(Suga Test Instruments公司製，SM Color Computer型式SM-T45)而測定a值。色調的判定基準係a值為10以下時當作合格，將超過10的情形當作不合格。 A chip-like polyester composition is filled in a measurement tank (

= 50 mm, height 20 mm), a value was measured using a color difference meter (manufactured by Suga Test Instruments, SM Color Computer Model SM-T45). The criterion for determining the hue is a pass when the value of a is 10 or less, and a case where it exceeds 10 is regarded as a fail.

(8) Haze of the solution (unit:%)

About 2 g of the measured sample was dissolved in 20 mL of OCP, and the measurement was performed by a integrating sphere photoelectric photometry using a haze meter (manufactured by Suga Test Instruments) HGM-2DP. The criterion for determining the transparency is a pass when the haze of the solution is 10% or less, and a pass when it exceeds 10%.

(9) Cross-sectional area of scratches (unit: μm ² ) (scratch suppression evaluation)

A film of 120 mm × 120 mm × 0.4 mm (horizontal × vertical × thickness) was prepared by melting and pressing 8 g of the chip-like polyester composition at 300 ° C. An ultra-thin film scratch tester (CSR5000, manufactured by RHESCA) was used to apply a load of 20 mN to the film using a 5 μm terminal to scratch the film surface (excitation amplitude: 10 μm, excitation frequency: 45 Hz, sample temperature: 25 ° C.). The scratches formed were observed with a shape measurement laser microscope (VK-X200, manufactured by KEYENCE), and the cross-sectional area of the scratches was calculated. The area was measured 6 times and averaged. If the cross-sectional area of the scratch exceeds 130 μm ² , it is regarded as a failure.

(Example 1)

In an esterification reactor containing 105 parts by weight of BHT dissolved at 250 ° C., a slurry containing 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times mole with respect to terephthalic acid) was slowly added, and Esterification. The temperature in the reaction system is controlled so as to reach 245 to 250 ° C. When the reaction rate reaches 95%, the esterification reaction is completed and BHT is obtained.

In the self-esterification reactor, 105 parts by weight of BHT was charged into a polymerization apparatus in a molten state, and the temperature was set to 255 ° C. Thereafter, to the obtained polyester composition, trimethyl phosphate equivalent to 1.43 mol / t was added. Next, a mixed solution of copper (II) acetate monohydrate equivalent to 0.26 mol / t and ethylene glycol equivalent to 3.33 mol / t potassium hydroxide was added, and then antimony trioxide equivalent to 0.145 mol / t was added. . Thereafter, the temperature in the polymerization apparatus was gradually raised to 290 ° C, and the pressure was reduced from normal pressure to 250 Pa or less, and the polymerization reaction was performed until a predetermined stirring torque was displayed at 290 ° C. After the completion of the polymerization reaction, the molten polyester in the polymerization device was discharged into a strand into a water tank and cooled, and then cut to obtain a granular polyester composition. The characteristics of the obtained polyester composition are shown in Table 1.

The obtained polyester composition system confirmed that the Cu element-containing particles having a particle diameter of 0.1 μm to 1.3 μm had good thermal stability, color tone, and transparency. In addition, the cross-sectional area of the scratch of the produced film was 118.4 μm ² , which was acceptable.

(Examples 2 to 21, Comparative Examples 1 to 5)

A polyester composition was obtained in the same manner as in Example 1 except that the type and amount of the metal compound or the compound containing an alkali metal element and / or an alkaline earth metal element were changed. The characteristics of the obtained polyester composition are shown in Tables 1 to 4.

In the polyester composition systems obtained in Examples 2 to 8, it was confirmed that particles containing Cu element having a particle diameter of 50 nm to 1.5 μm, and any of the thermal stability, hue, transparency, and scratch suppression were qualified. .

[Table 1]

The polyester composition obtained in Example 9 had a small value of M ₂ / M _{1 and} a red tone was also seen, but it was acceptable.

The polyester composition obtained in Example 10 had a large M ₂ / M ₁ value and a green tone was also seen, but it was acceptable.

The polyester composition obtained in Example 11 used copper (II) sulfate instead of copper (II) acetate monohydrate. The thermal stability, hue, transparency, and scratch resistance were good, although the haze of the solution increased. The tendency but qualified.

The polyester composition obtained in Example 12 used copper (I) iodide instead of copper (II) acetate monohydrate, and the thermal stability, hue, transparency, and scratches were suppressed to acceptable levels.

The polyester compositions obtained in Examples 13 and 14 used sodium hydroxide instead of potassium hydroxide. The thermal stability, hue, transparency, and scratch suppression were good, and the solution haze was acceptable although it tended to increase.

[Table 2]

The polyester compositions obtained in Examples 15 to 20 used palladium (II) acetate, platinum (II) nitrate, gold (III) acetate, iron (II) acetate, zinc (II) acetate, and silver acetate (I ) Instead of copper (II) acetate monohydrate. Compared with the case where copper (II) acetate monohydrate is added, the gelation rate tends to increase, but it is acceptable.

In the polyester composition obtained in Example 21, magnesium hydroxide was used instead of potassium hydroxide. Magnesium hydroxide has a low solubility in ethylene glycol and is in a slurry state. A red tint is seen, and the haze of the solution tends to increase, but it is at a qualified level.

[table 3]

In the polyester composition obtained in Comparative Example 1, antimony trioxide was added, but no basic compound was added, the gelation rate was high, and the thermal stability was insufficient. In addition, the scratch suppression was also unacceptable.

