JP2007119571A - Polyether ester elastomer and elastic fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyether ester elastomer that has high elasticity and heat stability and improved light resistance and a fiber. <P>SOLUTION: The polyether ester elastomer comprises a polybutylene terephthalate as a hard segment and a poly(oxytetramethylene)glycol as a soft segment. The polyether ester elastomer is produced by using a titanium compound as a main catalyst. The polyether ester elastomer contains 0-1.5 mols of a phosphorus compound based on the titanium compound. The elastic fiber is obtained by spinning the polyether ester elastomer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a copolymerized polyetherester elastomer having both high elasticity and light resistance and a fiber comprising the same.

Polyester, especially polyethylene terephthalate, has many excellent properties and is widely used for various clothing applications. However, it has a drawback in terms of elastic function.
In order to solve this problem, a polyester fiber having improved elastic performance by copolymerizing a component such as polyalkylene glycol with polyester has been proposed (for example, see Patent Document 1). In this method, the elastic performance is greatly improved, but the polyalkylene glycol copolymer polyester has a problem that the light resistance is extremely poor.
JP-A-5-71013

  An object of the present invention is to provide a polyether ester elastomer and an elastic fiber that solve the above-mentioned problems that have existed conventionally and that have high elasticity and improved light resistance.

In view of the prior art, the present inventors have intensively studied and have completed the present invention. That is, the object of the present invention is to
A polyether ester elastomer having polybutylene terephthalate as a hard segment and poly (oxytetramethylene) glycol as a soft segment, wherein the polyether ester elastomer is produced using a titanium compound as a main catalyst, and This can be achieved by a polyetherester elastomer characterized by containing a phosphorus compound in an amount exceeding 0-fold mol and less than 1.5-fold mol relative to the titanium compound, and an elastic fiber comprising the same.

  ADVANTAGE OF THE INVENTION According to this invention, the polyetherester elastomer which has high elasticity and light resistance can be provided. Furthermore, an elastic fiber having high light resistance can be provided by melt spinning the polyether ester elastomer.

Hereinafter, the present invention will be described in detail.
The polyether ester elastomer in the present invention is a polyester having a polybutylene terephthalate unit as a hard segment. Polyester having polybutylene terephthalate as the main repeating unit of the hard segment is preferable. Examples of the dicarboxylic acid component other than terephthalic acid that can be copolymerized with polybutylene terephthalate constituting the hard segment include, for example, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyloxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p- Mention may be made of aromatic, alicyclic or aliphatic bifunctional carboxylic acids such as oxybenzoic acid, adipic acid, sebacic acid or 1,4-cyclohexanedicarboxylic acid.

  Further, if the achievement of the object of the present invention is within a range that is not substantially impaired, tricarboxylic acid or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid, or glycerin, trimethylolpropane, or pentaerythritol Such a trifunctional or higher polyol may be used as a copolymerization component.

  Examples of diol components other than tetramethylene glycol that can be copolymerized include, for example, ethylene glycol, trimethylene glycol, cyclohexane-1,4-dimethanol, neopentyl glycol, poly (oxyalkylene) glycol, bisphenol A, bisphenol S, or Examples thereof include aliphatic, alicyclic or aromatic diol compounds such as compounds obtained by adding an ethylene glycol unit to the hydroxy group of these compounds.

Next, poly (oxytetramethylene) glycol or a derivative thereof as a soft segment of the polyether ester elastomer in the present invention is copolymerized for the purpose of improving the water absorption performance of the copolyester in addition to exhibiting properties as an elastomer. I am letting. The copolymerization amount of such poly (oxytetramethylene) glycol to the polyether ester elastomer is preferably 30 to 70% by weight, particularly preferably 35 to 65%, based on the total weight of the polyether ester elastomer. % By weight. That is, the hard segment: soft segment weight ratio is preferably 30:70 to 70:30, particularly preferably 35:65 to 65:35, based on the total weight of the polyetherester elastomer. The poly (oxytetramethylene) glycol component may be added to the reaction system at an arbitrary stage before completion of the production of the polyester, but is preferably added to the reaction system before the start of the polycondensation reaction. As described later, the hard segment: soft segment weight ratio can be calculated by measuring a ¹ H-NMR spectrum of a solution of a polyether ester elastomer and analyzing the spectrum pattern.

