HK1060581B - Polytrimethylene terephthalate polyester - Google Patents

Description

Poly (trimethylene terephthalate) -based polyesters

Technical Field

The present invention relates to polyesters. More particularly, the present invention relates to poly (trimethylene terephthalate) -based polyesters that are only slightly yellow after light irradiation and have improved light resistance.

Background

It is known that polyesters are widely used as fibers, resins, films and the like because of their excellent properties. In particular, polyester fibers comprising polyethylene terephthalate and having excellent properties of dimensional stability, heat resistance and chemical and light resistance have been widely used in the field of clothing as well as non-clothing.

In view of the present, polytrimethylene terephthalate-based polyester fibers and woven or knitted fabrics comprising the same, which are difficult to realize with conventional polytrimethylene terephthalate, are increasingly gaining importance in order to impart the hand and dyeability thereof [ e.g., JP-A (hereinafter, JP-A means "Japanese unexamined patent publication") No. 11-200175 ]. However, the polytrimethylene terephthalate-based polyester fiber has a problem that the yellowness under light irradiation is larger than that of polyethylene terephthalate and the light resistance thereof is also inferior to that of polyethylene terephthalate.

The improvement of the whiteness of poly (trimethylene terephthalate) is achieved by adding phosphorus compounds during the polymerization, see for example WO 99/11709. Although this method can improve melt stability, it cannot improve light resistance.

On the other hand, for example, JP-A3-234812 discloses a method of adding a manganese compound, an antimony compound and a germanium compound to polyethylene terephthalate, which is intended to improve the light resistance of polyester fibers. This method can suppress the strength of polyethylene terephthalate fibers from being impaired, but it is not a method for preventing yellowing, particularly of polytrimethylene terephthalate fibers.

U.S. patent 5872204 discloses the use of a manganese compound as a catalyst, as a method of adding a manganese compound to poly (trimethylene terephthalate) by using with an antimony compound catalyst. However, this method does not mention improvement of light resistance, and has a problem that foreign substances are easily generated in a spinneret during fiber formation due to the use of an antimony compound.

Disclosure of Invention

The object of the present invention is to solve the problems of the prior art and to provide a polytrimethylene terephthalate based polyester which is only slightly yellowed after light irradiation and has improved light resistance.

Detailed Description

Embodiments of the present invention are discussed in detail below.

Polytrimethylene terephthalate based polyesters are polyesters consisting essentially of repeating units of trimethylene terephthalate.

The phrase "consisting essentially of trimethylene terephthalate repeat units" means "trimethylene terephthalate repeat units constitute 85 mole% or more, preferably 90 mole% or more, of the total repeat units constituting the polyester".

The polyester of the present invention must contain at least one compound selected from the group consisting of alkali metal compounds, alkaline earth metal compounds and manganese compounds in an amount of 10 to 150ppm in terms of metal element. If the element content is less than 10ppm, the light resistance of the finally obtained polyester fiber will become poor. On the other hand, if the content exceeds 150ppm, there are caused problems such as an increase in the degree of bulk yellowing of the polyester polymer and an aggravation of the phenomena of yellowing and molecular weight reduction during remelting. The content of the element is preferably 150 to 120ppm, particularly preferably 20 to 100 ppm.

Examples of the alkali metal used in the present invention include lithium, sodium, potassium, rubidium and the like. Examples of alkaline earth metals include magnesium, calcium, strontium, and the like.

Acetate, benzoate, hydrochloride, formate, oxalate, nitrate, carbonate, etc. can be used as the alkali metal compound, alkaline earth metal compound, and manganese compound used in the present invention. From the viewpoint of stability of the polyester polymer, acetate and benzoate are preferable. Furthermore, these compounds may be hydrated or anhydrous.

Further, in the polyester of the present invention, the molar ratio of the total element content of the alkali metal element, the alkaline earth metal element and the manganese element to the content of the phosphorus element must satisfy the following relational expression

(I)：

0≤P/M≤1 (I)

Wherein P is the molar weight of phosphorus element in the polyester; m is the total molar amount of the alkali metal element, the alkaline earth metal element and the manganese element.

In the formula (I), if P/M is more than 1, the light fastness of the finally obtained fiber becomes poor. P/M is preferably 0 to 0.8, particularly preferably 0 to 0.6.

The polyester of the present invention preferably satisfies the following conditions (a) to (d) at the same time:

(a) the intrinsic viscosity is 0.5 to 1.6,

(b) the content of dipropylene glycol is 0.1 to 2.0% by weight,

(c) the content of the cyclic dimer is 0.01 to 5 wt%, and

(d) the b color value after crystallization is-5-10.

Now, as for the respective conditions, if the intrinsic viscosity is in the above range, the mechanical strength of the finally obtained fiber is sufficiently high and the workability is further improved. The intrinsic viscosity is more preferably 0.55 to 1.5, particularly preferably 0.6 to 1.4.

If the dipropylene glycol content is within the above range, the heat resistance of the polyester and the mechanical strength of the finally obtained fiber become sufficiently high. The content of dipropylene glycol is more preferably 0.15 to 1.8% by weight, particularly preferably 0.2 to 1.5% by weight.

