JPWO2017163974A1 - Polyester composition and method for producing the same - Google Patents

Abstract

Provided are a polyester composition having good thermal stability, and further having a good color tone, transparency, and scratch-suppressing effect when formed into a molded product, and a method for producing the same. A polyester composition comprising particles having a standard redox potential of −1.70 V or more and a metal element of 50 nm to 1.5 μm, and an alkali metal element and / or an alkaline earth metal element . [Selection figure] None

Description

  The present invention relates to a polyester composition having a good thermal stability, and having a good color tone, transparency, and a scratch suppressing effect when formed into a molded product, and a method for producing the same.

  Polyester is one of resins that are widely used in applications such as films, fibers, bottles, sheets, and containers because it is excellent in mechanical strength, chemical stability, transparency, and inexpensive.

  Conventionally, polyester has been subjected to problems such as generation of foreign matter due to gelation in molding processing such as melt extrusion, increase in the contamination of the die of the molding machine, and filter clogging in the manufacturing process.

  In addition, when a molded product such as a film is used, scratches may occur during film formation or processing. In particular, deterioration of quality due to scratches has been a problem in optical films and release films.

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 is improved by adding a copper salt or a halide.

Patent Document 2 describes that the thermal stability is improved by containing a metal halide.
Patent Document 3 describes that scratches due to the inclusion of fine aggregated particles are suppressed.

JP 2010-265459 A Japanese Patent Laying-Open No. 2015-67661 JP 2001-171061 A

However, just by containing a copper salt or a metal halide as in these conventional techniques, color tone and transparency are lowered. Moreover, since the fine aggregated particles have no effect of improving the thermal stability, there is a problem that the thermal stability is insufficient.

  The objective of this invention is providing the polyester composition which has favorable thermal stability, and also has the favorable color tone, transparency, and the crack suppression effect at the time of setting it as a molded article, and its manufacturing method.

As a result of intensive studies to solve the above problems, a polyester composition having a good thermal stability, a good color tone, transparency, and a scratch inhibiting effect when formed into a molded product and a method for producing the same have been found. The invention has been reached.
The object of the present invention is achieved by the following means.
(1) It contains 50 nm to 1.5 μm particles including a metal element having a standard oxidation-reduction potential of −1.70 V or more, and an alkali metal element and / or an alkaline earth metal element. Polyester composition.
(2) The polyester composition according to (1), wherein the metal element is selected from the group of Cu, Pd, Pt, Au, Fe, and Zn.
(3) The polyester composition as described in (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 ratio of the metal element content M ₁ (mol / t) and the alkali metal element and / or alkaline earth metal element content M ₂ (mol / t) satisfies the formula (I). The polyester composition according to any one of (1) to (4), which is characterized.

0.01 ≦ M ₂ / M ₁ ≦ 30 (I)
(6) The polyester composition according to any one of (1) to (5), wherein the amount of COOH end 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) When a polyester composition is produced by esterification or transesterification of dicarboxylic acid or dicarboxylic acid ester and diol, and then polycondensation reaction, a metal element having a standard oxidation-reduction potential of −1.70 V or more A method for producing a polyester composition, comprising adding a metal compound and a compound containing an alkali metal element and / or an alkaline earth metal element before the end of the polycondensation reaction.
(9) The method for producing a polyester composition as described in (8), wherein the compound containing an alkali metal element and / or an alkaline earth metal element is a basic compound.
(10) The polyester composition as described in (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 Manufacturing method.
(11) The metal element having a standard oxidation-reduction potential of −1.70 V or more is selected from the group of Cu, Pd, Pt, Au, Fe, and Zn, and the addition amount of the metal element is 0 with respect to the polyester composition. It is 0.01 mol / t or more and 30 mol / t or less, The manufacturing method of the polyester composition of any one of (8)-(10) characterized by the above-mentioned.
(12) and the amount _M 3 of the metal element contained in the metal compound (mol / t), the ratio of the amount _M 4 (mol / t) of the alkali metal element and / or alkaline earth metal element, formula (II The method for producing a polyester composition according to any one of (8) to (11), wherein:

0.01 ≦ M ₄ / M ₃ ≦ 30 (II)
(13) A compound containing a metal compound and an alkali metal element and / or an alkaline earth metal element is added between the end of the esterification reaction or transesterification reaction and the end of the polycondensation reaction (8) to The manufacturing method of the polyester composition of any one of (12).
(14) The 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 added as a solution in a solvent. Production method.
(15) The polyester composition according to any one of (8) to (14), wherein a compound solution containing a metal compound and an alkali metal element and / or an alkaline earth metal element is mixed and added. Manufacturing method.

  According to the present invention, it is possible to provide a polyester composition having a good thermal stability, a good color tone, transparency, and a scratch-suppressing effect when formed into a molded product, and a method for producing the same.