  The molecular weight of poly (oxytetramethylene) glycol or a derivative thereof is preferably in the range of 100 to 4000 in terms of number average molecular weight. When the molecular weight of the poly (oxytetramethylene) glycol or its derivative exceeds 4000, the heat resistance of the polyether ester elastomer is deteriorated. On the other hand, when the molecular weight is less than 1000, the elasticity of the polyether ester elastomer is deteriorated. It becomes difficult to obtain. In particular, the molecular weight is desirably in the range of 1000 to 4000. Specific examples of such poly (oxytetramethylene) glycol derivatives include polytetramethylene glycol (number average molecular weights 1000, 1500, 2000).

  Next, the titanium compound which is blended in the polyether ester elastomer and used as a main catalyst when producing the polyether ester elastomer will be described. The titanium compounds include tetraalkoxide titanate, tetraphenoxide titanate, hexaalkoxide dititanate, hexaphenoxide dititanate, octaalkoxide trititanate, octaphenoxide trititanate, decaalkoxide tetratitanate and decaffenoxide. There may be mentioned at least one titanium compound from the group consisting of side tetratitanate. Specifically, the alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a hexyloxy group. Of these, more preferred titanium compounds are tetraisopropoxy titanate and tetrabutoxy titanate. Further, the titanium compound can be used as a catalyst for transesterification or as a catalyst for esterification reaction, as a catalyst for polycondensation reaction, or as a catalyst for promoting both reactions.

  Next, the phosphorus compound which inactivates the titanium compound will be described. The phosphorus compounds include phosphoric acid esters such as trimethyl phosphate, triethyl phosphate or triphenyl phosphate, phosphites such as triphenyl phosphite or trisdodecyl phosphite, methyl acid phosphate, dibutyl phosphate or monobutyl phosphate acidity. Phosphorus esters, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, and other phosphorus compounds can be used. Among these, phosphorous acid, orthophosphoric acid, trimethyl phosphate, and the like are preferably used. Of these, it is particularly preferable to use phosphorous acid. A phosphorus compound may be used individually by 1 type, or may use 2 or more types together. The compounding amount of these phosphorus compounds is more than 0 times mol and less than 1.5 times mol, preferably 0.2 to 1.2 times mol based on the titanium compound of the catalyst used for the production of the polyether ester elastomer. It is preferable to mix (contain) so as to occupy, more preferably 0.5 to 1.0 times mol. Here, when the amount is too small, the effect of improving the inactivation of the reaction catalyst is not sufficiently exhibited. On the other hand, excessive blending may not exhibit the effect of improving the pack pressure during spinning and improving the light resistance of the polymer. The phosphorus compound is more preferably blended with the copolymer polyester or its low polymer immediately before the completion of the polycondensation reaction in the polyether ester elastomer.

［上記式中、Ｒ_１、Ｒ_２及びＲ_３は炭素数１〜１０の炭化水素基であり、それぞれ同一でも異なっていても良い。また、ｎは１〜５の整数である。Ｍはアルカリ金属又はアルカリ土類金属原子であり、Ｍがアルカリ金属の場合、ｍ＝１、Ｍがアルカリ土類金属の場合、ｍ＝２である。］ Further, as the phosphorus compound, a phosphonate represented by the following formula (I) may be used.

[In the above formula, R ₁ , R ₂ and R ₃ are hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different. Moreover, n is an integer of 1-5. M is an alkali metal or alkaline earth metal atom. When M is an alkali metal, m = 1, and when M is an alkaline earth metal, m = 2. ]

In the above formula _(I), the hydrocarbon group having 1 to 10 carbon atoms constituting R 1, _{R 2} and _{R 3,} include alkyl groups, aromatic groups having 6 to 10 carbon atoms having 1 to 10 carbon atoms It is done. Among these, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tertiary butyl group. In addition, examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group and a benzyl group. Of these, a methyl group, an ethyl group, an isopropyl group, or a tertiary butyl group is preferable. In the formula (I), n is an integer of 1 to 5, preferably 1 or 2. Further, M is an alkali metal atom or an alkaline earth metal atom. When M is an alkali metal atom, m = 1, and when M is an alkaline earth metal atom, m = 2. Examples of the alkali metal atom include potassium and sodium. Examples of alkaline earth metal atoms include calcium, magnesium, strontium, barium and the like. Preferably it is calcium.

  Specific examples of the compound represented by the formula (I) include calcium diethylbis (((3,5-dimethyl-4-hydroxyphenyl) methyl) phosphonate), magnesium diethylbis (((3,5-dimethyl-4-hydroxy). Phenyl) methyl) phosphonate), calcium diethylbis (((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) phosphonate), magnesium diethylbis (((3,5-bis (1 , 1-dimethylethyl) -4-hydroxyphenyl) methyl) phosphonate), calcium diethylbis (((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) ethyl) phosphonate), magnesium diethylbis ((((3,5-bis (1,1-dimethylethyl) -4-hydroxy Eniru) ethyl) phosphonate), and the like.