If the cyclic dimer content is in the above range, the yarn-forming properties of the polyester will be good. The content of the cyclic dimer is more preferably 0.02 to 1.8% by weight, particularly preferably 0.03 to 1.5% by weight.

In addition, if the b color value after crystallization is in the above range, the appearance of the finally obtained product is improved. The b color value is more preferably-4 to 9, and particularly preferably-3 to 8.

The polytrimethylene terephthalate-based polyester of the present invention can be copolymerized with components other than the terephthalic acid component and the trimethylene glycol component in amounts not to impair the characteristics of the polytrimethylene terephthalate-based polyester, preferably 10 mol% or less based on the total amount of the dicarboxylic acid component.

Examples of the copolymerization component include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylsulfonedicarboxylic acid, benzophenonedicarboxylic acid, phenylindanedicarboxylic acid, metal 5-sulfinyl (sulfoxy) isophthalate or 5-sulfinylisophthalate, aliphatic diols such as ethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, poly-1, 4-butanediol or cyclohexanediol, alicyclic diols such as 1, 4-cyclohexanedimethanol or 1, 4-cyclohexanediol, aromatic diols such as o-xylene glycol, m-xylene glycol, p-xylene glycol, 1, 4-bis (2-hydroxyethoxy) benzene, 1, 4-bis (2-hydroxyethoxyethoxy) benzene, 4 ' -bis (2-hydroxyethoxy) biphenyl, 4 ' -bis (2-hydroxyethoxyethoxy) biphenyl, 2-bis [4- (2-hydroxyethoxy) phenyl ] propane, 2-bis [4- (2-hydroxyethoxyethoxy) phenyl 1 propane, 1, 3-bis (2-hydroxyethoxy) benzene, 1, 3-bis (2-hydroxyethoxyethoxy) benzene, 1, 2-bis (2-hydroxyethoxy) benzene, 1, 2-bis (2-hydroxyethoxyethoxy) benzene, 4 ' -bis (2-hydroxyethoxy) diphenylsulfone or 4, 4' -bis (2-hydroxyethoxyethoxy) diphenylsulfone, diphenols such as hydroquinone, 2-bis (4-hydroxyphenyl) propane, resorcinol, catechol, dihydroxynaphthalene, dihydroxybiphenyl or dihydroxydiphenylsulfone. One kind of the copolymerization component may be used alone, or two or more kinds may be used in combination.

The poly (trimethylene terephthalate) -based polyester can be prepared by a conventionally known method. That is, there may be employed a transesterification method in which a lower alkyl terephthalate component is transesterified with a trimethylene glycol in the presence of a transesterification catalyst to form a bis (diol) ester and/or a supercondensate thereof, followed by polymerization in the presence of a polymerization catalyst, or a direct polymerization method in which terephthalic acid is directly esterified with a trimethylene glycol to produce an oligomer having a relatively low degree of polymerization, followed by polymerization in the presence of a polymerization catalyst, or the like.

In order to increase the molecular weight, decrease the content of terminal carboxyl groups, and the like, it is preferable to conduct the solid-phase polymerization by means of a conventionally known method.

In the present invention, examples of the compound used as the transesterification catalyst include manganese compounds, cobalt compounds, calcium compounds, titanium compounds, sodium compounds, potassium compounds, zinc compounds, magnesium compounds, and the like. These compounds may be used alone or in combination of two or more. If a titanium compound is used as the polycondensation catalyst, it may be added in advance before the transesterification, and it may be used as both the transesterification catalyst and the polycondensation catalyst.

Examples of the titanium compound preferably used as the polycondensation catalyst include pure titanium tetraalkoxide, a reaction product of at least one compound selected from phthalic acid, trimellitic acid, hemimellitic acid and pyromellitic acid or an anhydride thereof with titanium tetraalkoxide, a reaction product of titanium tetraalkoxide with a phosphonic acid compound, a reaction product of titanium tetraalkoxide with a phosphinic acid compound, a reaction product of titanium tetraalkoxide with a phosphoric acid ester compound, and a compound prepared by further reacting a reaction product of at least one compound selected from phthalic acid, trimellitic acid, hemimellitic acid and pyromellitic acid or an anhydride thereof with titanium tetraalkoxide with a phosphonic acid compound, a phosphinic acid compound or a phosphoric acid ester compound. Titanium tetrabutoxide is particularly preferably used as titanium tetraalkoxide.

The molar ratio of titanium tetraalkoxide to phthalic acid, trimellitic acid, hemimellitic acid, and pyromellitic acid or anhydrides thereof, phosphonic acid compounds, phosphinic acid compounds, and phosphate ester compounds is particularly preferably about 1.5 to 2.5 based on titanium tetraalkoxide.