  The present invention is described in detail below.

The polyester composition of the present invention contains particles having a standard redox potential of −1.70 V or more and containing a metal element of 50 nm to 1.5 μm, and an alkali metal element and / or an alkaline earth metal element. The polyester composition.
The term “containing a metal element having a standard redox potential of −1.70 V or higher” and a particle size of 50 nm or more and 1.5 μm or less and an alkali metal element and / or an alkaline earth metal element is used in the polyester composition. The thing contains these, Comprising: The chemical form in the particle | grains of each metal element and a polymer is not ask | required.

  In order to achieve the effects of the present invention, the polyester composition of the present invention has particles having a standard redox potential of −1.70 V or more and containing a metal element of 50 nm to 1.5 μm, and an alkali metal element and / or alkaline earth. It is necessary to contain both similar metal elements. When a metal element is contained, although the thermal stability of the polyester composition is improved, the effect of suppressing scratches when formed into a molded product is not exhibited, and there is a possibility that the polyester composition may be colored with metal ions. When the metal element is present in the polyester in the form of metal particles, particularly metal particles that are not ionized, a polyester composition that exhibits a good color tone and a flaw-suppressing effect is obtained. By including both the metal element and the alkali metal element and / or alkaline earth metal element, the metal element is finely divided. When the particles are finely dispersed, the cross-sectional area of the scratch formed when a load is applied is reduced, and a scratch suppressing effect can be imparted. By containing finely divided particles containing a metal element having a standard oxidation-reduction potential of −1.70 V or more and an alkali metal element and / or an alkaline earth metal element, coloring caused by metal ions or the like can be suppressed. It is possible to provide both thermal stability, color tone, and transparency, and to provide a scratch suppressing effect when formed into a molded product.

The polyester composition of the present invention contains particles having a standard redox potential of −1.70 V or more and containing a metal element of 50 nm or more and 1.5 μm or less, and the particle size is the longest diameter of the particles. . By containing such particles having finely dispersed metal elements, it is possible to improve the hardness of a film made using this polyester composition. When the hardness of a film becomes high, the generation | occurrence | production of the crack at the time of film forming can be suppressed, and also the film which has high hardness can be provided.
The polyester composition of the present invention needs to 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, the metal element can be made into particles, and the formed particles can be made into fine particles. It is possible to provide a polyester composition that exhibits an effect of suppressing scratches when it is made into a good color tone, transparency, and molded product. From the viewpoint of transparency, an alkali metal element is particularly preferable.

  The standard oxidation-reduction potential of the present invention is the value described in the electrochemical handbook 6th edition at 25 ° C. As a metal element having a standard oxidation-reduction potential of −1.70 V or more, Al, Ti, Zr, Mn, Ta, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, Sb, Bi, Cu, Hg, Examples thereof include Ag, Pd, Ir, Pt, and Au, and Cu, Pd, Pt, Au, Fe, and Zn are preferable from the viewpoint of transparency. Among these, Cu is particularly preferable because it is excellent in thermal stability and the effect of suppressing scratches on the molded product. Since metal ions composed of these metal elements easily interact with alkali metal elements and / or alkaline earth metal elements, both color tone and transparency can be achieved. In particular, the thermal stability of the polyester composition containing Cu is excellent, but when only Cu is contained, there is a problem that the color tone is lowered, the transparency is lowered, and the scratch suppressing effect is not exhibited. In the polyester composition of the present invention, the coexistence of these metal elements with an alkali metal element and / or an alkaline earth metal element improves the problem of coloring, a decrease in transparency and the effect of suppressing scratches.

  In the polyester composition of the present invention, the content of the metal element having a standard oxidation-reduction 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. Moreover, as an upper limit of content, it is more preferable that it is 10 mol / t or less, and it is further more preferable that it is 2.5 mol / t or less. By satisfying the above range, it has good thermal stability with little gelled foreign matter generated during melt molding without causing deterioration in color tone or transparency, and exhibits a scratch-inhibiting effect when formed into a molded product It is possible to provide a polyester composition.

In the present invention, the content of the alkali metal element and / or alkaline earth metal element is not particularly specified, but the content M ₁ (mol / t) of the metal element having a standard oxidation-reduction potential of −1.70 V or more, It is preferable that the ratio of the content M ₂ (mol / t) of the alkali metal element and / or alkaline earth metal element satisfies the relationship represented by the formula (I).
0.01 ≦ M ₂ / M ₁ ≦ 30 (I)
By making M ₂ / M ₁ within the above numerical range, the color tone and transparency of the resulting composition, and the effect of suppressing scratches when formed into a molded product become better. This is a specific effect due to the coexistence of a metal element and an alkali metal element and / or an alkaline earth metal element having a standard oxidation-reduction potential of −1.70 V or more in a specific ratio. If M ₂ / M ₁ is 0.01 or more, the effect of improving color tone, transparency, and scratch suppression when made into a molded product is remarkable. If M ₂ / M ₁ is 30 or less, excess alkali metal Coloring by elements and / or alkaline earth metal elements does not occur. Further, 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 end group amount of 20 eq / t or less. More preferably, it is 10 eq / t or less. By setting it as the said range, it is possible to provide the polyester composition excellent in heat resistance and hydrolysis resistance.

