JP2009091445A - Polyether ester and fiber thereof, finished yarn and woven or knitted goods - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyether ester effectively exploitable as a raw material for fibers or a raw material for resin molding excellent in oxidation stability, dry heat properties and wet heat properties (hereinafter, dry heat properties and wet heat properties may be comprehensively described as heat resistance), and whiteness. <P>SOLUTION: In the polyether ester, a main dicarboxylic acid component is terephthalic acid and a main diol component comprises 1,3-propylene glycol and a polyalkylene ether glycol having a copolymerization ratio of 35-80 wt.% and a number average molecular weight of 500-20,000, and the polyether ester satisfies the following conditions (1)-(4): (1) 1.0 dl/g≤reduced viscosity (ηsp/c)≤4.0 dl/g, (2) amount of terminal carboxyl groups ≤20 milliequiv. per 1 kg of the resin, (3) copolymerization ratio of bis(3-hydroxypropyl) ether≤1.8 wt.%, and (4) L* value≥70, -5≤b* value≤15 and -5≤a* value≤3. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a polyether ester useful as a fiber raw material and a resin molding raw material having excellent oxidation resistance and thermal stability and excellent whiteness.

  Thermoplastic polyetherester elastomer (hereinafter, abbreviated as PBT) for the hard segment and poly (tetramethylene oxide) glycol (hereinafter abbreviated as PTMG) for the soft segment (hereinafter, abbreviated as PBT) , May be abbreviated as PBT-based elastomer), because it has superior heat resistance compared to conventional olefin-based elastomers and thermoplastic polyurethane-based elastomers, such as CVJ boots and high-pressure hose coating materials. It is widely used as a molded product and is also used as an elastic fiber. However, PBT elastomers have insufficient elastic recovery characteristics, and further have excellent properties as elastic fibers, such as the stress value at the time of contraction is very low (the tightening force at the time of contraction is small) relative to the stress value at the time of expansion. It is impossible to achieve the same elastic properties as urethane yarns. Further, the PBT elastomer has a problem that the melting point is remarkably lowered when the soft segment content is increased in order to increase rubber elasticity.

On the other hand, a thermoplastic polyether ester using polytrimethylene terephthalate (hereinafter abbreviated as PTT) with excellent stretch properties for the hard segment and polytetramethylene glycol or poly (1,3-propylene oxide) glycol for the soft segment. Elastomers (hereinafter abbreviated as PTT-based elastomers) are also conventionally known (Document 1, Patent Document 1 and Patent Document 2). However, in these PTT elastomers, the polymer is reddish drastically in the pre-crystallization step and the drying step before melt spinning, and the fibers obtained from such PTT elastomers do not develop a beautiful color and are used for clothing. Can not be used as. Furthermore, even if the fibers obtained from the conventional PTT elastomers are not colored in the drying process, the tensile strength and elastic properties are significantly reduced in the heat setting process and the dyeing process before dyeing. The high elastic recovery characteristics required in the field and the appropriate tightening force during contraction cannot be exhibited. Further, such an elastomer having poor dry heat characteristics and wet heat characteristics is difficult to be used as a resin molded product.
The present inventors have found that these problems in the PTT elastomer are bis (3-hydroxypropyl) ether (HOCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ ), which is a by-product of PTT constituting a terminal carboxyl group and a hard segment. The inventors have found that this is caused by CH ₂ OH (hereinafter sometimes abbreviated as BPE), and reached the present invention.

Journal of the Korean Fiber Society vol. 37, no. 11,2000 JP-A-2-248425 Special table 2005-507972

  The object of the present invention is to solve the problems of the above-mentioned conventional PTT elastomers, oxidation resistance stability, dry heat characteristics and wet heat characteristics (hereinafter, dry heat characteristics and wet heat characteristics may be collectively described as heat resistance). Another object of the present invention is to provide a polyether ester that can be effectively used as a raw material for fibers or a raw material for resin molding, which has excellent whiteness. Another object of the present invention is to provide a polyetherester fiber that is excellent in elastic properties, can be vividly dyed, and hardly undergoes a decrease in tensile strength and a decrease in elastic recovery properties after dyeing.

That is, the present invention is as follows.
1. It is a polyether ester composed of terephthalic acid as the main dicarboxylic acid component, 1,3-propylene glycol as the main diol component and a polyalkylene ether glycol having a number average molecular weight of 500 to 20000 having a copolymerization ratio of 35 to 80% by weight. A polyether ester satisfying the following (1) to (4):
(1) 1.0 dl / g ≦ reduced viscosity (ηsp / c) ≦ 4.0 dl / g
(2) Terminal carboxyl group amount ≦ 20 meq / kg resin (3) Copolymerization ratio of bis (3-hydroxypropyl) ether ≦ 1.8% by weight
(4) L * value ≧ 70, −5 ≦ b * value ≦ 15, −5 ≦ a * value ≦ 3
2. The polyalkylene ether glycol is at least one selected from the group consisting of poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, and poly (tetramethylene oxide) glycol. 2. The polyether ester as described in 1 above, wherein
3. 3. The polyether ester as described in 1 or 2 above, wherein 3 to 30% of the repeating units of the polyalkylene ether glycol have the following structure.

4). Titanium oxide having an average particle diameter of 0.01 to 2 μm is contained in an amount of 0.01 to 3% by weight, and the aggregate having the longest portion in which the titanium oxide particles are collected has a length exceeding 10 μm / mg resin or less. The polyether ester composition according to any one of 1 to 3 above, which is
5). The polyetherester fiber comprised from the polyetherester in any one of said 1-4, or its composition.
6). 5. A polyetherester fiber comprising the polyetherester according to any one of 1 to 4 or a composition thereof and further satisfying the following (a) and (b).
(A) Tensile strength ≧ 0.3 cN / dtex and elongation ≧ 200%
(B) Either after heat treatment at 140 ° C. for 4 hours or after treatment with hot water at 95 ° C. for 4 hours, the elastic recovery rate after repeating 200% elongation three times is 70% or more, and the first time The stress retention at 100% elongation during the third contraction is 20% or more with respect to the stress at 100% elongation during elongation.

7). It is a polyether ester composed of terephthalic acid as the main dicarboxylic acid component, 1,3-propylene glycol as the main diol component and a polyalkylene ether glycol having a number average molecular weight of 500 to 20000 having a copolymerization ratio of 35 to 80% by weight. And a fiber composed of a polyether ester characterized by satisfying the following (1) to (3).
(1) 1.0 dl / g ≦ reduced viscosity (ηsp / c) ≦ 4.0 dl / g
(2) Terminal carboxyl group amount ≦ 20 meq / kg resin (3) Copolymerization ratio of bis (3-hydroxypropyl) ether ≦ 1.8% by weight
8). The fiber composed of the polyether ester according to the above 7, wherein the fiber composed of the polyether ester further satisfies the following (4) to (5).
(4) Tensile strength ≧ 0.3 cN / dtex and elongation ≧ 200%
(5) The elastic recovery is 70% or more after repeating 200% elongation three times after heat treatment at 140 ° C. for 4 hours or after treatment with hot water at 95 ° C. for 4 hours; The stress retention at 100% elongation during the third contraction is 20% or more with respect to the stress at 100% elongation during elongation.

9. 5 to 9.0% by weight of the finishing agent is adhered to the fiber surface, and 30 to 100% by weight of the following compound (I) is contained as a constituent of the finishing agent. The polyetherester fiber in any one.
(I) An organosilicon compound having a silicon atom content of 20 to 50% by weight and a viscosity at 25 ° C. of 2 to 50 centistokes. Aggregates containing 0.01 to 3% by weight of titanium oxide having an average particle diameter of 0.01 to 2 μm and the longest part length of the titanium oxide particles gathered is more than 7 μg / mg fiber The polyetherester fiber according to any one of 5 to 9 above, which is

11. The polyether ester fiber according to any one of 5 to 10 above, wherein the single yarn fineness is 1 to 100 dtex and the total fineness is 5 to 10,000 dtex.
12 A polyetherester composite yarn, wherein a fiber other than the polyetherester fiber is wound around the polyetherester fiber according to any one of 5 to 11 above.
13. A woven or knitted fabric containing the polyetherester fiber according to any one of 5 to 12 above.

  A polyether ester useful as a raw material for fibers and a raw material for resin molding having excellent oxidation resistance and thermal stability and excellent whiteness can be obtained.