Examples of phosphonic acid compounds intended to react with titanium tetraalkoxide include phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, tolylphosphonic acid, ditolylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthrylphosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2, 3-dicarboxyphenylphosphonic acid, 2, 4-dicarboxyphenylphosphonic acid, 2, 5-dicarboxyphenylphosphonic acid, 2, 6-dicarboxyphenylphosphonic acid, 3, 4-dicarboxyphenylphosphonic acid, 3, 5-dicarboxyphenylphosphonic acid, 2, 3, 4-tricarboxyphenylphosphonic acid, 2, 3, 5-tricarboxyphenylphosphonic acid, 2, 3, 6-tricarboxyphenylphosphonic acid, 2, 4, 5-tricarboxyphenylphosphonic acid, 2, 4, 6-tricarboxyphenylphosphonic acid, and the like.

Examples of the phosphinic acid compound include phenylphosphinic acid, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, tolylphosphinic acid, ditolylphosphinic acid, biphenylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, bis-methylphenylphosphinic acid, bis-xylylphosphinic acid, biphenylphosphinic acid, naphthylphosphinic acid, anthrylphosphinic acid, 2-carboxyphenylphosphinic acid, 3-carboxyphenylphosphinic acid, 4-carboxyphenylphosphinic acid, 2, 3-dicarboxylphenylphosphinic acid, 2, 4-dicarboxylphenylphosphinic acid, 2, 5-dicarboxylphenylphosphinic acid, 2, 6-dicarboxylphenylphosphinic acid, 3, 4-dicarboxylphenylphosphinic acid, 3, 5-dicarboxyphenylphosphinic acid, 2, 3, 4-tricarboxyphenylphosphinic acid, 2, 3, 5-tricarboxyphenylphosphinic acid, 2, 3, 6-tricarboxyphenylphosphinic acid, 2, 4, 5-tricarboxyphenylphosphinic acid, 2, 4, 6-tricarboxyphenylphosphinic acid, bis (2-carboxyphenyl) phosphinic acid, bis (3-carboxyphenyl) phosphinic acid, bis (4-carboxyphenyl) phosphinic acid, bis (2, 3-dicarboxyphenyl) phosphinic acid, bis (2, 4-dicarboxyphenyl) phosphinic acid, bis (2, 5-dicarboxyphenyl) phosphinic acid, bis (2, 6-carboxyphenyl) phosphinic acid, bis (3, 4-dicarboxyphenyl) phosphinic acid, bis (3, 5-dicarboxyphenyl) phosphinic acid, bis (2, 3, 4-tricarboxyphenyl) phosphinic acid, bis (2, 3, 5-tricarboxyphenyl) phosphinic acid, bis (2, 3, 6-tricarboxyphenyl) phosphinic acid, bis (2, 4, 5-tricarboxyphenyl) phosphinic acid, bis (2, 4, 6-tricarboxyphenyl) phosphinic acid and the like.

Further examples of phosphate ester compounds include monoalkyl and monoaryl phosphates such as monomethyl phosphate, monoethyl phosphate, monotrimethyl phosphate, mono-n-butyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, monolauryl phosphate, monooleyl phosphate, monotetradecyl phosphate, monophenyl phosphate, monobenzyl phosphate, mono (4-dodecyl) phenyl phosphate, mono (4-methylphenyl) phosphate, mono (4-ethylphenyl) phosphate, mono (4-propylphenyl) phosphate, mono (4-dodecylphenyl) phosphate, monomethylphenyl phosphate, monodimethylphenyl phosphate, monobiphenyl phosphate, mononaphthyl phosphate, monoanthryl phosphate and the like.

The poly (trimethylene terephthalate) -based polyester of the present invention may contain, if necessary, small amounts of additives such as lubricants, pigments, dyes, antioxidants, solid-phase polymerization accelerators, optical brighteners, antistatic agents, bactericides, ultraviolet light absorbers, light stabilizers, heat stabilizers, opacifiers, delusterants, and the like.

In the polyester of the present invention, at least one compound selected from the group consisting of alkali metal compounds, alkaline earth metal compounds and manganese compounds is contained in a high concentration in an amount of 150ppm to 10000ppm in terms of metal element, so that a polyester containing a high concentration of metal compounds is obtained. Melt kneading a poly (trimethylene terephthalate) -based polyester with 0.5 to 50 wt% of a polyester containing a high concentration of a metal compound. Whereby at least one compound selected from the group consisting of alkali metal compounds, alkaline earth metal compounds and manganese compounds is introduced so that the content of the at least one compound in the poly (trimethylene terephthalate) -based polyester is 10 to 150ppm in terms of metal element.

At this time, if the amount of the polyester containing a high concentration of the metal compound is 0.5% by weight or less, it is difficult to uniformly disperse the metal compound in the polyester. If the amount exceeds 50% by weight, the production efficiency of the poly (trimethylene terephthalate) -based polyester is poor because the amount of the polyester containing a high concentration of the metal compound used is too large. When the polyester containing a high concentration of metal compound is used, the amount thereof is preferably 0.7 to 40% by weight, more preferably 1 to 30% by weight.

When a polyester containing a high concentration of a metal compound is used, if the content of the metal element is 150ppm or less, in order to maintain the light resistance of the finally obtained fiber at an appropriate level, a correspondingly larger amount of the polyester containing a high concentration of a metal compound must be used. On the other hand, if the content of the metal element exceeds 10000ppm, since the yellowing of the polyester itself containing a high concentration of the metal compound is increased, it is difficult to control the quality of the finally obtained fiber, and if the content exceeds 10000ppm, the phenomenon of lowering of the molecular weight due to thermal degradation is remarkably increased, therefore, the content of the metal element is more preferably 300 to 8000ppm, particularly preferably 500 to 5000 ppm.