  The fact that at least a part of the titanium compound is inactivated by the incorporation (containment) of these phosphorus compounds is tested separately from the polycondensation reaction step or the polycondensation reaction step by a thermal stability evaluation method. This can be confirmed. That is, after the polymerization of the polyester having a sufficient intrinsic viscosity according to the intended use is completed, the reaction vessel in a high vacuum is returned to normal pressure and the polycondensation is completed. Next, the decrease in intrinsic viscosity when the polyester is discharged is calculated and evaluated as a change with time based on the discharge start time. Specifically, when there is a temperature at which the polyester can maintain a molten state even during ejection, the reactive catalyst used during the polycondensation reaction remains in the polyester. The decomposition reaction proceeds little by little and the intrinsic viscosity tends to decrease. On the other hand, if a phosphorus compound as described above is added before discharge to inactivate at least a part of the catalyst, a decrease in intrinsic viscosity during discharge is suppressed. Therefore, the deactivation of the remaining active catalyst can be evaluated by the change with time of the intrinsic viscosity of the polyester due to the discharge time. Note that this operation can be evaluated by a similar operation even if the polycondensation is once completed and the polyether ester elastomer is in a chip shape, after the chip is sufficiently dried, and then melted in a tank.

Next, the method for producing the polyetherester elastomer of the present invention will be described below by taking as an example a polyester having a butylene terephthalate unit as a main repeating unit.
First, dimethyl terephthalate and tetramethylene glycol are transesterified in the presence of a transesterification catalyst, terephthalic acid and tetramethylene glycol are directly esterified, or terephthalic acid and butylene oxide are reacted. By any of these methods, bis (ω-hydroxytetramethylene) terephthalate and / or its oligomer is formed. In this case, the transesterification reaction catalyst can be supplied at the initial stage of the transesterification reaction, in addition to the preparation of the raw material. Furthermore, the polycondensation catalyst can be supplied by the early stage of the polycondensation reaction step. The reaction temperature during the transesterification reaction is usually 200 to 230 ° C., and the reaction pressure is normal pressure to 0.2 MPa.

  Thereafter, in the presence of a polycondensation catalyst, melt polycondensation is carried out under high temperature and reduced pressure to obtain a polyether ester elastomer. The poly (oxytetramethylene) glycol and the phosphorus compound are subjected to any pre-polyester production. This is accomplished by adding the reaction system in stages. Preferably, the poly (oxytetramethylene) glycol component is preferably added at a stage prior to the formation of bis (ω-hydroxytetramethylene) terephthalate and / or its oligomer, and the phosphorus compound is added immediately before the completion of the polycondensation reaction. It is preferable to add. The reaction temperature during polycondensation is usually 230 to 270 ° C., and the reaction pressure is usually 60 to 0.1 kPa. Such a transesterification reaction and polycondensation reaction may be performed in one step or in multiple steps.

  In these reactions, any catalyst can be used as necessary, and among these, a titanium compound is preferably used as the catalyst used for the transesterification reaction, and a germanium compound is used as the polycondensation catalyst. , Antimony compounds, titanium compounds, and tin compounds are preferably used, and titanium compounds are particularly preferable. The amount of the catalyst used is not particularly limited as long as it is a necessary amount for proceeding the transesterification reaction and polycondensation reaction, and a plurality of catalysts can be used in combination. Specific examples of the titanium compound include the compounds described above. In addition, since the titanium compound can be used for any of the ester exchange reaction, esterification reaction and polycondensation reaction, the addition time is not limited to before the polycondensation reaction, and the initial stage, the middle of the ester exchange reaction or esterification reaction, etc. May be added.

  The polyether ester elastomer of the present invention has an intrinsic viscosity of usually 1.50 dL / g or more, preferably 1.5 to 2.0 dL / g, particularly preferably 1.80 to 1.20 dL / g. Is preferred. When the intrinsic viscosity is less than 1.50 dL / g, the physical properties such as the strength and the stretch moldability are likely to deteriorate. On the other hand, when the intrinsic viscosity is too high, the productivity is deteriorated. The moldability such as stretching tends to decrease. Intrinsic viscosity can be achieved within this range by appropriately selecting the polymerization temperature, the degree of vacuum (pressure) in the polymerization reactor, and the reaction time. Depending on the conditions, the decomposition reaction may also proceed in parallel. Therefore, by increasing the temperature extremely or increasing the reaction time in order to obtain a high intrinsic viscosity, the low intrinsic viscosity polyether ester can be obtained. It is also possible to obtain an elastomer.