In the polyester compositions obtained in Comparative Examples 2 to 5, copper compounds were added, but basic compounds were not added. Therefore, the hue and / or transparency were reduced, and scratches were suppressed as unacceptable. Moreover, although the particle | grains containing Cu element were confirmed, the particle diameter was 1.8 micrometers or more.

[Table 4]

(Example 22)

In an esterification reactor containing 105 parts by weight of BHT dissolved at 250 ° C., a slurry containing 86 parts by weight of terephthalic acid and 37 parts by weight of ethylene glycol (1.15 times mole with respect to terephthalic acid) was slowly added, and Esterification. The temperature in the reaction system is controlled so as to reach 245 to 250 ° C. When the reaction rate reaches 95%, the esterification reaction is completed and BHT is obtained.

In the self-esterification reactor, 105 parts by weight of BHT was charged into a polymerization apparatus in a molten state, and the temperature was set to 255 ° C. Thereafter, to the obtained polyester resin, trimethyl phosphate equivalent to 1.43 mol / t and antimony trioxide equivalent to 0.145 mol / t were added, and the reaction was started. After the polymerization reaction was performed until 80% of the predetermined stirring torque was displayed at 290 ° C, the inside of the polymerization apparatus was returned to normal pressure, and copper (II) acetate monohydrate equivalent to 0.26 mol / t and 3.33 mol / t equivalent were added. A solution of potassium hydroxide in ethylene glycol. After the addition, the pressure in the polymerization apparatus was reduced again from normal pressure to 250 Pa or less, and the polymerization reaction was performed until a predetermined stirring torque was displayed. The characteristics of the obtained polyester composition are shown in Table 5.

The obtained polyester composition had good thermal stability, color tone, transparency, and scratch resistance, but the solution haze was slightly higher than that of Example 1.

(Example 23)

A copper (II) acetate monohydrate and potassium hydroxide were added in the solid state without separately preparing a mixed solution, and were carried out in the same manner as in Example 1. The characteristics of the obtained polyester composition are shown in Table 5.

Compared with Example 1, the obtained polyester composition had reduced hue, transparency, and scratch resistance, but it was at an acceptable level.

(Example 24)

It carried out similarly to Example 1 except having not mixed copper (II) acetate monohydrate and the ethylene glycol solution of potassium hydroxide, and added each separately. The characteristics of the obtained polyester composition are shown in Table 5.

The obtained polyester composition had good thermal stability, color tone, transparency, and scratch resistance, but the color tone tended to be lower than that of Example 1.

[table 5]

Claims (15)

A polyester composition characterized in that it contains particles of 50 nm to 1.5 μm containing metal elements with a standard redox potential of -1.70 V or more, and alkali metal elements and / or alkaline earth metal elements. The polyester composition according to claim 1, wherein the metal element is selected from the group consisting of Cu, Pd, Pt, Au, Fe, and Zn. For example, the polyester composition of claim 1 or 2, wherein the content of the metal element is 0.01 mol / t or more and 30 mol / t or less with respect to the polyester composition. The polyester composition as claimed in claim 2, wherein the metal element is Cu. For example, the polyester composition of claim 1, wherein the ratio of the content of the metal element M ₁ (mol / t) to the content of the alkali metal element and / or alkaline earth metal element M ₂ (mol / t) satisfies the formula (I) : 0.01

M ₂ / M ₁

30 (I). For example, the polyester composition of claim 1 has a COOH terminal group content of 20 eq / t or less. The polyester composition according to claim 1, wherein the polyester is polyethylene terephthalate. A method for producing a polyester composition, characterized in that when a dicarboxylic acid or a dicarboxylic acid ester and a diol are subjected to an esterification reaction or a transesterification reaction, followed by a polycondensation reaction to produce a polyester composition, Before the completion of the condensation reaction, a metal compound containing a metal element having a standard redox potential of -1.70 V or more, and a compound containing an alkali metal element and / or an alkaline earth metal element are added. The method for producing a polyester composition according to claim 8, wherein the compound containing an alkali metal element and / or an alkaline earth metal element is a basic compound. A method for producing a polyester composition as claimed in claim 8, which contains alkali gold The compounds of the element and / or alkaline earth metal element are alkali metal and / or alkaline earth metal hydroxide. For example, the method for producing a polyester composition according to claim 8, wherein the metal element having a standard redox potential of -1.70V or more is selected from the group of Cu, Pd, Pt, Au, Fe, and Zn, and the amount of the metal element added It is 0.01 mol / t or more and 30 mol / t or less with respect to the polyester composition. The method for producing a polyester composition according to claim 8, wherein the amount of the metal element contained in the metal compound M ₃ (mol / t) and the amount of the alkali metal element and / or alkaline earth metal element M ₄ (mol / t ), Satisfying formula (II): 0.01

M ₄ / M ₃

30 (II). For example, the method for producing a polyester composition according to claim 8 comprises adding a metal compound and a compound containing an alkali metal element and / or an alkaline earth metal element from the end of the esterification reaction or the transesterification reaction to the end of the polycondensation reaction. The method for producing a polyester composition according to claim 8, wherein a compound containing an alkali metal element and / or an alkaline earth metal element is added as a solution dissolved in a solvent. The method for producing a polyester composition according to claim 8, which comprises adding a metal compound to a compound solution containing an alkali metal element and / or an alkaline earth metal element.