  The polyester constituting the polyester composition of the present invention is preferably polyethylene terephthalate from the viewpoint of sufficiently achieving the effects of the present invention. Moreover, the 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 is evaluated by the gelation rate when the polyester composition is heat-treated at 300 ° C. for 6 hours in a nitrogen atmosphere having an oxygen concentration of 1%. In the step of melt-molding the polyester composition, a nitrogen purge is generally performed in order to suppress thermal deterioration during melting, but a trace amount of oxygen is mixed. The measurement condition of the gelation rate of the present invention is a condition that assumes this molding step, and the smaller the gelation rate, the better the thermal stability.

  The polyester composition of the present invention preferably has a gelation rate of 15% or less, more preferably 2% or less when treated under the above conditions. By setting it as the said range, it becomes possible to provide the polyester composition suitable for the film use etc. in which high thermal stability is requested | required.

  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 a is large, the polyester composition has a remarkable red color, and when the value a is small, the polyester composition has a significant green color. In order to make the polyester composition of the present invention a polyester composition with good color tone, the a value is preferably in the range of −4 to 10. The lower limit is more preferably −3.5 or more, and further preferably −2.5 or more. More preferably, it is 3 or less as an upper limit, More preferably, it is -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, it causes a decrease in color tone. . In the present invention, by ionizing the metal element, ionization of the metal element is suppressed and a good color tone is realized.

  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 polyester composition. 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. More preferably, it is 3% or less, More preferably, it is 1% or less. By satisfy | filling the said range, it becomes possible to provide the polyester composition suitable for the film etc. in which high transparency is requested | required.

The flaw suppression effect of the polyester composition of the present invention is evaluated by the cross-sectional area of the flaw formed when a 20 mN load is applied to a film made using the polyester composition at a terminal of 5 μm. 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 , no damage is caused even when a load of 20 mN is applied. By satisfy | filling the said range, the crack generation | occurrence | production at the time of film forming can be suppressed, and also it is possible to provide the film which has high hardness.

Next, it describes about the manufacturing method of the polyester composition of this invention.
The method for producing a polyester composition of the present invention comprises the following two-stage processes using a dicarboxylic acid component or an ester thereof and a diol component as main raw materials. That is, a first stage process comprising (A) esterification reaction or (B) transesterification reaction, followed by a second stage process comprising (C) polycondensation reaction.

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

  The dicarboxylic acid of the present invention is terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyl 4,4′-dicarboxylic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, malon. Examples include acids and dimer acids. The dicarboxylic acid ester 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 their alkyl esters.

  Examples of the diol of the present invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, hexanediol, neopentylglycol and other aliphatic diols, Cyclohexanedimethanol, cyclohexanediethanol, decahydronaphthalene diethanol, decahydronaphthalene diethanol, norbornane dimethanol, norbornane diethanol, tricyclodecane dimethanol, tricyclodecane ethanol, tetracyclododecane dimethanol, tetracyclo Saturated alicyclic primary diols such as dodecane diethanol, decalin dimethanol, decalin diethanol, 2,6-dihydroxy-9-oxabicyclo [3,3,1] no 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 adamantyldiol, paraxylene glycol, bis 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. Ethylene glycol is preferable in that the effects of the present invention can be sufficiently achieved and a polyester composition that can be easily processed into a film or fiber can be obtained.

  In the production method of the present invention, among the steps of the first step, (A) the esterification reaction step is an esterification reaction of dicarboxylic acid and diol at a predetermined temperature, and the reaction is continued until a predetermined amount of water is distilled off. This is a step for obtaining a low polymer. When obtaining a low polymer by esterification reaction, from the viewpoint of esterification reactivity and heat resistance, the molar ratio of dicarboxylic acid to diol (diol / dicarboxylic acid) before starting the esterification reaction is 1.05 or more and 1.40. The following range is preferable. 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 setting it as the said range, since it has favorable reactivity and the production | generation of by-products, such as a dimer of diol, can be suppressed, heat resistance can be made favorable.