The polyether ester of the present invention is composed of terephthalic acid as the main dicarboxylic acid component, 1,3-propylene glycol as the main diol component and a polyalkylene glycol having a number average molecular weight of 500 to 20000 having a copolymerization ratio of 35 to 80% by weight. The polyether ester is characterized in that the following (1) to (4) are satisfied.
(1) 1.0 dl / g ≦ reduced viscosity (ηsp / c) ≦ 4.0 dl / g
(2) Terminal carboxyl group content ≦ 20 meq / kg resin (3) Bis (3-hydroxypropyl) ether copolymerization ratio ≦ 1.8 wt%
(4) L * value ≧ 70, −5 ≦ b * value ≦ 15, −5 ≦ a * value ≦ 3

The polyether ester of the present invention is composed of terephthalic acid as the main dicarboxylic acid component, 1,3-propylene glycol as the main diol component, and a polyalkylene glycol having a number average molecular weight of 500 to 20000 having a copolymerization ratio of 35 to 80% by weight. Is done. By having such a polymer main skeleton, it is possible to exhibit an excellent elastic recovery characteristic as compared with an elastic fiber made of a conventional PBT elastomer.
The number average molecular weight of the polyalkylene ether glycol of the polyether ester of the present invention needs to be 500 to 20000 from the viewpoints of elastic properties and heat resistance. When the number average molecular weight of the polyalkylene ether glycol is less than 500, the melting point is low and excellent heat resistance cannot be exhibited, and the elastic properties are also inferior. On the other hand, if the number average molecular weight of the polyalkylene ether glycol exceeds 20000, it is difficult to form a better phase separation structure between the crystalline phase and the amorphous phase. Preferably it is 1000-4500, Most preferably, it is the range of 1500-4000.

  Furthermore, when the copolymerization ratio of the polyalkylene ether glycol is controlled within the range of 35 to 80% by weight of the polyether ester, excellent elastic properties and heat resistance can be exhibited. If the copolymerization ratio of the polyalkylene ether glycol is less than 35% by weight, excellent elastic properties cannot be exhibited, and if it exceeds 80% by weight, the melting point is drastically lowered and the plastic deformation at the time of elongation is large, resulting in elasticity. Characteristics are degraded. Preferably it is 45 to 75% by weight.

  The polyalkylene ether glycol is at least one selected from the group consisting of poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, and poly (tetramethylene oxide) glycol. Is preferred, and poly (1,3-propylene oxide) glycol and poly (tetramethylene oxide) glycol are more preferred from the viewpoint of improving elastic properties. Furthermore, in polyalkylene ether glycol, 3 to 30% of the polyether oxide repeating units can be neopentylene oxide structural units having the following structure (1).

The use of a polyalkylene ether glycol copolymerized with neopentylene oxide in the present invention improves the low-temperature characteristics of the polyether ester, and surprisingly, the polyalkylene ether glycol having the same molecular weight and the same content can be used as a polyalkylene ether glycol. When comparing the polyether ester copolymerized with (tetramethylene oxide) glycol and the polyether ester copolymerized with poly (tetramethylene oxide) glycol with 3-30% neopentylene oxide structural units, the latter The melting point of becomes higher than 20 ° C.
In addition, the polyether ester copolymerized with poly (tetramethylene oxide) glycol copolymerized with 3-30% neopentylene oxide structural unit, the tendency of the crystal component to crystallize efficiently and strongly is recognized remarkably, Furthermore, the feature that the temperature difference from the start to the end of the crystal becomes small is recognized.
Because of these characteristics, it becomes easy to control the crystallization temperature in the spinning production process, film or resin molding process using polyether ester as a raw material, and the obtained elastic fiber, film or resin can be obtained from unraveling and molds. It is extremely easy to take out and does not impair the physical properties of fibers and films.
From the viewpoint of enhancing the melting point and moldability of the thermoplastic polyetherester elastomer, the copolymerization ratio of the polyalkylene ether glycol of the neopentylene oxide structural unit is more preferably 5 to 20%, most preferably 8 to 15%. .

The polyether ester of the present invention is less than 10% by weight of the polymer weight, and terephthalic acid, 1,3-propylene glycol and Components of the fourth component or more other than the specified polyalkylene ether may be copolymerized. The fourth and higher components include isophthalic acid, naphthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, aromatic sodium carboxylic acid such as 5-sodium sulfoisophthalic acid, sebacic acid, 1,3 -Or 1,4-cyclohexanedicarboxylic acid, adipic acid, dodecanedioic acid, glutaric acid, succinic acid, oxalic acid, azelaic acid, dimethylmalonic acid, fumaric acid, citraconic acid, allylmalonic acid, 4-cyclohexene-1,2- Dicarboxylic acid, pimelic acid, suberic acid, 2,5-diethyladipic acid, 2-ethylsuberic acid, 2,2,3,3-tetramethylsuccinic acid, cyclopentanedicarboxylic acid, decahydro-1,5- (or 2,6-) Naphthalenedicarboxylic acid, 4,4'-bicyclohexyldicarboxylic acid, 4,4'-methylenebis Cyclohexyl carboxylic acid), 3,4-furandicarboxylate, and 1,1-cyclobutanedicarboxylate, aliphatic or cycloaliphatic dicarboxylic acids, 1,2-butanediol, 1,3-butanediol, 1,4 -Butanediol, neopentyl glycol, 1,5-pentamethylene glycol, 1,6-pentamethylene glycol, heptamethylene glycol, octamethylene glycol, decamethylene glycol, dodecamethylene glycol, 1,4-cyclohexanediol, 1,3 Short chain glycol components such as -cyclohexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol may be copolymerized. Further, a known polyvalent carboxylic acid, trivalent diol, polyvalent amide, polyvalent ester or the like having a valence of 3 or more may be crosslinked at 0.01 to 5% by weight based on the weight of the polyether ester.

  The polyether ester of the present invention needs to have a reduced viscosity (ηsp / c) of 1.0 to 4.0 dl / g. The reduced viscosity is an index of the degree of polymerization, and the mechanical properties (tensile strength and tear tensile strength) or elastic recovery properties of the thermoplastic polyether ester elastomer are greatly affected by the degree of polymerization. When the reduced viscosity is less than 1.0 dl / g, the mechanical properties and the elastic recovery properties are low, and it cannot be used as clothing fibers or resin molded products. On the other hand, it is practically difficult to exceed the reduced viscosity of 4.0 with the thermoplastic polyetherester elastomer having the composition of the present invention. Preferably it is 1.2-3.5 dl / g, More preferably, it is 1.3-3.0 dl / g.

  The amount of terminal carboxyl groups of the polyether ester of the present invention is required to be 20 meq / kg resin or less. When the amount of terminal carboxyl groups exceeds 20 meq / kg resin, intense coloring occurs during heating and the molecular weight decreases during melt spinning. Suppression of polymer coloring (redness) during precrystallization and drying, suppression of molecular weight reduction during melt spinning, and suppression of reduction in tensile strength and elastic recovery properties in the heat setting process and dyeing process before dyeing of the obtained fiber Therefore, the amount of terminal carboxyl groups of the thermoplastic polyether ester elastomer of the present invention is preferably 20 meq / kg resin or less, more preferably 15 meq / kg resin or less.

The polyether ester of the present invention needs to have a copolymerization ratio of bis (3-hydroxypropyl) ether (hereinafter sometimes abbreviated as BPE) of 1.8% by weight or less. BPE is produced by dimerization of 1,3-propylene glycol (see the following formula), and is copolymerized with the polymer as it is.
2HOCH ₂ CH ₂ CH ₂ OH → HOCH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OH

  Although it is already known that BPE copolymerized with a polymer reduces the heat resistance and light resistance of the polymer, the present inventors have shown that BPE in a polyether ester is a polymer coloring (red) or dyeing process. It became clear that there was a very strong causal relationship with the deterioration of physical properties, and the inventors further studied and found that the upper limit was 1.8% by weight or less. From the viewpoint of oxidation resistance stability, water resistance, heat resistance and whiteness of the polymer, the amount of BPE contained in the thermoplastic polyetherester elastomer of the present invention is preferably 1.3% by weight or less, more preferably 1 0.0% by weight or less.

The polyether ester of the present invention has an L * value of 70 or more as a lightness index, a b * value of −5 to 15 as a yellowness index, and an a * value of −5 to 3 as a redness index. It is necessary to be. The L * value is 80 or more, the b * value is 0 to 12, and the a * value is −2 to 2 from the viewpoint of realizing clear color developability when dyeing the elastic fiber made from the polyether ester of the present invention. It is more preferable that

  The polyether ester of the present invention has a cyclic dimer content of trimethylene terephthalate of 2.0% by weight with respect to the polyether ester from the viewpoint of improving moldability and exhibiting excellent elastic recovery properties of the obtained fiber. The following is preferable. If the cyclic dimer exceeds 2.0% by weight, the fibers become sticky in the spinning process, making it difficult to continue spinning and stretching stably. Although the mechanism is not clear, the cyclic dimer is a substance that is very easy to crystallize, and the cyclic dimer serves as a nucleus in the molding process, and promotes faster and faster crystallization. It is speculated that this is because the difference becomes large and the fiber structure is difficult to be fixed, and further, it becomes difficult to form a better phase separation structure of the crystalline phase and the amorphous phase. The smaller the amount of cyclic dimer, the better. However, it is more preferably 1.5% by weight or less, and most preferably 1.0% by weight or less.