  The obtained polyetherester elastomer is chipped by a conventional method. The average particle size of the chip is usually in the range of 2.0 to 5.5 mm, preferably 2.2 to 4.0 mm. In terms of weight, the range of 10 to 40 mg per chip is preferable.

  The polyether ester elastomer of the present invention can be stably molded under a wide range of molding conditions, and a normal melt spinning method can be applied. Thereby, an elastic fiber can be obtained. The cross-sectional shape of the fiber is not limited to a round cross-section, and may be an irregular cross-section such as a flat shape, a triangular cross-section, and a multi-leaf cross-sectional shape. In addition, heat stabilizers, antioxidants, and a small amount of additives as necessary, such as lubricants, pigments, dyes, antioxidants, fluorescent whitening agents, antistatic agents, for the purpose of improving heat stability during molding , Antibacterial agents, ultraviolet absorbers, infrared absorbers, light stabilizers, shading agents, matting agents, and the like. These stabilizers are preferably added immediately before the completion of the polycondensation reaction.

  The temperature at which the polyetherester elastomer of the present invention is melt-spun depends on the melting point of the polyetherester elastomer, but is suitably 200 to 270 ° C, preferably 220 to 250 ° C. If the temperature is lower than 200 ° C., the temperature is too low to be in a stable molten state, and if it exceeds 270 ° C., the polyether ester elastomer is thermally decomposed and the spinning yarn is insufficiently cooled. Problems such as the occurrence of fusing occur. Next, the spun yarn may be taken up at a predetermined speed and then wound up once, and the obtained undrawn yarn may be drawn by a separate drawing machine, or after the spun yarn is taken up, it is continuously unwound. A direct spinning drawing method may be applied in which the film is drawn and wound.

  Here, the direct spinning drawing method includes, for example, a method in which spinning is performed at a speed of 400 to 2000 m / min and then wound at a speed of 450 to 2500 m / min. Further, heat setting is possible as required, and the roller temperature of the heat setting is preferably 130 to 160 ° C. When the temperature is within this range, the heat setting property is sufficient and the fiber is not melt cut. Any method can be used for stable yarn production.

  The filament form of the fiber of the present invention thus obtained may be either a filament or a staple, and the total yarn fineness, single yarn fineness, number of twists, number of entanglements, etc. are appropriately set according to the purpose of use of the fiber. be able to.

  Further, when the fiber of the present invention is made into a fabric, the elastic fiber of the present invention may be used 100% or may be used in combination with other fibers. Here, when used in combination with other fibers, when used as a composite yarn, it may be a mixed fiber or a composite false twisted yarn. Polyester such as nylon 6, polyamide such as nylon 66 or nylon 66, para-type or meta-type aramid, polyolefin such as polyethylene, polypropylene or acrylic, or modified and / or composite fibers thereof, as well as natural fibers, recycled fibers, semi-synthetic It can be freely selected from fibers and the like.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention does not receive any limitation by this. In addition, each value in an Example was calculated | required according to the following method.
(1) Intrinsic viscosity (hereinafter abbreviated as IV):
A predetermined amount of the polymer was weighed and dissolved in o-chlorophenol at 35 ° C. to a concentration of 0.012 g / ml, etc., and then determined according to a conventional method.
(2) Col-L, Col-b, Lb (hue):
The polymer heat-dried in a dryer at 160 ° C. for 60 minutes was determined using a CR-200 color difference meter manufactured by Minolta Co., Ltd.
(3) Light resistance (fade measurement):
A fabric was prepared by the following operation, and the fabric was treated with a fade meter (model: FAL-AU.H.B) manufactured by Suga Test Instruments Co., Ltd. at a temperature of 70 ° C. and a humidity of 33 RH% for 5 hours. After the treatment, the tensile strength of the yarn obtained by unwinding the tubular knitting was measured, and the retention was calculated from the value before the treatment.
(4) Elastic recovery rate A 10 cm sample yarn was stretched to 20 cm and held for 10 seconds. Thereafter, the recovery length when the tension was released was measured, and the value divided by 10 cm was multiplied by 100 to obtain the elastic recovery rate (%).
(5) Tensile elongation, tensile strength:
It calculated | required based on the method of JISL1013 description.
(6) Fabric creation:
Fabric was made using a small cylinder knitting machine (CR-B type: needle 3.5 inches × 220 needles) manufactured by Koike Seisakusho. The evaluation results of the fabric are shown in Table 2.
(7) Hard segment: soft segment weight ratio:
After dissolving the polymer sample in deuterated trifluoroacetic acid / deuterated chloroform = 1/1 (volume ratio) mixed solvent, JEOL A-600 superconducting FT-NMR manufactured by JEOL Ltd. was used for nuclear magnetic resonance spectrum. ( ¹ H-NMR) was measured. The hard segment: soft segment weight ratio was calculated from the spectrum pattern according to a conventional method.
(8) Measurement of titanium content and phosphorus content in polyetherester elastomer:
A polymer sample was heated and melted to prepare a circular disk, and quantified using a fluorescent X-ray apparatus ZSX100e type manufactured by Rigaku Corporation.