  The step (B) transesterification is a step in which a dicarboxylic acid alkyl ester and a diol are transesterified and reacted until a predetermined amount of alcohol is distilled to obtain a low polymer. When a low polymer is obtained by transesterification, the molar ratio of the dicarboxylic acid alkyl ester to the diol (diol / dicarboxylic acid alkyl ester) is in the range of 1.7 or more and 2.3 or less from the viewpoint of reactivity and heat resistance. Preferably there is. By setting it as the said range, since transesterification can be advanced efficiently and the byproduct of the dimer of diol can be suppressed, heat resistance can be made favorable.

Among the processes of the second stage, (C) polycondensation reaction is a process for obtaining a polyester composition from a low polymer obtained by (A) esterification reaction or (B) 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, (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 even without a catalyst due to the autocatalytic action of the carboxylic acid. Moreover, as a catalyst used for (B) transesterification reaction, a well-known transesterification catalyst can be used. Examples of transesterification catalysts include organomanganese compounds, organomagnesium compounds, organocalcium compounds, organocobalt compounds, and organolithium compounds. Specifically, carbonates, acetates, benzoates, oxides, hydroxides There are things, but it is not limited to this.

In addition, as the catalyst used in the (C) polycondensation reaction, a known polycondensation catalyst can be used. Examples thereof include compounds such as antimony, titanium, aluminum, tin, and germanium.
Examples of antimony compounds include antimony oxides, antimony carboxylates, and antimony alkoxides.
Examples of the titanium compound include titanium chelate complexes, titanium alkoxides, titanium oxides obtained by hydrolysis of titanium alkoxides, and the like.

  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.

The metal compound may be a hydrate.
Among these, it is preferable to use an antimony compound as a polycondensation reaction catalyst from the viewpoint of polymerization time and color tone.

In the method for producing a polyester composition of the present invention, adding a metal compound containing a metal element having a standard oxidation-reduction potential of −1.70 V or more and a compound containing an alkali metal element and / or an alkaline earth metal element may be added. is necessary.
In the method for producing a polyester composition of the present invention, the metal compound containing a metal element having a standard oxidation-reduction potential of −1.70 V or more and the compound containing an alkali metal element and / or an alkaline earth metal element are the above (A). Although it may be added at any stage of the esterification reaction or (B) transesterification reaction step and subsequent (C) polycondensation reaction step, by adding it before the end of the polycondensation reaction, the amount of COOH end groups is 20 eq. / T or less, and a polyester composition having good transparency can be obtained.

  As a metal compound containing a metal element having a standard oxidation-reduction potential of −1.70 V or more, Al, Ti, Zr, Mn, Ta, Zn, Cr, Fe, Cd, Co, Ni, Sn, Pb, Sb, Bi, Cu , Hg, Ag, Pd, Ir, Pt, and a compound containing a metal element, such as Cu, Pd, Pt, Au, Fe, and Zn are preferable from the viewpoint of transparency. Among these, a Cu compound is particularly preferable from the viewpoint of excellent thermal stability and a flaw suppression effect when formed into a molded product.

  Moreover, the addition aspect, a form, and the form in a polyester composition do not ask | require the metal compound which provides the metal element whose standard oxidation-reduction potential is -1.70V or more. For example, acetates containing the above metal elements, aliphatic carboxylates such as propionates, aromatic carboxylates such as benzoates, nitrates, nitrites, sulfates, sulfites, phosphates, iodides, Examples thereof include halides such as bromide and chloride, hydroxides, oxides, methylates, ethylates, and ethylene glycolates. These may be used in combination of two or more. Among these, the use of metal acetate is particularly preferred from the viewpoint of excellent transparency.

  It is preferable that the addition amount of the metal element whose standard oxidation-reduction potential contained in a metal compound is -1.70 V or more to the polyester composition of the present invention is 0.01 mol / t or more and 30 mol / t or less. The lower limit of the addition amount is more preferably 0.35 mol / t or more. Moreover, as an upper limit of addition amount, it is more preferable that it is 10 mol / t or less, and it is further more preferable that it is 2.5 mol / t or less. By satisfying the above range, a polyester composition having good thermal stability with little gelling foreign matter generated during melt molding without causing deterioration in color tone and transparency, and a scratch-suppressing effect when formed into a molded product Can be provided.