  The polyether ester of the present invention has an average particle size of 0.01 to 2 μm from the viewpoint of reducing the friction coefficient when used as a matting agent when used as a fiber raw material, and as a fiber raw material and a resin molded body raw material. It is preferable that the number of aggregates containing 0.01 to 3 wt% of a certain titanium oxide and further having a longest part length of more than 5 μm in which the titanium oxide particles are collected is 10 / mg resin or less.

  Polyether ester fibers having rubber-like elastic properties have a very high friction coefficient, and have a problem that fluff and yarn breakage frequently occur in the spinning process (including spinning and drawing processes). By containing 0.01 to 3% by weight of titanium oxide having an average particle size of 0.01 to 2 μm in the elastomer used as a raw material for fibers, the friction coefficient is reduced and the occurrence of fuzz and the like in the yarn making process is suppressed. At the same time, it also has the effect of suppressing the glare of the fibers. In addition, by controlling the aggregate having a longest part length of more than 5 μm where the titanium oxide particles contained in the elastomer are 10 μg / mg resin or less, the increase in the spinneret pack pressure and the nozzle dirt due to filter clogging are eliminated, A fiber or a molded object can be manufactured stably for a long period of time. More preferably, it is 7 pieces / mg resin or less, and most preferably 5 pieces / mg resin or less.

The polyether ester of the present invention preferably contains a hindered phenol-based oxidation stabilizer in a range of 5% by weight or less with respect to the polyether ester from the viewpoint of suppressing thermal decomposition in the melt polymerization step and the melt molding step. The types of hindered phenol oxidation stabilizers used in the present invention include pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,3 ′, 3. ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(mesitylene-2,4,6-triyl) tri-p-cresol, 1,1,3-tris (2 -Methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3 , 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspir [5,5] undecane, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzene) isophthalic acid, triethylglycol-bis [3- (3-tert-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], diethyl [[3, 5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphate.
Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,3 ′, 3 ″, 5, from the viewpoint of reducing the terminal carboxyl group content and BPE content 5 ', 5 "-hexa-tert-butyl-a, a', a"-(mesitylene-2,4,6-triyl) tri-p-cresol, diethyl [[3,5-bis (1,1- Most preferred is dimethylethyl) -4-hydroxyphenyl] methyl] phosphate.

  Moreover, it is preferable that the polyether ester of this invention contains the phosphorus compound corresponded to 5-250 ppm of phosphorus elements with respect to polyether ester from a viewpoint of suppressing the thermal decomposition at the time of melt molding. Examples of the phosphorus compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, phosphoric acid, phosphorous acid, diethyl [[3,5-bis (1 , 1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphate.

Furthermore, the polyether ester of the present invention can be added to various additives other than those described so far, for example, heat stabilizers other than phosphorus compounds, hindered phenols, as long as the elastic properties and moldability are not impaired. Copolymerizing antioxidants other than compounds, antifoaming agents, color adjusters, flame retardants, ultraviolet absorbers, infrared absorbers, crystal nucleating agents, fluorescent brighteners, matting agents other than titanium oxide, pigments, etc. You may mix.
Still further, the polyether ester of the present invention includes bisphenol A-glycidyl ether, bisphenol-glycidyl ether, bisphenol S-glycidyl ether, isocyanuric acid-triglycidyl ether, pentaerythritol, 4,4-diphenylmethane diisocyanate, N, N′-. Containing at least one chain extender selected from terephthaloylbiscaprolactam and 3,3 ′, 4,4′-diphenyltetracarboxylic anhydride within a range of less than 10% by weight based on the polyether ester. Also good.

The method for producing the polyether ester of the present invention will be described below.
A dicarboxylic acid mainly composed of terephthalic acid and / or its lower alcohol ester derivative, polyalkylene ether glycol and 1,3-propylene glycol (hereinafter abbreviated as PDO) at a temperature of 180 to 240 ° C. in the presence of a transesterification catalyst. The esterification reaction or / and the transesterification reaction is carried out for 2 to 10 hours. From the viewpoint that the transesterification reaction proceeds smoothly and the BPE production is suppressed when the charge ratio of PDO to the dicarboxylic acid or / and its lower alcohol ester derivative is in the range of 0.8 to 3 in terms of molar ratio. preferable. More preferably, it is 1.4 to 2.5, and most preferably 1.5 to 2.3.

  Examples of esterification reaction catalysts and / or transesterification catalysts include titanium alkoxides represented by titanium tetrabutoxide and titanium tetraisopropoxide, titanium oxide having a particle diameter of 1 to 100 nm, calcium acetate, magnesium acetate, manganese acetate, acetic acid Sodium, calcium formate, magnesium formate, manganese formate and the like can be mentioned, and it is preferable to add 0.02 to 2% by weight to the dicarboxylic acid used. If the amount of the transesterification catalyst is less than 0.02% by weight, the transesterification reaction takes a long time, leading to an increase in the amount of terminal carboxyl groups and the content of BPE. On the other hand, when the transesterification catalyst amount exceeds 2% by weight, the thermal decomposition reaction is accelerated and the terminal carboxyl group amount increases. More preferably, it is 0.05-1.5 weight%, Most preferably, it is 0.1-1 weight%.

Thereafter, titanium alkoxide represented by titanium tetrabutoxide or titanium tetraisopropoxide, titanium oxide having a particle size of 1 to 100 nm is used, and at least 1 torr or less, preferably 0.5 torr or less in the presence of a polycondensation reaction catalyst. The polycondensation reaction is performed within a temperature range of 200 to 260 ° C. under reduced pressure. When these titanium catalysts are used for the esterification reaction catalyst or / and the transesterification catalyst, they need not be added, and may be added to increase the reaction rate. In the polycondensation reaction, the polycondensation reaction catalyst amount is preferably 0.02 to 2% by weight, more preferably 0.05 to 1.5% by weight, and most preferably 0.1% by weight based on the dicarboxylic acid used. ˜1% by weight. The polycondensation reaction temperature and the reaction time are preferably adjusted from the viewpoint of obtaining a target elastomer by adjusting the amount of terminal carboxyl groups of the prepolymer so as to be 20 meq / kg resin or less. From the viewpoint of increasing the polycondensation reaction rate and suppressing the thermal decomposition reaction, it is preferable to adjust the polycondensation reaction time within the range of 220 to 245 ° C.

Hereinafter, the polycondensation reaction step will be described in more detail.
First, from the viewpoint of controlling the amount of terminal carboxyl groups and BPE content of the polyether ester within the scope of the present invention, it is the timing of completion of the esterification reaction or transesterification reaction. It is preferable to complete the transesterification reaction and start the polycondensation reaction when the reaction rate ranges from 65% to 95%. Usually, the esterification reaction or transesterification reaction ends when the generated water or methanol distills in a theoretical amount with respect to the amount of the dicarboxylic acid or its lower alcohol ester derivative charged (that is, the reaction rate is 100%). To polycondensation reaction. However, the present inventors have found that in the polyether ester of the present invention, the reaction rate greatly affects the terminal carboxyl group content and BPE content of the final elastomer, and the upper limit is 95% transesterification reaction rate. It revealed that. On the other hand, when the transesterification rate is less than 65%, the degree of polymerization is not increased in the polycondensation reaction, and the reduced viscosity of the final elastomer is less than 1.0 dl / g. More preferably, the transesterification reaction is completed at a transesterification rate of 70% to 90%, most preferably 75% to 88%.

  Next, what is important from the viewpoint of controlling the copolymerization ratio of BPE within the scope of the present invention is the time required to reach a high degree of vacuum (at least 1 torr or less) for carrying out the polycondensation reaction from normal pressure. , Preferably within 45 minutes. If it exceeds 45 minutes, the copolymerization ratio of BPE increases and exceeds the scope of the present invention. This time is preferably as short as possible, but bumping occurs when the pressure reduction rate is too high. Therefore, it is preferably 20 to 45 minutes.

  Moreover, in order to control the amount of terminal carboxyl groups within the scope of the present invention, it is important to suppress the thermal decomposition reaction in the polycondensation reaction step, and the PDO is efficiently distilled off during the polycondensation reaction. It is necessary to shorten the polycondensation reaction time. For that purpose, it is important to increase the specific surface area of the polymer. For example, using a helical stirrer, a disc ring reactor, etc., the polymer is stirred up and efficiently stirred so as to form a thin film. The ratio of the raw material charge to the volume of the kettle is preferably 40 vol% or less, more preferably 35 vol%. Furthermore, it is preferable to stop the polycondensation reaction while the viscosity of the polymer in the polycondensation reaction step increases with time.

  When adding a hindered phenolic antioxidant or a phosphorus compound, it may be added at any stage of the polymerization, and may be added at once or in several batches. From the viewpoint of suppressing the thermal decomposition of the polyalkylene ether glycol, it is preferable to add it before the start of the transesterification reaction or esterification reaction, and the phosphorus compound may be added after the end of the transesterification reaction or esterification reaction. This is preferable because coloring can be suppressed without inhibiting the reaction or esterification reaction.