The method for melt-kneading the polyester containing a high concentration of a metal element compound with the poly (trimethylene terephthalate) -based polyester is not particularly limited; however, examples of the method include a method of adding a solid or molten polyester containing a high concentration of a metal element compound to a polyester based on poly (trimethylene terephthalate) which is melted by a twin-screw extruder such as a side feeder or the like, a method of web-blending a polyester based on poly (trimethylene terephthalate) with a polyester containing a high concentration of a metal element compound and then melt-kneading the blended web, a method of adding a polyester web containing a high concentration of a metal element compound to a polymerization vessel at a certain polymerization reaction stage of a polyester based on poly (trimethylene terephthalate) which is polymerized by a batch method, and the like.

The fiber comprising the poly (trimethylene terephthalate) -based polyester of the present invention can be manufactured by melt-spinning the poly (trimethylene terephthalate) -based polyester at a temperature of 238 to 275 ℃, and if the melt-spinning temperature is within this range, yarn breakage does not occur during spinning. The melt spinning temperature is preferably 239-270 ℃, particularly preferably 240-265 ℃. And when melt spinning is carried out, the spinning speed is set to be 400-5000 m/min. When the spinning speed is within this range, a fiber having sufficient strength is obtained and the fiber can be stably wound. The spinning speed is more preferably 500 to 4700m/min, particularly preferably 600 to 4500 m/min.

The shape of the spinneret used in the spinning process is not particularly limited, and any of circular, deformed cross-section, solid, hollow shapes, and the like can be employed.

The poly (trimethylene terephthalate) -based drawn polyester yarn of the present invention can be obtained by winding a poly (trimethylene terephthalate) polyester fiber, or by not winding a polyester fiber, and then continuously drawing the fiber.

The intrinsic viscosity of the poly (trimethylene terephthalate) -based polyester fiber and the drawn polyester yarn of the present invention is preferably 0.5 to 1.5. When the intrinsic viscosity is within this range, the finally obtained fiber has a sufficiently high mechanical strength and the handleability is also improved. The intrinsic viscosity is more preferably 0.52 to 1.4, particularly preferably 0.55 to 1.3.

The fabric obtained using the polyester fiber and/or the drawn polyester yarn of the present invention has an increment of 2 or less in b color value after irradiation in a solar weatherometer at a humidity of 50% RH and 60 ℃ for 80 hours.

Examples

The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. The values in the examples were determined as follows:

(1) intrinsic viscosity:

the intrinsic viscosity was measured at 35 ℃ according to a conventional method using o-chlorophenol as a solvent.

(2) And (3) measuring the calcium content, rubidium content, manganese content, cobalt content and phosphorus content in the polyester:

the polymer samples were hot-melted to prepare wafers, and then the contents were measured according to a conventional method using a fluorescent X-ray apparatus manufactured by Rigaku corporation.

(3) Determination of sodium content, potassium content, lithium content and magnesium content in polyester:

a1 g sample of the polymer was dissolved in 10ml of o-chlorophenol, mixed with 20ml of 0.5N hydrochloric acid, and then left to stand overnight. The content was obtained by measuring the supernatant of the hydrochloric acid solution by a conventional method using a zeeman polarized atomic absorption spectrophotometer z-6100 manufactured by Hitachi, ltd.

(4) Content of dipropylene glycol

The polymer sample was sealed in a tube together with an excess of methanol, and then methanolyzed in an autoclave at 260 ℃ for 4 hours, followed by measuring the amount of dipropylene glycol in the decomposition product by a gas chromatograph (HP 6890 series GC system manufactured by Hewlett-Packard Company). Thus, the weight percent of dipropylene glycol based on the weight of the polymer tested was obtained.

(5) Content of cyclic dimer

A 1mg sample of the polymer was dissolved in 1ml hexafluoroisopropanol. The resulting solution was diluted with chloroform until the volume reached 10ml, and then the prepared sample solution was injected into a model 486 liquid chromatograph manufactured by Waters Corporation, in which two GPC TSK gel columns G2000H8 manufactured by Waters Corporation were connected. Chloroform was used as a developing solvent, and the cyclic dimer content in the polymer was obtained from a previously prepared standard cyclic dimer calibration curve.

(6) B color number after crystallization

The color of the web after drying at 130 ℃ for 2 hours was measured using a Minolta co, ltd color difference meter (model CR-200) according to a conventional method, and then the color of the fibers after the fibers were woven into a woven fabric.

(7) Tensile Strength and tensile Length

The test was carried out according to the method described in JIS L1070.

(8) Evaluation of light resistance

The fibers were woven into a woven fabric, and the prepared sample was irradiated in a sun weatherometer (manufactured by Suga Test Instruments Co. Ltd.) at 60 ℃ and humidity 50% RH without rainfall for 80 hours. The b-color value of the sample before and after the irradiation was measured, and the increment of the b-color value was calculated.