Further, in the method for producing a polyester composition of the present invention, it is necessary to add a compound containing an alkali metal element and / or an alkaline earth metal element.
The addition mode, type, and form in the polyester composition of the compound containing the alkali metal element and / or alkaline earth metal element of the present invention are not limited. 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 is a compound that satisfies the definition of Lewis base or Arrhenius base. A hydroxide is more preferable, and an alkali metal hydroxide is more preferable. When an alkali metal hydroxide is used, a polyester composition with better color tone can be obtained. Of these, potassium hydroxide and sodium hydroxide are particularly preferred. When potassium hydroxide and sodium hydroxide are used, a polyester composition having particularly excellent color tone and transparency can be obtained. Two or more of these may be used in combination.
The method for producing a polyester composition according to the present invention comprises using a metal compound containing a metal element having a standard oxidation-reduction potential of −1.70 V or more and a compound containing an alkali metal element and / or an alkaline earth metal element in combination. The present inventors have found that the composition can be imparted with excellent thermal stability, better color tone, transparency, and a scratch suppressing effect when formed into a molded product. By adding a specific amount of a metal compound containing a metal element having a standard oxidation-reduction potential of −1.70 V or more, good thermal stability can be imparted to the polyester composition, but a scratch-suppressing effect when imparted to a molded product is imparted. Can not. Further, coloring of the polyester composition occurs due to the ions derived from the metal, and the transparency of the polyester composition decreases due to aggregation of the metal compound. In the present invention, by adding a compound containing an alkali metal element and / or an alkaline earth metal element, a part of the diol component which is a raw material of the polyester composition is subjected to a dehydration reaction to generate a reducing aldehyde component. . As a result, metal ions that cause a deterioration in color tone are reduced, and fine particles of metal without coloration are formed, thereby enabling a good color tone and high transparency. Furthermore, the formation of metal fine particles in the polyester composition exerts a scratch suppressing effect when molded. When the 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 fine particles is affected by the standard redox potential of the metal element. That is, in order to achieve the effect of the present invention, the combined use of a specific metal compound and a compound containing an alkali metal element and / or an alkaline earth metal element is particularly important. By using this specific metal compound in combination with a compound containing an alkali metal element and / or an alkaline earth metal element, particles having a standard oxidation-reduction potential of 50 nm or more and 1.5 μm or less containing a metal element having a standard oxidation-reduction potential of −1.70 V or more can be produced. It can be formed in the object.
The amount _M 3 of the metal element standard oxidation-reduction potential is greater than or equal to -1.70V contained in the metal compound (mol / t), amount _M 4 of the alkali metal element and / or alkaline earth metal element (mol / It is preferable that the ratio of t) satisfies the relationship represented by the formula (II).
0.01 ≦ M ₄ / M ₃ ≦ 30 (II)
By making M ₄ / M ₃ within the above numerical range, the color tone, transparency, and the effect of suppressing scratches when formed into a molded product are further improved. The lower limit of M ₄ / M ₃ is more preferably 0.3 or more. Further, the upper limit of M ₄ / M ₃ is more preferably 10 or less. If M ₄ / M ₃ is 0.01 or more, the color tone, transparency, and the effect of suppressing scratches when formed into a molded product are remarkable. If M ₄ / M ₃ is 30 or less, excess alkali metal elements and Neither coloring with alkaline earth metal elements occurs.

  The color tone and transparency of the polyester composition are clearly superior when used in combination with a compound containing an alkali metal element and / or an alkaline earth metal element, rather than adding the metal compound alone to the polyester composition.

  In the method for producing a polyester composition of the present invention, in order to sufficiently achieve the effects of the present invention, a metal compound is formed between (A) the esterification reaction or (B) the transesterification reaction and (C) the polycondensation reaction. And a compound containing an alkali metal element and / or an alkaline earth metal element are preferably added. The end point of the esterification reaction or transesterification reaction is that the reaction is substantially completed when the reaction rate reaches 95% or more. When added in the middle of (A) esterification reaction or (B) transesterification reaction, the aggregation of metal compounds or metal particles may be coarsened in the (C) polycondensation reaction stage. Further, when added after the (C) polycondensation reaction stage, the effect of improving transparency may be insufficient.

  In the method for producing a polyester composition of the present invention, it is preferable to add a compound containing an alkali metal element and / or an alkaline earth metal element as a solution in a solvent, and to add the compound in the form of an ethylene glycol solution. Is more preferable. In the presence of the above compound, ethylene glycol undergoes a dehydration reaction to produce a reducing aldehyde. At this time, the metal ion is converted into metal fine particles by the reaction between the metal ion derived from the metal compound used in combination and the aldehyde, and the coloring problem due to the metal ion is improved. By dissolving in a solvent, fine metal particles can be formed uniformly.

  In the method for producing a polyester composition of the present invention, a solution of 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 is mixed. It is preferable to add. By mixing and adding, a polyester composition having a better color tone can be obtained.

  As the solvent, water or glycol which is a raw material of polyester can be used, but it is preferable to unify with glycol of raw material from the viewpoint of handleability and the quality of the obtained polyester composition, for example, if it is polyethylene terephthalate It is preferable to use ethylene glycol.

  It is preferable to stir the reaction system at and after the addition of a metal compound containing a metal element having a standard oxidation-reduction potential of −1.70 V or more and a compound containing an alkali metal element and / or an alkaline earth metal element. By stirring, the additive can be more uniformly dispersed and the transparency can be improved.