When adding titanium oxide, after adding titanium oxide to the solvent and stirring, the titanium oxide dispersion solution from which the aggregate of titanium oxide has been removed using a centrifuge, filter, etc., is polymerized at any stage of the polymerization. To complete the polycondensation reaction. The titanium oxide used in the present invention is preferably an anatase type because it has low hardness and good dispersibility in a solvent. Moreover, it is preferable that the average particle diameter of a titanium oxide is 0.01-2 micrometers, More preferably, it is 0.05-1 micrometer.
Here, the average particle diameter is an average value of the diameters of all the particles, and is distinguished from a so-called median diameter indicating a particle diameter with a frequency of 50% or a mode diameter indicating the largest distribution value. Those having an average particle size of less than 0.01 μm are difficult to obtain practically and easily form aggregates. On the other hand, when the average particle size exceeds 2 μm, it is difficult to reduce the number of aggregates having the longest portion having a length exceeding 5 μm. The particle size distribution of the titanium oxide used is preferably such that the particle size component of 1 μm or more is 20% by weight or less, more preferably 10% by weight.

The titanium oxide used in the present invention is used by dispersing in a solvent, but it is dispersed in PDO from the viewpoint of reducing the number of aggregates having the longest part exceeding 5 μm, and after centrifugation, the longest part is used by using a filter. It is preferable to perform an operation of removing aggregates having a length exceeding 5 μm.
Although there is no limitation in particular as the slurry density | concentration of a titanium oxide, the range of 10 to 40 weight% is preferable. When the slurry concentration of titanium oxide is less than 10% by weight, the amount of 1,3-propylene glycol is large, and it takes a long time to reduce the pressure from normal pressure to normal pressure. Invite. When the slurry concentration of titanium oxide exceeds 40% by weight, when the dispersion is added to a polymer exceeding 200 ° C., reaggregation of titanium oxide is likely to occur due to heat shock, and the length of the longest part contained in the final elastomer is increased. The number of titanium oxide aggregates exceeding 5 μm exceeds 10 / mg resin. More preferably, it is 15 to 30% by weight. The titanium oxide dispersion is preferably added after adding a polycondensation reaction catalyst, a phosphorus compound, and a hindered phenol-based antioxidant, after sufficiently stirring for at least 1 minute. Further, the temperature at the time of addition is preferably 200 to 240 ° C. from the viewpoint of preventing reaggregation of titanium oxide due to heat shock.

  From the viewpoint of increasing the reduced viscosity of the polymer or reducing the amount of terminal carboxyl groups, bisphenol A-glycidyl ether, bisphenol F-glycidyl ether, bisphenol S-glycidyl ether, isocyanuric acid-triglycidyl ether, pentaerythritol, 4 , 4-diphenylmethane diisocyanate, N, N′-terephthaloyl biscaprolactam, 3,3 ′, 4,4′-diphenyltetracarboxylic anhydride, etc. It can be added within the range, preferably within the range of 0.5 to 5% by weight. Although there is no restriction | limiting in particular about the time to add, It is preferable to add just before completion | finish of a polycondensation reaction.

  The polyether ester obtained by the above method is made into chips, powders, fibers, plates, blocks, and 160 to 220 in the presence of an inert gas such as argon, or under a reduced pressure of 100 torr, preferably 10 torr. Solid phase polymerization can be carried out at 3 ° C. for 3 to 48 hours. By performing solid phase polymerization, the reduced viscosity of the elastomer can be raised without increasing the amount of terminal carboxyl groups, and the content of the sublimable cyclic dimer can be reduced.

The polyether ester fiber of the present invention can be produced by melt spinning the polyether ester of the present invention.
The polyether ester fiber of the present invention preferably has a tensile strength of 0.3 cN / dtex or more and an elongation of 200% or more.
When the tensile strength is less than 0.3 cN / dtex, it is difficult to withstand practical use as a fiber for clothing, and when the elongation is less than 200%, the fabric is ruptured when stretched and is also difficult to withstand practical use as fiber for clothing. The higher the tensile strength, the better. However, it is difficult to exceed the tensile strength of 10 cN / dtex with the composition of the present invention. The tensile strength is preferably 0.5 to 10 cN / dtex, more preferably 0.8 to 5 cN / dtex. Further, since the required elongation differs depending on the intended use, it is not necessary to set an upper limit value for the elongation, but in reality it is 2000% or less.

  The polyether ester fiber of the present invention has an elastic recovery rate of 70% or more after repeating 200% elongation three times after either heat treatment at 140 ° C. for 4 hours or treatment with hot water at 95 ° C. for 4 hours. In addition, the stress retention rate at 100% elongation during the third contraction needs to be 20% or more with respect to the stress at 100% elongation during the first elongation. The elastic recovery rate after heat treatment or hydrothermal treatment under these conditions is 70% or more and the stress retention rate is 20% or more, thereby suppressing changes in elastic recovery characteristics in the heat setting process before dyeing or in the actual dyeing process. can do. The elastic recovery rate is preferably 75% or more, the stress retention rate is 25% or more, more preferably the elastic recovery rate is 80% or more, and the stress retention rate is 30% or more.

Since the polyetherester fiber of the present invention has rubber-like elastic properties, the surface friction resistance is remarkably high. In handling the fiber, it is preferable to apply a finishing agent to the fiber surface in order to reduce the surface frictional resistance. As a constituent of the finishing agent, a finishing agent containing 30 to 100% by weight of the following compound (I) is preferably used.
(I) An organosilicon compound having a silicon atom content of 20 to 50% by weight and a viscosity at 25 ° C. of 2 to 50 centistokes

  The adhesion amount of the finishing agent on the fiber needs to be 0.5 to 9.0% by weight with respect to the fiber weight. If it is less than 0.5% by weight, the effect of reducing the surface frictional resistance becomes small. On the other hand, if it exceeds 9.0% by weight, the resistance of the fiber during running becomes too large, or the finishing agent adheres to the roll, hot plate, guide, etc. and soils them. Preferably it is 2.0 to 8.0 weight%, More preferably, it is 3.0 to 8.0 weight%. Of course, a part of the finishing agent may penetrate into the fiber.

Hereinafter, preferable components of the finish will be described.
The organosilicon compound of compound (I) is a component that improves the smoothness of the surface of the polyetherester fiber and improves the wear properties by sliding. As such a component, an organosilicon compound having a viscosity at 25 ° C. of 2 to 50 centistokes is preferable.
As the organosilicon compound, a silicone derivative is particularly preferable. Examples of the repeating unit of silicone include dimethylsiloxane, methylethylsiloxane, and phenylmethylsiloxane, and the terminal includes a hydroxyl group and a trimethylsilyl group. Part or all of the hydrogen of the repeating unit siloxane may be modified with polyethylene oxide, polypropylene oxide, polybutylene oxide having 1 to 100 repeating units, or a block or random copolymer thereof. As content of the organosilicon compound in a finishing agent, 70 to 95 weight% is preferable, More preferably, it is 80 to 90 weight%. The viscosity at 25 ° C is more preferably 5 to 30 centistokes.
In addition to the organosilicon compound, the finish may contain an ester compound having a molecular weight of 300 to 1500, mineral oil, emulsifier, and antistatic agent, and the total amount is in the range of 5 to 30% by weight with respect to the weight of the finish. .

Examples of the ester compound include isooctyl stearate, octyl stearate, octyl palmitate, isooctyl palmitate, 2-ethylhexyl stearate, oleyl laurate, isotridecyl stearate, oleyl oleate, dioleyl adipate, trilauric acid Examples include glycerin ester, bisphenol A dilaurate, dilaurate of bisoxyethyl bisphenol A, and dioctanate of bisoxyethyl bisphenol A. As mineral oils, aliphatic alcohol esters and coconut oils whose molecular weight exceeds 500 or become solid at room temperature And polyhydric alcohol esters such as rapeseed oil. Particularly preferred are mineral oils having a redwood viscosity of 40 to 800 seconds at 30 ° C., such as octyl stearate, oleyl oleate, lauryl oleate, and oleyl oleate. The ester compound and mineral oil are preferably less than 10% by weight based on the weight of the finishing agent.

The emulsifier is a compound in which ethylene oxide or propylene oxide is added to at least one selected from alcohols, carboxylic acids, amines and amides having 5 to 30 carbon atoms, and the added mole number of the oxide is 1 to 1. Specific examples of emulsifiers that include 100 nonionic surfactants include polyoxyethylene stearyl ether, polyoxyethylene stearyl oleyl ether, polyoxyethylene oleyl ether, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether , Monobutyl ether copolymerized with propylene oxide / ethylene oxide, polyoxyethylene bisphenol A dilaurate, polyoxyethylene bisphenol A laurate, polyoxyethylene bisphenol A distea Polyoxyethylene bisphenol A stearate, polyoxyethylene bisphenol A diolate, polyoxyethylene bisphenol A oleate, polyoxyethylene stearylamine, polyoxyethylene laurylamine, polyoxyethylene oleylamine, polyoxyethylene oleic acid amide, poly Examples thereof include oxyethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene lauric acid ethanolamide, polyoxyethylene oleic acid ethanolamide, polyoxyethylene oleic acid diethanolamide, and diethylenetriamine oleic acid amide.
The content of the emulsifier is preferably 2 to 15% by weight based on the weight of the finishing agent from the viewpoint of improving emulsifying properties, fiber sizing properties, finishing agent adhesion, and abrasion resistance.