[Example 1]
100 parts by weight of dimethyl terephthalate, 65 parts by weight of tetramethylene glycol and 170 parts by weight of polytetramethylene glycol (number average molecular weight 2000) as polyalkylene ether glycol are charged into a reactor, and tetrabutoxy titanate is used as a transesterification catalyst. 120 mmol% of dimethyl terephthalate was added. The transesterification was carried out while distilling off by-produced methanol out of the system to complete the transesterification. The reaction product was heated to 210 ° C. to initiate the polymerization reaction. The polymerization reaction is 3-4 MPa over 30 minutes, 60 Pa or less in the next 30 minutes, and then, after continuing the polymerization reaction for 120 minutes, Irg1425 (trade name of Ciba Specialty Chemicals manufactured by Ciba Specialty Chemicals) (Abbreviation) was reacted under high temperature and high vacuum for about 20 minutes after addition of an amount of 0.5 times mol of tetrabutoxy titanate. As a result, a copolymerized polybutylene terephthalate ether elastomer having a polybutylene terephthalate portion as a hard segment and a polytetramethylene glycol portion as a soft segment was obtained. The hard segment: soft segment weight ratio was 40/60.

The obtained polybutylene terephthalate ether elastomer composition was dried at 130 ° C. for 4 hours and then spun at 80 dtex / 12 fil at a spinning temperature of 260 ° C. and a winding speed of 400 m / min to obtain a hygroscopic elastic yarn.
The resulting elastic yarn had a strength of 0.79 cN / dtex and a light resistance strength retention of 82%. The elastic recovery rate was 87%. The physical properties of the elastomer and the spun elastic yarn are shown in Table 1.

[Example 2]
In Example 1, the same operation was performed except that the amount of Irg1425 added as the phosphorus compound was changed. The results are summarized in Table 1.

[Example 3]
In Example 1, the same operation was performed except that phosphorous acid as a phosphorus compound was used and the addition amount was changed in the same manner as in Examples 1 to 3. The results are summarized in Table 1.
In the above description and Table 1, Irg1425 is calcium diethylbis (((3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) phosphonate) (alias: calcium bis {ethyl ((3 , 5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) methyl) phosphonate}). This compound is a compound of R ₁ = R ₂ = t-butyl group, R ₃ = ethyl group, n = 1, m = 2, M = Ca in the formula (I) (manufactured by Ciba Specialty Chemicals) Represents.

[Comparative Examples 1-3]
The same operation was performed except that the phosphorus compound was not used in Example 1, or the type and amount of the phosphorus compound were changed as shown in Table 1. The results are summarized in Table 1.

  According to the present invention, it is possible to provide a polyetherester elastomer having both high elasticity and heat stability, and furthermore, by melt spinning the polyetherester elastomer, an elastic fiber having high elasticity and light resistance. Can be provided. According to the present invention, the use of the elastic fiber can be expanded, and its industrial significance is great.

Claims (4)

  A polyether ester elastomer having polybutylene terephthalate as a hard segment and poly (oxytetramethylene) glycol as a soft segment, wherein the polyether ester elastomer is produced using a titanium compound as a main catalyst, and A polyether ester elastomer comprising a phosphorus compound in an amount exceeding 0-fold mol and less than 1.5-fold mol relative to a titanium compound.   The polyetherester elastomer according to claim 1, which has an intrinsic viscosity of 1.50 dL / g or more.   The polyether ester elastomer according to any one of claims 1 to 2, wherein a ratio of hard segment: soft segment is in a range of 30:70 to 70:30 based on weight.   The elastic fiber which consists of a polyetherester elastomer of any one of Claims 1-3.