  Moreover, in the manufacturing method of the polyester composition of this invention, in order to obtain a high molecular weight polyester composition, you may perform a solid phase polymerization. The solid-state polymerization is not particularly limited in apparatus and method, but is carried out by heat-treating the polyester composition 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 composition, and examples thereof include nitrogen, helium, carbon dioxide gas, etc. Nitrogen is preferably used from the viewpoint of economy. Further, under reduced pressure conditions, it is advantageous to use a higher vacuum because the time required for the solid-phase polymerization reaction can be shortened. Specifically, it is preferable to maintain 110 Pa or less.

Hereinafter, although the specific example of the manufacturing method of the polyester composition in this invention is given, it is not restrict | limited to this.
To an esterification reactor charged with bishydroxyethyl terephthalate (hereinafter referred to as BHT) dissolved at 255 ° C., a slurry of terephthalic acid and ethylene glycol (1.15 moles relative to terephthalic acid) was gradually added. The esterification reaction proceeds. The temperature in the reaction system is controlled to be 245 to 250 ° C., and the esterification reaction is terminated when the reaction rate reaches 95%.

  The esterification reaction product at 255 ° C. thus obtained was transferred to a polymerization apparatus, and a phosphorus compound, a metal compound containing a metal element having a standard oxidation-reduction potential of −1.70 V or more, an alkali metal element and / or an alkaline earth metal Add compound containing element, polycondensation catalyst, etc. In these operations, the temperature in the system is preferably maintained at 240 to 255 ° C. so that the esterified product does not solidify.

  Thereafter, while gradually raising the temperature in the polymerization apparatus to 290 ° C., the pressure in the polymerization apparatus is gradually reduced from normal pressure to 250 Pa or less to distill ethylene glycol. The reaction is terminated when a predetermined stirring torque is reached, the inside of the reaction system is brought to atmospheric pressure with nitrogen gas, and the molten polyester is discharged into cold water in a strand form and cut to obtain a polyester composition.

  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, bottles, 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 each product such as a film, fiber, bottle, injection molded product, taking advantage of excellent thermal stability, high transparency, and scratch suppression effect when made into a molded product, In particular, since it has excellent thermal stability, it can be preferably used for film applications.

  Molded articles produced from the polyester composition of the present invention are excellent in thermal stability, color tone, and transparency, and therefore are used for agricultural materials, horticultural materials, fishery materials, civil engineering / building materials, stationery, medical supplies, automobiles. It is useful for parts, electrical / electronic parts or other applications.

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 composition (unit: dl / g)
Orthochlorophenol (hereinafter referred to as OCP) was used as a solvent and measured at 25 ° C.

(2) COOH end group amount of polyester composition (unit: eq / t)
It was measured by the method of Maurice (literature MJ Maurice, F. Huizinga, Anal. Chem. Acta, 22, 363 (1960)).

(3) Confirmation of particle containing metal element, measurement of particle diameter, and analysis of metal element contained in particle A thin film of a polyester composition having a thickness of 0.1 μm to 0.2 μm was prepared, and a transmission electron microscope (Hitachi, H-7650) was used to confirm the particle and particle size. The particle diameter is the longest diameter in the particle. After confirming the particles, the thin film sample was transferred to EDX (Super Xerophy S-779XI, manufactured by Horiba, Ltd.), and measured by energy dispersive X-ray spectroscopy to confirm the metal element.
In the case where particles containing a metal element having a standard oxidation-reduction potential of −1.70 V or more with a particle diameter of 50 nm or more and 1.5 μm or less were contained, it was evaluated as “◯”.

(4) Quantification of Cu, Pd, Pt, Au, Fe, Zn, Ag elements and alkali metal elements in the polyester composition (unit: mol / t)
The amount was determined by atomic absorption analysis (Hitachi, Ltd .: polarized Zeeman atomic absorption photometer 180-80. Frame: acetylene-air) and converted to the amount in the polyester composition 1t.

(5) Determination of Sb and Mg elements in the polyester composition (unit: mol / t)
Quantification was performed using a fluorescent X-ray analyzer (model number: 3270) manufactured by Rigaku Corporation and converted to the amount in the polyester composition 1t.

(6) Gelation rate (unit:%)
The polyster composition was pulverized with a freeze pulverizer (Splex CertiPerp), and 0.5 g was weighed in a stainless beaker. After vacuum drying at 50 ° C. for 2 hours using a vacuum dryer, the oxygen concentration was adjusted to 1% with a mixed gas of air and nitrogen, and the mixed gas with an oxygen concentration of 1% was sufficiently passed through the pipe through the sample-containing container. Thereafter, the container was immersed in an oil bath at 300 ° C. and subjected to heat treatment for 6 hours under a nitrogen flow with an oxygen concentration of 1% (flow rate 0.5 L / min). 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 (manufactured by Shibata Kagaku Co., 3GP40), and the glass filter was washed with dichloromethane. The glass filter is dried at 130 ° C. for 2 hours, and the weight of the OCP insoluble matter (gel) remaining on the filter is calculated from the increment of the weight of the filter before and after filtration, and is based on the polyester weight (0.5 g) of the OCP insoluble matter. The weight fraction was determined and used as the gelation rate (%).