As the antistatic agent, any of known anionic surfactants, cationic surfactants, and amphoteric surfactants may be used. In particular, the use of an anionic surfactant is antistatic and wear resistant. From the viewpoint of imparting emulsifying properties and rust prevention properties, sulfonate compounds, higher alcohols, higher alcohols to which ethylene oxide is added, alkylphenol phosphate esters, and higher fatty acid salts are particularly preferable.
The content of the antistatic agent is preferably 3 to 15% by weight based on the weight of the finishing agent from the viewpoint of imparting antistatic property, wear resistance, emulsifying property, and rust prevention property to the fiber.

The polyetherester fiber of the present invention contains 0.01 to 3% by weight of titanium oxide having an average particle diameter of 0.01 to 2 μm, and further has an aggregate in which the longest part length of the titanium oxide particles is more than 5 μm. Is preferably 7 pieces / mg resin or less. From the viewpoint of suppressing yarn breakage and fluff generation during post-processing such as false twisting and weaving, it is more preferably 5 pieces / mg resin or less, and most preferably 3 pieces / mg resin or less.
The polyether ester fiber of the present invention preferably has a YI value of −30 to 5 as an index of yellowness of the fiber and a WI value of 50 to 150 as an index of whiteness of the fiber. The YI value is preferably -20 to 4.5, more preferably -10 to 3. The WI value is preferably 60 to 100, more preferably 70 to 90.

The form of the polyetherester fiber of the present invention may be either a long fiber or a short fiber, and may be bonded to another component and a side-by-side type or an eccentric sheath-core type. Moreover, in the case of a long fiber, any of a multifilament and a monofilament may be sufficient, and it may be processed into the nonwoven fabric by the spunbond method, the microweb method, etc. Furthermore, the cross-sectional shape is not particularly limited, such as a round shape, a triangular shape, a flat shape, a star shape, a W shape, 3 to 10 leaves, and may be solid or hollow.
Although there is no restriction | limiting in particular as the total fineness of the polyetherester fiber of this invention, 5-1000 dtex is preferable when using it for the objects for clothing. The single yarn fineness is not particularly limited, but is preferably 1 to 100 dtex, more preferably 2 to 70 dtex, and most preferably 5 to 50 dtex.

  The polyetherester fiber of the present invention provides a polyetherester processed yarn having a high degree of stretchability, durability, heat resistance, chlorine resistance and the like by winding fibers other than the polyetherester fiber around it. You can also. Such processed yarns include single cover yarns wound with long fibers, double cover yarns, twisted yarns, pliers, core spun yarns wound with short fibers, and processed yarns wound with both long fibers and short fibers. Known techniques can be used. The weight% of the polyetherester fiber contained in the processed yarn is usually 0.5 to 50% by weight, preferably 1 to 30% by weight. The elongation of the processed yarn thus obtained is usually 50 to 300%, and the elastic recovery rate at 50% elongation is 80 to 100%. In order to obtain such performance, the weight of the polyetherester fiber in the processed yarn weight is 3 to 90% by weight. In these processed yarns, fibers other than polyetherester fibers include polyester fibers, nylon fibers, acrylic fibers, polylactic acid fibers and other synthetic fibers, Bemberg, rayon, polynosic, acetate and other chemical fibers, cotton, wool, silk Natural fibers and the like.

The polyether ester fiber of the present invention is composed of a normal method in which spinning and stretching are performed in separate steps, a straight stretching method in which spinning and stretching are continuously performed, a high-speed spinning method in which fibers are fully oriented at once without a stretching step, Although it may be produced by any of the POY methods that are partially oriented, the method for producing the polyetherester fiber of the present invention will be described below using the usual method as an example.
In order to produce the polyetherester fiber of the present invention, it is important to use the above-described polyetherester of the present invention. The polyether ester used as a raw material needs to be dried to a moisture content of 30 ppm or less with a dryer. Here, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate from the viewpoint of suppressing oxidative degradation and coloring (redness) in the drying step and the melt spinning step. 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] A hindered phenolic antioxidant represented by phosphate is mixed in an amount of 0.2 to 5% by weight based on the weight of the elastomer. If the antioxidant is less than 0.2% by weight, oxygen that may be mixed in the drying process cannot be sufficiently trapped, and if it exceeds 5% by weight, the oxygen is not obtained in the melt spinning process. Causing a decrease in tensile strength and elastic recovery characteristics, more preferably 0.3 to 3% by weight, and most preferably 0.5 to 2% by weight.

  The melt spinning temperature varies depending on the composition of the elastomer, but is preferably 200 to 260 ° C, more preferably 210 to 245 ° C. If the melt spinning temperature is less than 200 ° C., the temperature is too low to be in a stable molten state, resulting in large fiber spots, and the desired high elongation cannot be achieved. Further, when the spinning temperature exceeds 260 ° C., thermal decomposition is severe, and even if the polyether ester of the present invention is used, it is difficult to control the terminal carboxyl group amount of the elastic fiber to 20 meq / kg fiber or less.

  The winding speed of the fiber is not particularly limited, but is usually 3500 m / min or less, preferably 2500 m / min or less, more preferably 2000 m / min or less. If the winding speed exceeds 3500 m / min, the stretching ratio cannot be increased in the stretching process, so that the molecules cannot be oriented and sufficient tensile strength and elastic properties cannot be exhibited. Further, the bobbin is tightly wound by the winding thread, and the bobbin cannot be removed from the winder. The draw ratio at the time of drawing is preferably 1.2 to 7 times, more preferably 1.5 to 6 times, and most preferably 1.8 to 5 times. By combining such a stretching treatment and a heat treatment described later, an elastic fiber that stably satisfies the tensile strength and the elastic properties can be obtained.

The temperature during stretching is preferably 0 to 65 ° C., more preferably 10 to 60 in the stretching zone.
° C, most preferably 15-50 ° C. You may preheat at 25-60 degreeC as needed. If the temperature of the drawing zone is less than 0 ° C. or exceeds 65 ° C., yarn breakage frequently occurs, and elastic fibers satisfying the desired physical properties cannot be obtained stably.
Although heat treatment after stretching may or may not be performed, heat treatment may be performed for the purpose of avoiding changes over time. The upper limit of the temperature when the heat treatment is performed is 180 ° C. When the heat setting temperature exceeds 180 ° C., the fiber is cut in the heat setting zone and cannot be drawn.

  The drawn yarn is preferably wound with the winding speed set to 70 to 97% relative to the drawing speed. If it exceeds 97%, thread breaks occur frequently. Further, after the winding, the fiber contracts and the winding of the package occurs. Therefore, the unpacking failure of the package occurs, or if it is severe, the package cannot be removed from the spindle. On the other hand, if the winding speed setting is less than 70% relative to the drawing speed, yarn breakage or fluffing occurs due to yarn fluctuation. A more preferable winding speed is 75 to 95%, most preferably 80 to 93% relative to the stretching speed.

The elastic fiber obtained as described above may be used alone, but when mixed with fibers of other materials, it becomes a fabric having excellent elastic characteristics and excellent color development in dyeing. Other material fibers are not particularly limited, but conventionally known by mixing with synthetic fibers such as polyester fibers and nylon fibers, chemical fibers such as Bemberg, rayon, polynosic and acetate, and natural fibers such as cotton, wool and silk. It is possible to exhibit elastic recovery characteristics and color developability that cannot be obtained with this mixed fabric.
As an application example of the polyether ester fiber of the present invention, it can be used for woven and knitted fabrics. The structure and production method of the woven or knitted fabric of the present invention are not particularly limited, and known techniques can be used. The form of the fiber of the present invention can be used as it is or as a woven or knitted fabric as the processed yarn described above.