Reference example 1

Catalyst for the production of a catalyst comprising the reaction product of titanium tetrabutoxide and trimellitic anhydride

Titanium tetrabutoxide was added to a propylene glycol solution (0.2%) of trimellitic anhydride in an amount of 0.5mol of trimellitic anhydride, and the resulting mixture was then kept at 80 ℃ under normal pressure in air and reacted for 60 min. The resulting reaction mixture was then cooled to normal temperature, and the resulting catalyst was recrystallized from 10-fold amounts of acetone. The precipitate was filtered with filter paper and then dried at 100 ℃ for 2 hours to obtain the objective catalyst.

Reference example 2

Catalyst for the preparation of a reaction product comprising titanium tetrabutoxide and phenylphosphonic acid

Titanium tetrabutoxide was added to a propylene glycol solution (0.2%) of phenylphosphonic acid in an amount of 0.5mol of phenylphosphonic acid, and the resulting mixture was kept at 120 ℃ under normal pressure in air and reacted for 60min to obtain the objective catalyst in the form of a white slurry.

Reference example 3

Catalyst for the preparation of a reaction product comprising titanium tetrabutoxide and phenylphosphinic acid

Titanium tetrabutoxide was added to a propyleneglycol solution of phenylphosphinic acid (0.2%) in an amount of 0.5mol of phenylphosphinic acid, and the resulting mixture was kept at 120 ℃ under normal pressure in air and reacted for 60min to obtain the objective catalyst in the form of a white slurry.

Example 1

To a reactor equipped with a stirrer, a rectifying column and a methanol distillation condenser were added 100 parts by weight of dimethyl terephthalate, 70.5 parts by weight of propylene glycol and 0.0316 part by weight of manganese acetate tetrahydrate as a transesterification catalyst, and then a transesterification reaction was carried out while slowly raising the temperature of the mixture from 140 ℃ and distilling off methanol generated by the reaction out of the system, the internal temperature rose to 210 ℃ 3 hours after the start of the reaction.

To the resulting reaction product was added 0.0526 parts by weight of titanium tetrabutoxide as a polymerization catalyst. The resulting mixture was then transferred to another reactor equipped with a stirrer and a glycol distillation condenser, and then polymerization was carried out while heating the mixture from 210 ℃ to 265 ℃ and reducing the pressure from atmospheric pressure to a high vacuum of 70 Pa. The melt viscosity of the reaction system was monitored, and the polymerization was terminated if the intrinsic viscosity reached 0.75.

The molten polymer was extruded from the bottom of the reactor in strands into cooling water and cut into sheets with a strand cutter. The results are given in table 1.

The obtained web was melted at 250 ℃ using an extrusion spinning apparatus equipped with a spinneret having 36 circular spinneret holes with a hole diameter of 0.27mm, and the spinning productivity was 34g/min and the spinning speed was 2400 m/min. The resultant undrawn yarn was fed to a drawing treatment apparatus equipped with a 60 ℃ heated roll and a 160 ℃ plate heater and subjected to drawing treatment at a drawing ratio of 1.7 times to obtain 83 dtex/36 monofilament (filament) drawn yarn, the results of which are given in table 2.

Example 2

The steps were carried out in the same manner as in example 1 except that 0.0316 parts by weight of manganese acetate tetrahydrate and 0.0038 parts by weight of cobalt acetate tetrahydrate were used in combination as a transesterification catalyst in example 1. The results are given in tables 1 and 2.

Example 3

The steps were carried out in the same manner as in example 1 except that titanium tetrabutoxide was not used as the polymerization catalyst in example 1 but the catalyst prepared in reference example 1 was used in an amount of 30 mmol% in terms of titanium atom. The results are given in tables 1 and 2.

Example 4

The steps were carried out in the same manner as in example 1 except that titanium tetrabutoxide was not used as the polymerization catalyst in example 1 but the catalyst prepared in reference example 2 was used in an amount of 30 mmol% in terms of titanium atom. The results are given in tables 1 and 2.

Example 5

Each procedure was carried out in the same manner as in example 1 except that titanium tetrabutoxide was not used as the polymerization catalyst in example 1 but the catalyst prepared in reference example 3 was used in an amount of 30 mmol% in terms of titanium atom. The results are given in tables 1 and 2.

Example 6

The steps were carried out in the same manner as in example 1 except that 0.009 parts by weight of trimethyl phosphate was added after the end of the transesterification reaction in example 1. The results are given in tables 1 and 2.

Example 7

The steps were carried out in the same manner as in example 2 except that 0.009 parts by weight of trimethyl phosphate was added after the end of the transesterification reaction in example 2. The results are given in tables 1 and 2.

Example 8

The web obtained in the procedure of example 1 was melted at 250 ℃ using an extrusion spinning apparatus equipped with 36 circular spinneret holes having a hole diameter of 0.27mm at a spinning productivity of 36g/min and a spinning speed of 3600 m/min. The obtained undrawn yarn was fed to a drawing treatment apparatus equipped with a heating roll at 60 ℃ and a plate heater at 160 ℃ and subjected to drawing treatment at a draw ratio of 1.2 to obtain 83 dtex/36 monofilament drawn yarn. The results are given in tables 1 and 2.