(7) Color tone (a value)
The chip-shaped polyester composition was filled in a measurement cell (φ = 50 mm, height 20 mm), and the a value was measured using a color difference meter (SM color computer model SM-T45, manufactured by Suga Test Instruments Co., Ltd.). The criterion for the color tone was acceptable if the a value was 10 or less, and unacceptable if it exceeded 10.

(8) Solution haze (unit:%)
About 2 g of a sample to be measured was dissolved in 20 mL of OCP, and measurement was performed by an integrating sphere photoelectric photometry method using a haze meter (manufactured by Suga Test Instruments Co., Ltd.) HGM-2DP type. Transparency criteria are
When the solution haze was 10% or less, it was judged as acceptable, and when it exceeded 10%, it was judged as unacceptable.

(9) Scratch cross-sectional area (unit: μm ² ) (scratch suppression evaluation)
A film of 120 mm × 120 mm × 0.4 mm (width × length × thickness) was prepared by melting and pressing 8 g of the chip-like polyester composition at 300 ° C. The film surface was scratched by applying a load of 20 mN to the film using an ultra-thin scratch tester (Resca, CSR5000) using a 5 μm terminal (excitation amplitude 10 μm, excitation frequency 45 Hz, sample temperature 25 ° C.). . The formed scratches were observed with a shape measurement laser microscope (manufactured by Keyence, VK-X200), and the cross-sectional area of the scratches was calculated. The area was measured 6 times and averaged. When the cross-sectional area of the scratch exceeded 130 μm ² , it was rejected.

Example 1
To an esterification reactor charged with 105 parts by weight of BHT 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 moles relative to terephthalic acid) was gradually added. 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 BHT.

From the esterification reactor, 105 parts by weight of BHT was charged into the polymerization apparatus in a molten state, and the temperature was set to 255 ° C. Thereafter, trimethyl phosphate corresponding to 1.43 mol / t was added to the obtained polyester composition. Next, an ethylene glycol mixed solution of copper (II) acetate equivalent to 0.26 mol / t and potassium hydroxide equivalent to 3.33 mol / t was added, and then antimony trioxide equivalent to 0.145 mol / t was added. Added. Thereafter, the temperature in the polymerization apparatus was gradually raised to 290 ° C., the pressure was reduced from normal pressure to 250 Pa or less, and a polymerization reaction was performed at 290 ° C. until a predetermined stirring torque was exhibited. After completion of the polymerization reaction, the molten polyester in the polymerization apparatus was discharged into a water tank in a strand form, cooled, and then cut to obtain a pellet-shaped polyester composition. The properties of the obtained polyester composition are shown in Table 1.
The obtained polyester composition confirmed the particle | grains containing Cu element whose particle diameter is 0.1 micrometer-1.3 micrometer, and all were favorable in heat stability, color tone, and transparency. In addition, the cross-sectional area of the crack of the produced film was 118.4 micrometers ² , and was a pass.

(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 kind of the metal compound or the compound containing the alkali metal element and / or the alkaline earth metal element and the addition amount thereof were changed. Properties of the obtained polyester composition are shown in Tables 1 to 4.
The polyester compositions obtained in Examples 2 to 8 confirmed particles containing Cu element having a particle diameter of 50 nm to 1.5 μm, and all of thermal stability, color tone, transparency and scratch suppression were acceptable levels. It was.

The polyester composition obtained in Example 9 had a small value of M ₂ / M ₁ and redness was observed, but was a pass.
The polyester composition obtained in Example 10 had a large value of M ₂ / M ₁ and greenishness was observed, but it was a pass.
The polyester composition obtained in Example 11 uses copper (II) sulfate instead of copper (II) acetate monohydrate, and has good thermal stability, color tone, transparency and scratch suppression, Although haze was increasing, it was acceptable.
The polyester composition obtained in Example 12 uses copper (I) iodide instead of copper (II) acetate monohydrate, and the thermal stability, color tone, transparency and scratch control are acceptable levels. It was.
In the polyester compositions obtained in Examples 13 and 14, sodium hydroxide was used in place of potassium hydroxide. Thermal stability, color tone, transparency and scratch suppression were good, and the solution haze was increasing but passed.