The ratio of the polyetherester fiber contained in the woven or knitted fabric of the present invention is not particularly limited, but is preferably 0.2 to 40% by weight, more preferably 1 to 4% from the viewpoints of elastic properties, handleability, form stability, and the like. 20% by weight. On the other hand, in the case of a processed yarn, there is no particular limitation, and any mixing ratio can be taken.
The woven structure applied to the woven fabric of the present invention includes a plain woven fabric, a double woven fabric, a twill woven fabric, etc., but a plain woven fabric is preferable in that it is easy to increase the woven density. As the weave density, the cover factor K defined by the following formula is preferably in the range of 500 to 4000, more preferably 1000 to 2500.
Cover factor K =
{Warn Density x (Warn Denier) ^0.5 } x {Weft Density x (Weft Denier) ^0.5 }

In the knitted fabric of the present invention, in order to exhibit performance, wale / wrinkle is 10 to 100, preferably 12 to 50, and course / wrinkle is 10 to 200, preferably 12 to 100.
The basis weight of the woven or knitted fabric of the present invention is usually 10 to 1000 g / m ² . When the basis weight is less than 10 g / m ² , the durability is deteriorated. If it exceeds 1000 g / m ² , the knitted fabric may become hard and elastic properties may not be obtained. Preferably, a 20 to 500 g / ^{m 2.}

The cover factor K ′ of the knitted fabric of the present invention is preferably 50 to 800, particularly preferably 100 to 800, from the viewpoints of elastic properties and durability. This is because the cut resistance is lowered when the ratio is less than 50, and the durability is deteriorated when the ratio is more than 800.
The cover factor K ′ is represented by the following formula.
K ′ = (D1 + D2) × Dr ^1/2
D1: Number of knitting wales per 1 cm D2: Number of knitting courses per 1 cm Dr: Fineness of fibers used in the knitting (unit: decitex)

  The structure of the knitted fabric of the present invention may be a commonly used one, and may be either a warp knitting or a weft knitting, a flat knitting, a rubber knitting, a pearl knitting, a tuck knitting, a floating knitting, a piece. Examples include knitting knitting, lace knitting, double knitting knitting, splicing knitting, knitting knitting knitting, Meridian, tricot, Russell, double tricot, and the like.

The knitted fabric of the present invention may be adhered or impregnated with a resin on the surface or a part or all of the inside for the purpose of improving durability, weather resistance, light resistance and the like.
As the resin to be impregnated, a conventionally known thermoplastic resin or thermosetting resin may be used as it is or after modification, and a plurality of types of resins may be mixed as necessary. Usable resins include, for example, thermoplastic resins such as silicon resins, fluorine resins, rubbers (natural rubber, isoprene rubber, chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, polybutadiene rubber, acrylate rubber, Urethane rubber, silicone rubber, etc.), urethane resin, polyamide resin such as nylon 6, nylon 6, 6, etc., polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyolefin resin such as polyethylene, polypropylene, polyethersulfone, polyetherimide, Polycarbonate, polyether ketone and the like can be mentioned. Examples of the thermosetting resin include unsaturated polyester resins, vinyl ester resins, epoxy resins, phenol resins, bismaleimide resins, and the like.
The amount of resin to be impregnated is preferably in the range of 5 to 90% by weight, more preferably 200 to 80% by weight of the knitted fabric.

The woven or knitted fabric of the present invention may be dyed. For example, after knitting or weaving, the knitted or knitted fabric can be dyed through the steps of refining, presetting, dyeing, and final setting by a conventional method. Further, if necessary, an alkali weight loss treatment can be carried out by a conventional method after refining and before dyeing.
Scouring can be carried out in the temperature range of 40 to 98 ° C., but scouring while relaxing is preferable from the viewpoint of maintaining and improving the elastic recovery characteristics.

  One or both of the heat sets before and after dyeing can be omitted, but both are preferably performed in order to improve the form stability and dyeability of the fabric. When performing heat setting, it is necessary to control the temperature and time within a specific range in order to obtain a woven or knitted fabric excellent in elastic recovery characteristics and color developability. The heat setting temperature is preferably 100 to 180 ° C., more preferably 110 to 160 ° C., and the heat setting time is preferably 10 seconds to 3 minutes, more preferably 20 seconds to 1 minute 30 seconds. If the heat setting temperature exceeds 180 ° C., even if the heat setting temperature is within the setting time, the elastic recovery characteristics and color developability of the dyed product obtained are impaired and the texture is also lowered. On the other hand, if the heat setting time exceeds 3 minutes, even if the heat setting is performed at a temperature of 100 to 180 ° C., it is not possible to obtain a dyed product excellent in target elastic recovery characteristics and color development. The K / S value is an index of the color developability of the dyed product, and is a value that can be practically used for clothing, which is 0.5 or more. However, the fabric containing the polyether ester fiber of the present invention at least in part is described above. A dyed product having a K / S value of 0.5 or more is obtained by dyeing through the steps of refining, pre-setting, dyeing, and final setting.

Hereinafter, the present invention will be described in more detail with reference to examples. The main measured values of physical properties were measured by the following methods.
(1) Relative viscosity (η _{SP / C} )
The relative viscosity is 35 ° C in an Ostwald viscosity tube using o-chlorophenol,
It calculated | required by ratio of specific viscosity (eta) _SP and density | concentration C (g / dl).

(2) Number average molecular weight of polyalkylene ether glycol, copolymerization ratio of polyalkylene ether glycol, copolymerization ratio of bis (3-hydroxypropyl) ether, amount of cyclic dimer of trimethylene ester Sample: Solvent: TMS (tetramethylsilane ) In a CDCl ₃ / HFIP-d (deuterated hexafluoroisopropanol) mixed solvent (9/1) at a concentration of ¹ to 2 vol% and dissolved in ¹ H-NMR (AVANCE II AV400M manufactured by Bruker BioSpin Corporation) ).

  In the case of a polyether ester in which the dicarboxylic acid component is terephthalic acid, the diol component is 1,3-propylene glycol, and the polyalkylene ether glycol component is polytetramethylene glycol, the number average molecular weight of the polyalkylene ether glycol is based on the attribution of the following spectrum. The copolymerization ratio of polyalkylene ether glycol, the copolymerization ratio of bis (3-hydroxypropyl) ether, and the cyclic dimer amount of trimethylene ester were determined.

・ Phenyl proton a of main chain: peak near 8.1 ppm ・ Methylene proton b of PDO linked to phenyl ester b: peak near 4.5 ppm ・ Methylene proton c of PDO c: peak near 2.3 ppm ・ Phenyl ester PTMG methylene proton d directly linked to the peak: peak near 4.3 ppm PTMG second and third methylene protons e: several peaks around 1.7-1.9 ppm directly linked to ether group PTMG methylene proton f: peak around 3.5 ppm

  -Methylene proton of PDO linked to the ether group of BPE g: peak around 3.8 ppm

  ・ Phenyl proton h of cyclic dimer: peak near 7.6 ppm

(3) Amount of terminal carboxyl group 1 g of a sample was dissolved in 25 ml of benzyl alcohol, and then 25 ml of chloroform was added, followed by titration (VA) (ml) with a 1/50 N potassium hydroxide benzyl alcohol solution. On the other hand, the titer (V0) was determined by blank titration without pellets. From these values, the amount of terminal carboxyl groups per 1 kg of pellets was determined by the following formula.
Terminal carboxyl group (milli equivalent / kg) = (VA−V0) × 20

(4) Color tone (L * value, b * value, a * value)
Fill a glass cell (inner diameter: 40 mm, depth: 30 mm) with a cylindrical pellet of polyether ester up to 90-100% of the depth, and use a color difference meter (CM-3500) manufactured by Minolta Co., Ltd. The L * value, the a * value, and the b * value were measured using the CIE-L * a * b * (CIE 1976) color system.

(5) Average particle diameter of titanium oxide and number of titanium oxide aggregates The average particle diameter of titanium oxide as a raw material was determined by dispersing titanium oxide in a 1 g / l aqueous solution of sodium hexametaphosphate, and laser diffraction-scattering method manufactured by Beckman Coulter. It measured using the average particle diameter measuring apparatus (model: LSI3320).

The number of titanium oxide aggregates contained in the polyetherester composition or fiber was measured by the following method.
1 mg of the sample was sandwiched between two 15 mm × 15 mm cover glasses and melted at a temperature of (melting point + 20-30) ° C. on a hot plate. After melting, a load of 100 g was applied to the cover glass, and the cover was spread in close contact with the two cover glasses so that the melt did not protrude from the cover glass. By rapid cooling, crystallization of the polymer is hindered and the dispersed state of titanium oxide can be easily observed. The same operation was performed five times to prepare five samples sandwiched between cover glasses.

Using this optical microscope, the resin composition spread between the cover glasses was magnified at a magnification of 200 times, and the entire area of the resin composition spread within the cover glasses was observed. Titanium oxide aggregates are larger than dispersed titanium oxide particles, but the aggregates that can be seen through a microscope and whose longest part exceeds 5 μm are aggregates of titanium oxide, and the number of the aggregates is counted and used. Converted to the number per unit weight of the polyetherester composition or fiber. The same observation was performed for all the five prepared samples, and the average value was defined as the number of aggregates (unit: pieces / mg resin or pieces / mg fiber).

(6) Melting point A sample was heated from room temperature to 250 ° C. at 50 ° C./min with a DSC (Pyris-1 manufactured by Perkin Elmer Co., Ltd.) at a rate of 50 ° C./min, held at 250 ° C. for 3 minutes, and then 0 ° C. Until cooling at a cooling rate of 20 ° C./min. The cooled sample was further heated to 250 ° C. at a temperature increase rate of 20 ° C./min. The melting point (Tm) was determined from the second heating curve.