Example 9

The web obtained by the procedure of example 1 was melted by an extrusion spinning apparatus equipped with 36 circular spinneret holes having a hole diameter of 0.27mm at a spinning productivity of 34g/min and a spinning speed of 2400m/min, and the yarn was fed without being wound up to a drawing treatment apparatus equipped with a 60 ℃ heated roll and a 160 ℃ plate heater and subjected to a drawing treatment at a drawing ratio of 1.7 to obtain 83 dtex/36 monofilament drawn yarn. The results are given in tables 1 and 2.

Example 10

To a reactor equipped with a stirrer, a rectifying column and a methanol distilling condenser were added 100 parts by weight of dimethyl terephthalate, 70.5 parts by weight of propylene glycol and 0.0526 parts by weight of titanium tetrabutoxide catalyst, together with 0.0126 part by weight of potassium acetate, and then an ester exchange reaction was carried out while slowly raising the temperature of the mixture from 140 ℃ and distilling off methanol produced by the reaction. The internal temperature reached 210 ℃ 3 hours after the start of the reaction.

The resulting reaction product was transferred to another reactor equipped with a stirrer and a glycol distillation condenser, and then subjected to polymerization while heating the reaction product from 210 ℃ to 265 ℃ and reducing the pressure from normal pressure to a high vacuum of 70 Pa. The melt viscosity of the reaction system was monitored, and the polymerization was terminated if the intrinsic viscosity reached 0.75.

The molten polymer was extruded from the bottom of the reactor in strands into cooling water and cut into sheets with a strand cutter. The results are given in table 1.

The obtained web was melted at 250 ℃ using an extrusion spinning apparatus equipped with a spinneret having 36 circular spinneret holes with a hole diameter of 0.27mm, and the spinning productivity was 34g/min and the spinning speed was 2400 m/min. The obtained undrawn yarn was fed to a drawing treatment apparatus equipped with a heating roll at 60 ℃ and a plate heater at 160 ℃ and subjected to drawing treatment at a draw ratio of 1.7 to obtain 83 dtex/36 monofilament drawn yarn. The results are given in table 2.

Example 11

The procedures were carried out in the same manner as in example 10 except that in example 10 potassium acetate was used in an amount of not 0.0126 parts by weight but 0.00758 parts by weight of potassium acetate was used. The results are given in tables 1 and 2.

Example 12

The procedures were carried out in the same manner as in example 10 except that 0.0126 parts by weight of potassium acetate was not used in example 10 but 0.0175 parts by weight of sodium acetate trihydrate was used. The results are given in tables 1 and 2.

Example 13

The procedures were carried out in the same manner as in example 10 except that 0.0126 parts by weight of potassium acetate was not used but 0.0085 parts by weight of lithium acetate was used in example 10. The results are given in tables 1 and 2.

Example 14

The steps were carried out in the same manner as in example 10 except that 0.0126 parts by weight of potassium acetate was not used in example 10 but 0.0186 parts by weight of rubidium acetate was used. The results are given in tables 1 and 2.

Example 15

The steps were carried out in the same manner as in example 10 except that 0.0126 parts by weight of potassium acetate was not used in example 10 but 0.0227 parts by weight of calcium acetate monohydrate was used. The results are given in tables 1 and 2.

Example 16

The steps were carried out in the same manner as in example 10 except that 0.0126 parts by weight of potassium acetate was not used in example 10 but 0.0276 parts by weight of magnesium acetate tetrahydrate was used. The results are given in tables 1 and 2.

Example 17

The steps were carried out in the same manner as in example 10 except that titanium tetrabutoxide was not used any more in example 10 but the catalyst prepared in reference example 1 was used in an amount of 30 mmol% in terms of titanium atom. The results are given in tables 1 and 2.

Example 18

The steps were carried out in the same manner as in example 10 except that titanium tetrabutoxide was not used any more in example 10 but the catalyst prepared in reference example 2 was used in an amount of 30 mmol% in terms of titanium atom. The results are given in tables 1 and 2.

Example 19

The steps were carried out in the same manner as in example 10 except that 0.009 parts by weight of trimethyl phosphate was added to the reaction system immediately after the end of the transesterification reaction in example 10. The results are given in tables 1 and 2.

Example 20

The web obtained in the procedure of example 10 was melted at 250 ℃ using an extrusion spinning apparatus equipped with 36 circular spinneret holes having a hole diameter of 0.27mm at a spinning productivity of 36g/min and a spinning speed of 3600 m/min, and the resultant undrawn yarn was fed to a drawing treatment apparatus equipped with a 60 ℃ heating roll and a 160 ℃ plate heater and subjected to a drawing treatment at a drawing ratio of 1.7 to obtain 83 dtex/36 monofilament drawn yarn. The results are given in tables 1 and 2.

Example 21

The web obtained in the procedure of example 10 was melted at 250 ℃ using an extrusion spinning apparatus equipped with 36 circular spinneret holes having a hole diameter of 0.27mm at a spinning productivity of 34g/min and a spinning speed of 2400m/min, and the resultant undrawn yarn was fed to a drawing treatment apparatus equipped with a 60 ℃ heating roll and a 160 ℃ plate heater without winding at all and subjected to a drawing treatment at a drawing ratio of 1.7 to obtain 83 dtex/36 monofilament drawn yarn. The results are given in tables 1 and 2.