The polyester compositions obtained in Examples 15 to 20 were prepared by replacing palladium (II) acetate monohydrate with palladium (II) acetate, platinum (II) nitrate, gold (III) acetate, iron (II) acetate, Zinc acetate (II) and silver acetate (I) were used. Compared with the addition of copper acetate (II) monohydrate, the gelation rate tends to increase, but it was at an acceptable level.
The polyester composition obtained in Example 21 used magnesium hydroxide instead of potassium hydroxide. The solubility of magnesium hydroxide in ethylene glycol was low, and it was in a slurry state. Although redness was seen and the solution haze was increasing, it was an acceptable level.

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. Scratch suppression was also unacceptable.
In the polyester compositions obtained in Comparative Examples 2 to 5, the copper compound was added, but since the basic compound was not added, the color tone and / or transparency was lowered, and the scratch control was unacceptable. Moreover, although the particle | grains containing Cu element were confirmed, the particle size was 1.8 micrometers or more.

(Example 22)
To an esterification reactor charged with 105 parts by weight of BHT 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 moles relative to terephthalic acid) was gradually added. 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 BHT.
From the esterification reactor, 105 parts by weight of BHT was charged into the polymerization apparatus in a molten state, and the temperature was set to 255 ° C. Thereafter, trimethyl phosphate equivalent to 1.43 mol / t and antimony trioxide equivalent to 0.145 mol / t were added to the resulting polyester resin to initiate the reaction. After carrying out the polymerization reaction at 290 ° C. until it shows 80% of the predetermined stirring torque, the inside of the polymerization apparatus is returned to normal pressure, and copper (II) acetate monohydrate equivalent to 0.26 mol / t and 3.33 mol / t are obtained. A corresponding solution of potassium hydroxide in ethylene glycol was added. 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 carried out until a predetermined stirring torque was exhibited. The properties of the obtained polyester composition are shown in Table 5.
The obtained polyester composition was good in thermal stability, color tone, transparency and scratch control, but the solution haze was slightly higher than that in Example 1.

(Example 23)
The same procedure as in Example 1 was carried out except that copper (II) acetate monohydrate and potassium hydroxide were not added to the mixed solution but were added separately in a solid state. The properties of the obtained polyester composition are shown in Table 5.
The obtained polyester composition was at a pass level, although color tone / transparency and scratch suppression were reduced as compared with Example 1.

(Example 24)
The same procedure as in Example 1 was performed, except that copper (II) acetate monohydrate and an ethylene glycol solution of potassium hydroxide were not mixed and added separately. The properties of the obtained polyester composition are shown in Table 5.
The obtained polyester composition had good thermal stability, color tone, transparency and scratch control, but the color tone tended to be lower than that of Example 1.

Claims (15)

A polyester composition comprising particles having a standard redox potential of −1.70 V or more and a metal element of 50 nm to 1.5 μm, and an alkali metal element and / or an alkaline earth metal element . 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. 3. The polyester composition according to claim 1, 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 according to claim 2, wherein the metal element is Cu. The ratio of the metal element content M ₁ (mol / t) to the alkali metal element and / or alkaline earth metal element content M ₂ (mol / t) satisfies the formula (I). The polyester composition according to claim 1.
0.01 ≦ M ₂ / M ₁ ≦ 30 (I) The polyester composition according to claim 1, wherein the amount of COOH end groups is 20 eq / t or less. The polyester composition according to claim 1, wherein the polyester is polyethylene terephthalate. A metal compound containing a metal element having a standard oxidation-reduction potential of −1.70 V or more when a polyester composition is produced by esterification or transesterification of dicarboxylic acid or dicarboxylic acid ester and diol and then polycondensation reaction And a compound containing an alkali metal element and / or an alkaline earth metal element is added before the end of the polycondensation reaction. 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. 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 an alkali metal and / or an alkaline earth metal hydroxide. The metal element having a standard oxidation-reduction potential of −1.70 V or more is selected from the group of Cu, Pd, Pt, Au, Fe, and Zn, and the addition amount of the metal element is 0.01 mol / mol with respect to the polyester composition. It is t or more and 30 mol / t or less, The manufacturing method of the polyester composition of Claim 8 characterized by the above-mentioned. Satisfy the amount _M 3 of the metal element contained in the metal compound (mol / t), the ratio of the amount _M 4 of the alkali metal element and / or alkaline earth metal element (mol / t) is represented by the formula (II) is The manufacturing method of the polyester composition of Claim 8 characterized by the above-mentioned.
0.01 ≦ M ₄ / M ₃ ≦ 30 (II) The polyester according to claim 8, wherein a compound containing a metal compound and an alkali metal element and / or an alkaline earth metal element is added between the end of the esterification reaction or transesterification reaction and the end of the polycondensation reaction. A method for producing the composition. 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 in a solvent. The method for producing a polyester composition according to claim 8, wherein a compound solution containing a metal compound and an alkali metal element and / or an alkaline earth metal element is mixed and added.