(7) Spinning and Drawing Conditions The sample was dried at 115 ° C. for 6 hours using a dehumidifying dryer Pearl rotary joint (manufactured by Showa Giken Kogyo Co., Ltd.) to a moisture content of 50 ppm or less. Attach a spinneret to Capillograph-1B (manufactured by Toyo Seiki Co., Ltd.) with a barrel diameter of 9.55 mmφ and a barrel length of 350 mm (effective length of 250 mm), and after reaching the set spinning temperature, put the dried sample into the barrel. A polydimethylsiloxane having a viscosity of 20 centistokes at 25 ° C. (silicon content: 38 wt%) / polyoxyethylene decadiol dioleyl ether is extruded into a non-stretched yarn that has been extruded at an extrusion speed of 50 m / min. Oleyl laurate = 90/5/5 (weight ratio) A finishing agent having a molecular weight of 6% by weight was applied to the fiber weight, and wound around a yarn tube using a winder. Subsequently, the unstretched yarn was stretched by using a horizontal stretching machine at a supply roll of 5 m / min and adjusting the take-up roll speed so that the elongation was about 400% (stretching temperature: room temperature). The drawn yarn was wound with the winding speed set to 85% relative to the take-up roll speed (drawing speed).

(8) Strong elongation of fiber The high elongation of the fiber was measured according to JIS-L-1013.
(9) Heat resistance and hot water resistance evaluation No heat treatment, heat recovery, elastic recovery rate after hot water treatment and stress retention at load removal were evaluated by the following methods. (A) 200% elongation elastic recovery rate Fiber distance between chucks 20 cm And attached to a constant-speed extension type tensile tester, stretched to a stretch rate of 200% at a pulling speed of 20 cm / min, contracted at the same speed, and repeated this three times to draw a stress-strain curve. The elongation when the stress becomes zero during the third contraction is defined as the residual elongation (La). The elastic recovery rate was determined according to the following formula (FIG. 1).
Elastic recovery factor = (200−La) / 200 × 100 (%)
(B) Stress retention at load removal In the 200% elongation repetition test of (a), stress at 100% elongation during the first elongation (S1) and stress at 100% elongation during the third contraction (S2) Therefore, it calculated | required according to the following formula | equation (refer FIG. 2).
Stress retention at load removal = (S2) / (S1) × 100 (%)

(10) YI value / WI value The YI value that is yellowness was measured by the method according to ASTM D1925-70, and the WI value that was whiteness was measured by the method according to ASTM-E313-73 under the following conditions. .
Apparatus: Spectrophotometer Macbeth CE-3000 (manufactured by Macbeth)
Measurement conditions Field of view ... 2 °
Light source ... C (CIE 1964)
Specular gloss ... Including the calculation, YI value and WI value were determined according to the following equations.
YI = 100 × (1.28X−1.06Z) / Y
WI = 4 × 0.847Z-3Y
Here, X, Y, and Z are tristimulus values in the XYZ color system of the material.

[Example 1]
In a 3 L reaction vessel, 267 g of dimethyl terephthalate, 734 g of polytetramethylene glycol (PTMG) having a number average molecular weight of 1800, 210 g of 1,3-propylene glycol (PDO), 0.71 g of titanium tetrabutoxide, antioxidant: Irga Nox 1010 (manufactured by Ciba Specialty Chemicals) (5.0 g) was added, and a transesterification (EI) reaction was carried out at a heater temperature of 220 ° C. in a nitrogen atmosphere. The transesterification reaction was conducted when 77% of the theoretical amount of methanol was distilled off. Ended with. 0.17 g of trimethyl phosphate was added, and after 5 minutes, 0.71 g of titanium tetrabutoxide was added. After 5 minutes, the titanium oxide slurry prepared by the following method was adjusted to 0.5% by weight based on the weight of the polyether ester. Added. Thereafter, the pressure was reduced from normal pressure to 0.2 torr over 42 minutes, and a polycondensation reaction was performed at 245 ° C. for 4 hours. The obtained resin was pelletized to 3 mm square. The obtained pellets were excellent in color tone and did not turn red after drying under the conditions described in (7). Table 2 shows the physical properties of the pellets.
Further, the obtained pellets were subjected to spinning drawing at a spinning temperature of 245 ° C. under the conditions described in (7) (specific conditions: described in Table 3). The obtained fiber showed excellent elastic recovery characteristics and stress retention during load removal, and the characteristics were not lost even after heat treatment and hydrothermal treatment. Table 3 shows the physical properties of the fibers.

(Method for adjusting titanium oxide slurry)
21% by weight of anatase-type titanium oxide having an average particle size of 0.5 μm was added to PDO and stirred at 1000 rpm for 10 hours. Thereafter, the filter was passed through a 500 mesh filter once and further centrifuged at 6000 rpm for 25 minutes to isolate only the supernatant. The content of titanium oxide in the treatment liquid was 20% by weight.

[Example 2]
Except for adding 352 g of dimethyl terephthalate, 642 g of PTMG having a number average molecular weight of 1800, 276 g of PDO, adding titanium oxide, and terminating the EI reaction at the EI reaction rate described in Table 1 to control the high vacuum arrival time, A polymerization reaction was carried out in the same manner as in Example 1. Further, spinning and stretching were performed under the conditions described in Table 3. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Example 3]
The polymerization reaction was performed in the same manner as in Example 2 except that the EI reaction was terminated at the EI reaction rate described in Table 1 and the high vacuum arrival time was controlled. Further, spinning and stretching were performed under the conditions described in Table 3. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Example 4]
394 g of dimethyl terephthalate, 596 g of PTMG having a number average molecular weight of 1800, and 309 g of PDO were added. Reaction was performed. Further, spinning and stretching were performed under the conditions described in Table 3. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Example 5]
PTMG734g having a number average molecular weight of 3000 in polyalkylene ether glycol
The polymerization reaction was carried out in the same manner as in Example 1 except that the EI reaction was completed at the EI reaction rate described in Table 1 and the high vacuum arrival time was controlled. Further, spinning and stretching were performed under the conditions described in Table 3. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Example 6]
642 g of poly (1,3-propylene oxide) glycol (PPG) having a number average molecular weight of 2000 is added to the polyalkylene ether glycol, and the EI reaction is completed at the EI reaction rate shown in Table 1 to control the high vacuum arrival time. The polymerization reaction was carried out in the same manner as in Example 2 except that. Further, spinning and stretching were performed under the conditions described in Table 3. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Example 7]
Add 642g of PTMG having a number average molecular weight of 1800 to polyalkylene ether glycol and 10% of neopentylene oxide copolymerized, and terminate the EI reaction at the EI reaction rate shown in Table 1 to control the high vacuum arrival time. The polymerization reaction was carried out in the same manner as in Example 2 except that. Further, spinning and stretching were performed under the conditions described in Table 3. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Example 8]
Add 596 g of PTMG having a number average molecular weight of 1800 to polyalkylene ether glycol and 10% copolymerized neopentylene oxide, and terminate the EI reaction at the EI reaction rate described in Table 1 to control the high vacuum arrival time. The polymerization reaction was carried out in the same manner as in Example 4 except that. Further, spinning and stretching were performed under the conditions described in Table 3. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Example 9]
The pellet obtained in Example 7 was subjected to solid phase polymerization at 175 ° C. for 8 hours in a nitrogen atmosphere. The cyclic dimer content of trimethylene terephthalate in the polyether ester pellets subjected to solid-phase polymerization is 0.9% by weight, and the undrawn yarn from the pellets does not feel sticky, and the unraveling of the yarn during drawing is performed in Example 7. Smoother than (cyclic dimer content 2.1% by weight). In addition, the fiber spun and drawn under the conditions described in Table 3 improved the strength, the elastic recovery characteristics, and the stress retention rate when the load was removed. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Example 10]
642 g of poly (1,2-propylene oxide) glycol (PPG) having a number average molecular weight of 2000 is added to the polyalkylene ether glycol, and the EI reaction is completed at the EI reaction rate shown in Table 1, and the high vacuum arrival time is controlled. The polymerization reaction was carried out in the same manner as in Example 2 except that. Further, spinning and stretching were performed under the conditions described in Table 3. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Comparative Example 1]
Polymerization was conducted in the same manner as in Example 1 except that 647 g of dimethyl terephthalate, 321 g of PTMG having a number average molecular weight of 1800, and 507 g of PDO were added, the EI reaction was terminated at the EI reaction rate described in Table 1, and the high vacuum arrival time was controlled. Reaction was performed. Further, spinning and stretching were performed under the conditions described in Table 3. The obtained fiber had an elastic recovery rate of less than 40% and was inferior in elastic properties. The pellet physical properties and fiber physical properties are shown in Tables 2 and 3.

[Comparative Example 2]
A polymerization reaction was carried out in the same manner as in Example 2 except that the EI reaction was terminated at an EI reaction rate of 63%. The obtained pellets had a reduced viscosity of less than 1.0 dl / g and were highly colored in the drying process. Further, the fiber could not be solidified during spinning, and the undrawn yarn could not be wound.