Comparative example 1

The steps were carried out in the same manner as in example 1 except that in example 1, 0.0525 parts by weight of titanium tetrabutoxide was used for the transesterification reaction without using manganese acetate tetrahydrate, and then the polymerization reaction was carried out without any further addition. The results are given in table 1.

Comparative example 2

The steps were carried out in the same manner as in example 1 except that the amount of manganese acetate tetrahydrate added in example 1 was changed to 0.0885 parts by weight. The results are given in tables 1 and 2.

Comparative example 3

The steps were carried out in the same manner as in example 6 except that the addition amount of trimethyl phosphate was changed to 0.027 parts by weight in example 6. The results are given in tables 1 and 2.

Comparative example 4

The procedures were carried out in the same manner as in example 10 except that the amount of potassium acetate added was changed to 0.0405 part by weight in example 10. The results are given in tables 1 and 2.

Comparative example 5

The steps were carried out in the same manner as in example 10 except that the addition amount of trimethyl phosphate was changed to 0.027 parts by weight in example 10. The results are given in tables 1 and 2.

(Table 1)

Example 14	RbOAc	25	TBT	30	-	111	-	-	0.0	0.75	0.24	2.1	7.2
														Example 15	Ca(OAc)2·H2O	25	TBT	30	-	-	52	-	0.0	0.75	0.23	2.2	6.0
Example 16	Mg(OAc)2·4H2O	25	TBT	30	-	-	32	-	0.0	0.75	0.21	2.0	5.6
														Example 17	KOAc	25	TMT	30	-	51	-	-	0.0	0.75	0.22	2.1	6.7
Example 18	KOAc	25	TPO	30	-	51	-	-	0.0	0.75	0.20	2.1	6.8
														Example 19	KOAc	25	TBT	30	12.5	51	-	-	0.5	0.75	0.21	1.9	5.5
Example 20	KOAc	25	TBT	30	-	51	-	-	0.0	0.75	0.21	2.1	6.6
														Example 21	KOAc	25	TBT	30	-	51	-	-	0.0	0.75	0.21	2.1	6.6
(12)	TBT	30	-	-	-	-	-	-		0.75	0.21	2.0	5.1
														(13)	Mn(OAc)2·4H2O	70	TBT	30	-	-	-	185	0.0	0.75	0.25	2.1	10.5
(14)	Mn(OAc)2·4H2O	25	TBT	30	37.5	-	-	66	1.5	0.75	0.22	2.0	5.5
														(15)	KOAc	70	TBT	30	-	142	-	-	0.0	0.75	0.25	2.1	10.5
(16)	KOAc	25	TBT	30	37.5	51	-		1.5	0.75	0.22	2.0	5.5

Note that: the abbreviations in the table have the following respective meanings.

Mn(OAc)₂·4H₂O: manganese acetate tetrahydrate

KOAc (Koac): potassium acetate

LiOAc: lithium acetate

Ca(OAc)₂·H₂O: calcium acetate monohydrate

Co(OAc)₂·4H₂O: acetic acid cobalt tetrahydrate

NaOAc·3H₂O: sodium acetate trihydrate

RbOAc: rubidium acetate

Mg(OAc)₂·4H₂O: tetrahydrate magnesium acetate

DPG: dipropylene glycol

TBT: titanium tetrabutoxide

TMT: reaction product of titanium tetrabutoxide-trimellitic anhydride at 1/2 molar ratio

TPO: reaction product of titanium tetrabutoxide-phenylphosphonic acid in 1/2 molar ratio

TPI: reaction product of titanium tetrabutoxide-phenylphosphinic acid in 1/2 molar ratio

(1) Denotes a "transesterification catalyst"

(2) Denotes a "polymerization catalyst".

(3) Represents "trimethyl phosphate".

(4) Represents the "alkali metal element content".

(5) Represents the "alkaline earth metal element content".

(6) Represents "manganese element content".

(7) Means "intrinsic viscosity".

(8) Indicating the "DPG content".

(9) Denotes the "cyclic dimer content".

(10) Indicating "post-crystallization color".

(11) Means "in terms of titanium atom".

(12) This represents "comparative example 1".

(13) This represents "comparative example 2".

(14) This represents "comparative example 3".

(15) This represents "comparative example 4".

(16) This represents "comparative example 5".

(Table 2)

Example 18	2400	1.7	0.72	83	3.0	39	2.5	2.8	0.3
										Example 19	2400	1.7	0.71	83	3.1	40	2.3	2.6	0.3
Example 20	3600	1.2	0.71	83	3.1	42	2.7	2.8	0.1
										Example 21	2400	1.7	0.71	83	3.0	43	2.7	2.9	0.2
(10)	2400	1.7	0.73	83	3.3	42	2.2	4.7	2.5
										(11)	2400	1.7	0.71	83	2.9	39	5.6	5.8	0.2
(12)	2400	1.7	0.72	83	3.1	41	2.5	4.7	2.2
										(13)	2400	1.7	0.71	83	2.9	39	5.6	5.8	0.2
(14)	2400	1.7	0.72	83	3.1	41	2.5	4.7	2.2

Note that:

(1) the expression "spinning speed". (12) represents "comparative example 3".

(2) Denotes the "draw ratio". (13) represents "comparative example 4".

(3) Means "intrinsic viscosity". (14) denotes "comparative example 5".

(4) The term "fineness".

(5) The term "tensile strength" is used.

(6) Indicating the "stretch length".

(7) Denotes "before light irradiation".

(8) Means "after light irradiation".

(9) The expression "increment before and after irradiation".

(10) This represents "comparative example 1".

(11) This represents "comparative example 2".

Industrial applicability

The poly (trimethylene terephthalate) -based polyester provided by the present invention can improve the light resistance of poly (trimethylene terephthalate) -based polyester and is suitable for manufacturing molded products satisfying various needs since molding conditions such as yarn-making conditions are not strictly limited. The invention has significant industrial application value.

Claims (18)

1. A poly (trimethylene terephthalate) -based polyester comprising 85 mol% or more of trimethylene terephthalate repeating units, comprising at least one compound selected from the group consisting of alkali metal compounds, alkaline earth metal compounds and manganese compounds in an amount of 10 to 150ppm in terms of metal elements, the molar ratio of the total element content of the contained alkali metal elements, alkaline earth metal elements and manganese elements to the contained phosphorus element content satisfying the following relational formula (I):

O≤P/M≤1 (I)

wherein P is the molar weight of phosphorus element in the polyester; m is the total molar amount of the alkali metal element, the alkaline earth metal element and the manganese element.

2. The polyester according to claim 1, wherein the following conditions (a) to (d) are satisfied simultaneously:

(a) an intrinsic viscosity of 0.5 to 1.6,

(b) the dipropylene glycol is present in an amount of 0.1 to 2.0 wt%, based on the total weight of the polyester,

(c) the cyclic dimer is contained in an amount of 0.01 to 5 wt% based on the total weight of the polyester, and

(d) the b color value after crystallization is-5-10.

3. The polyester of claim 1, wherein the alkali metal compound is a compound selected from the group consisting of lithium compounds, sodium compounds, potassium compounds, rubidium compounds.

4. The polyester of claim 1, wherein the alkaline earth metal compound is a magnesium compound and/or a calcium compound.

5. The polyester of claim 1, wherein the manganese compound is a compound selected from the group consisting of manganese acetate, manganese benzoate and manganese chloride.

6. A process for producing a poly (trimethylene terephthalate) -based polyester, which comprises producing the polyester of claim 1 using a titanium compound as a polymerization catalyst.

7. The process according to claim 6, wherein the titanium compound is titanium tetraalkoxide.

8. The production process according to claim 6, wherein the titanium compound is a reaction product of at least one compound selected from phthalic acid, trimellitic acid, hemimellitic acid, and pyromellitic acid or an acid anhydride thereof with titanium tetraalkoxide.

9. The production process according to claim 6, wherein the titanium compound is a reaction product of titanium tetraalkoxide and phosphonic acid compound.

10. The production process according to claim 6, wherein the titanium compound is a reaction product of titanium tetraalkoxide and phosphinic acid compound.

11. The production process according to claim 6, wherein the titanium compound is a reaction product of titanium tetraalkoxide and a phosphate compound.

12. The production process according to claim 6, wherein the titanium compound is a reaction product of at least one compound selected from phthalic acid, trimellitic acid, hemimellitic acid, and pyromellitic acid or an acid anhydride thereof with a titanium tetraalkoxide and a phosphonic acid compound.

13. The production process according to claim 6, wherein the titanium compound is a reaction product of at least one compound selected from phthalic acid, trimellitic acid, hemimellitic acid, and pyromellitic acid or an acid anhydride thereof with a titanium tetraalkoxide and a phosphinic acid compound.

14. The production process according to claim 6, wherein the titanium compound is a reaction product of at least one compound selected from phthalic acid, trimellitic acid, hemimellitic acid, and pyromellitic acid or an acid anhydride thereof with a titanium tetraalkoxide and a phosphoric acid ester compound.

15. A poly (trimethylene terephthalate) -based polyester fiber obtained by melt-spinning the poly (trimethylene terephthalate) -based polyester of claim 1 at a melt temperature of 238 to 275 ℃ and a spinning speed of 400 to 5000 m/min.

16. A poly (trimethylene terephthalate) -based drawn polyester yarn obtained by winding the fiber of claim 15 once or without winding and then continuously drawing the fiber.

17. A fabric comprised of a polyester comprising the poly (trimethylene terephthalate) -based polyester fiber of claim 15, having a b-color value with an increase of 2 or less after 80 hours of irradiation with a solar weatherometer at 60 ℃.

18. A fabric comprised of polyester comprising poly (trimethylene terephthalate) -based drawn polyester yarn of claim 16, having a b-color value that increases by 2 or less after 80 hours of irradiation at 60 ℃ with a solar weatherometer.