[Comparative Example 3]
The polymerization reaction was carried out in the same manner as in Example 2 except that the high vacuum arrival time was controlled at 63 minutes. The obtained pellets were intensely colored in the drying step, and the obtained fibers were remarkably reduced in the elastic recovery rate and the stress retention rate during load removal by heat treatment and hot water treatment.

[Comparative Example 4]
A polymerization reaction was performed in the same manner as in Example 2 except that the EI reaction was terminated at an EI reaction rate of 96%. The obtained pellet had a terminal carboxyl group amount and BPE exceeding the range of the present invention, and the coloring in the drying process was large. Furthermore, the fiber obtained had an elastic recovery rate and a stress retention rate when the load was removed significantly reduced by heat treatment and hydrothermal treatment.

[Comparative Example 5]
Polymerization was conducted in the same manner as in Example 1 except that 1,4-butanediol was used in place of PDO to synthesize a polyetherester polymer having a reduced viscosity of 2.0 dl / g.
Polyether ester fibers were prepared using this polymer, and the obtained fibers had significantly reduced elastic recovery rates and stress retention rates at the time of load removal regardless of whether or not heat treatment was performed (Table 3).

[Example 11]
Full coverage yarn of polyetherester fiber (18 dtex / 3f) prepared as in Example 1 (bottom twist Z direction 2400 T / m, upper twist S direction 2200 T / m) using nylon 66 fiber 13 dtex / 5f as coating yarn )created. Subsequently, the fabric of the sock obtained by knitting a shoe base with a sock knitting machine having a diameter of 360 needles using the yarn and dyeing by a conventional method is soft, and the appearance is a needle line, It was extremely high quality with almost no surface irregularities and loop disturbance.

[Example 12]
Full coverage yarn of polyetherester fiber (18 dtex / 3f) prepared as in Example 7, using nylon 66 fiber 13dtex / 5f as the covering yarn (bottom twist Z direction 2400T / m, upper twist S direction 2200T / m) )created. Subsequently, the fabric of the sock obtained by knitting a shoe base with a sock knitting machine having a diameter of 360 needles using the yarn and dyeing by a conventional method is soft, and the appearance is a needle line, It was extremely high quality with almost no surface irregularities and loop disturbance.

[Examples 13 to 15]
Nylon 6 fibers (44 dtex / 34f) were placed on the front and back, and polyether ester fibers 310 dtex obtained by the methods of Examples 1, 6 and 7 were placed in the middle, and a Russell knitted fabric was knitted under the following conditions. The elastic yarn was stretched by 100% and warped.

[Russell knitting conditions]
Knitting machine Russell knitting machine manufactured by KARL MAYER 56 gauge / 2 inch organization Front 20/02/20/24/42/24 Middle 00/44/22/66/22/44 Back 00/22/00/22/00 / 22 Runner length Front 122cm / 480 course Middle 11.4cm / 480 course Back 16.0cm / 480 course Onboard course 75 course / inch Relax the obtained knitted fabric in 90 ° C warm water, and after presetting at 190 ° C, Dyeing was performed at 95 ° C. for 30 minutes, and finishing set was performed at 170 ° C. to finish C / W (knitting density) shown in Table 1. The physical properties of the resulting knitted fabric are shown in Table 4.
A long girdle was prepared using the obtained fabric and was worn by three panelists. The thigh displacement was measured by measuring the lift after standing upright, deciding the thigh line at a predetermined position, and repeating the crouching action 10 times. A feeling of wearing shows the result of the questionnaire survey of attachment and detachment and wearing feeling, and was evaluated as follows.
◎◎: Very good and soft texture, ◎: Very good, ○: Good ×: Insufficient fit Russell using the polyetherester fiber of the present invention has excellent stretchability and feel when worn as clothing Also excellent.

[Comparative Example 6]
Polyether ester fibers were made by the method of Comparative Example 5 and Example 12 was repeated. The obtained Russell had low elastic characteristics and insufficient wearing feeling (Table 4).

[Example 16]
A plain weave with a cover factor of 2000 was prepared using the fibers of Examples 11 and 12. The obtained woven fabric exhibited excellent stretch properties, and the yellowness and whiteness (YI value / WI value) of the fabric were as good as 3.4 / 82 and 2.8 / 85. On the other hand, the same processed yarn was prepared using the polyether ester fibers of Comparative Examples 4 and 5, and the same plain woven fabric was prepared, but the stretchability and elastic recovery were clearly inferior. Further, the (YI value / WI value) of the plain fabric obtained from Comparative Example 4 was clearly colored as 7.6 / 55.

  Since the polyether ester of the present invention is excellent in oxidation resistance and thermal stability and excellent in whiteness, it is useful as a raw material for fibers and for resin molding.

(A) Measurement of 200% elongation elastic recovery (B) Measurement of stress retention at load removal

Claims (13)

It is a polyether ester composed of terephthalic acid as the main dicarboxylic acid component, 1,3-propylene glycol as the main diol component and a polyalkylene ether glycol having a number average molecular weight of 500 to 20000 having a copolymerization ratio of 35 to 80% by weight. A polyether ester satisfying the following (1) to (4):
(1) 1.0 dl / g ≦ reduced viscosity (ηsp / c) ≦ 4.0 dl / g
(2) Terminal carboxyl group amount ≦ 20 meq / kg resin (3) Copolymerization ratio of bis (3-hydroxypropyl) ether ≦ 1.8% by weight
(4) L * value ≧ 70, −5 ≦ b * value ≦ 15, −5 ≦ a * value ≦ 3   The polyalkylene ether glycol is at least one selected from the group consisting of poly (ethylene oxide) glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, and poly (tetramethylene oxide) glycol. The polyetherester according to claim 1, wherein The polyether ester according to claim 1 or 2, wherein 3 to 30% of the repeating units of the polyalkylene ether glycol have the following structure.

  Titanium oxide having an average particle diameter of 0.01 to 2 μm is contained in an amount of 0.01 to 3% by weight, and the aggregate having the longest portion in which the titanium oxide particles are collected has a length exceeding 10 μm / mg resin or less. The polyetherester composition according to any one of claims 1 to 3, wherein   The polyetherester fiber comprised from the polyetherester in any one of Claims 1-4, or its composition. A polyetherester fiber comprising the polyetherester according to any one of claims 1 to 4 or a composition thereof and further satisfying the following (a) and (b):
(A) Tensile strength ≧ 0.3 cN / dtex and elongation ≧ 200%
(B) Either after heat treatment at 140 ° C. for 4 hours or after treatment with hot water at 95 ° C. for 4 hours, the elastic recovery rate after repeating 200% elongation three times is 70% or more, and the first time The stress retention at 100% elongation during the third contraction is 20% or more with respect to the stress at 100% elongation during elongation. It is a polyether ester composed of terephthalic acid as the main dicarboxylic acid component, 1,3-propylene glycol as the main diol component and a polyalkylene ether glycol having a number average molecular weight of 500 to 20000 having a copolymerization ratio of 35 to 80% by weight. And a fiber composed of a polyether ester characterized by satisfying the following (1) to (3).
(1) 1.0 dl / g ≦ reduced viscosity (ηsp / c) ≦ 4.0 dl / g
(2) Terminal carboxyl group amount ≦ 20 meq / kg resin (3) Copolymerization ratio of bis (3-hydroxypropyl) ether ≦ 1.8% by weight The fiber composed of the polyether ester according to claim 7, wherein the fiber composed of the polyether ester further satisfies the following (4) to (5).
(4) Tensile strength ≧ 0.3 cN / dtex and elongation ≧ 200%
(5) The elastic recovery is 70% or more after repeating 200% elongation three times after heat treatment at 140 ° C. for 4 hours or after treatment with hot water at 95 ° C. for 4 hours; The stress retention at 100% elongation during the third contraction is 20% or more with respect to the stress at 100% elongation during elongation. The finishing agent is attached to the fiber surface in an amount of 0.5 to 9.0% by weight, and contains 30 to 100% by weight of the following compound (I) as a constituent of the finishing agent. The polyetherester fiber according to any one of the above.
(I) An organosilicon compound having a silicon atom content of 20 to 50% by weight and a viscosity at 25 ° C. of 2 to 50 centistokes   Aggregates containing 0.01 to 3% by weight of titanium oxide having an average particle diameter of 0.01 to 2 μm and the longest part length of the titanium oxide particles gathered is more than 7 μg / mg fiber The polyetherester fiber according to any one of claims 5 to 9, wherein   The polyetherester fiber according to any one of claims 5 to 10, wherein the single yarn fineness is 1 to 100 dtex and the total fineness is 5 to 10,000 dtex.   A polyether ester composite yarn, wherein a fiber other than the polyether ester fiber is wound around the polyether ester fiber according to any one of claims 5 to 11.   A woven or knitted fabric containing the polyetherester fiber according to any one of claims 5 to 12.

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