JP6988891B2 - polyester - Google Patents

Description

The present invention relates to a polyester having excellent hygroscopicity.

Due to its excellent properties, polyester has a wide range of applications in fields such as textiles, films and plastics. However, due to its regular structure, polyester is highly hydrophobic, and compared to natural fibers such as cotton or linen, polyester fibers have poor water absorption and hygroscopicity, and in environments that require hygroscopicity. The use of polyester fibers is severely restricted. When a woven fabric obtained from polyester fibers is used for underwear, polyester fibers are not suitable for summer clothes because the hygroscopicity of the polyester fibers is poor and causes sultry heat.

Those skilled in the art have considered many methods to solve the problem of low water absorption and hygroscopicity of polyester fibers. For example, the surface of the fiber is modified mainly so as to make the surface of the fiber porous and improve the hygroscopicity of the fiber by using the capillary principle. Modification of the fiber surface can also be achieved by methods such as discharge treatment, photograft modification, and low temperature plasma treatment. However, after the fibers obtained by these methods are made into a woven fabric, there is little effect such as reducing the heat and humidity in a sweating state, and there is no refreshing feeling of natural fibers such as cotton and linen. In addition to these methods, there is a method of coating the fiber surface with a hydrophilic film, but this method often has a drawback that the affinity between the fiber and the film is poor and the durability after washing is poor.

It is also possible to improve the hygroscopicity of the fibers by chemically grafting the polyester fibers. For example, by graft-copolymerizing polyethylene terephthalate (PET) fiber with about 15% acrylic acid and methacrylic acid and then performing sodium ion exchange treatment, a moisture absorption rate equivalent to that of cotton can be obtained. However, such fibers are not industrially produced because the moisture absorption rate is very slow, the basic characteristics of polyester fibers are largely lost, and there is basically no applicability.

High-molecular-weight polyether compounds are also used to improve moisture absorption, but the high-molecular-weight polyether compounds are not completely copolymerized with the polyester matrix, and most of them are present in the polyester in the state of a separated phase. As a result, when the polymer is melted and held, it is coarsened to form an unstable phase-separated structure, and the discharge after the completion of the polymerization reaction and the discharge of the base portion during spinning become unstable. , Fiber fineness spots, increased dyeing spots, and fluffing occur. In JP-A-2007-70467, a special copolymerization of PEG and PET is used in order to improve the hygroscopicity of PET. However, if the amount of PEG added is too small, the hygroscopicity is not high, so that a large amount of PEG must be added. As a result, the polyester loses the basic properties of the fiber after being formed as a fiber, and has heat resistance and water resistance. , Oxidation heat resistance is significantly reduced, and the utility value is very low.

Japanese Unexamined Patent Publication No. 2007-070467

An object of the present invention is to provide a polyester having excellent heat resistance and heat generation resistance, and a polyester having excellent hygroscopicity, in which the fibers obtained by spinning have excellent heat resistance and heat generation resistance.

The technical proposal of the present invention is as follows.

A polyester, which is a polymer formed by using an aromatic dicarboxylic acid or a derivative thereof and an aliphatic diol as a main composition component and polyethylene glycol as a copolymerization component, and the number average molecular weight of polyethylene glycol is 2000 to 30,000 g / mol. The copolymerization rate is 25 to 55 wt%, and the polyester contains a half-hindered phenolic antioxidant represented by the formula 1.

(In the formula, R1 is a group to which one or more of hydrocarbons, oxygen and nitrogen are bonded, and R2 is a group to which one or more of hydrogen, hydrocarbons, oxygen and nitrogen are bonded. Is the basis.)

The content of the half-hindered phenolic antioxidant preferably occupies 1.0 to 8.0 wt% of the total weight of the polyester.

The half-hindered phenolic antioxidant is preferably 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-), which is an antioxidant represented by the formula 2. 5-Methylphenyl) propanoyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, or 1,3,5-tris (4-tert-butyl) represented by formula 3. -3-Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione.

The copolymerization rate of the polyethylene glycol is preferably 35 to 55 wt%.

When the aliphatic diol is preferably ethylene glycol or 1,4-butanediol, and the aliphatic diol is preferably ethylene glycol, the number average molecular weight of the polyethylene glycol is preferably 4000 to 30,000 g / mol. Is.

In the polyester of the present invention, the copolymerization rate of polyethylene glycol is high, the hygroscopicity of the polyester chip is excellent, and the difference in hygroscopicity before and after fiber dyeing after the polyester is formed on the fiber is small. In addition, polyester has good heat resistance, excellent yellowing resistance, and high application value.

The polyester of the present invention is a polyether ester obtained by copolymerizing an aromatic dicarboxylic acid or a derivative thereof, an aliphatic diol as a main monomer, and polyethylene glycol as a copolymerization component, and has good heat resistance and mechanical properties. Has.

Specific examples of the aromatic dicarboxylic acid or a derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, sodium isophthalic acid-5-sulfonate, lithium isophthalic acid-5-sulfonate, and 5- (tetraalkyl) -isophthal. Examples thereof include, but are not limited to, an acid sulfonic acid phosphorus compound, 4,4'-biphenyldicarboxylic acid, and 2,6-naphthalenedicarboxylic acid, and among them, terephthalic acid is preferable.

Specific examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexanediol, cyclohexanehexanediol, diethylene glycol, hexamethylene glycol, and neopentyl glycol. Not limited to these. In particular, ethylene glycol, propylene glycol, and 1,4-butanediol are preferable because they are easy to handle during production and use. Ethylene glycol is more preferable from the viewpoint of heat resistance and mechanical properties, and 1,4-butanediol is more preferable from the viewpoint of crystallinity.

In the polyester of the present invention, the number average molecular weight of polyethylene glycol, which is a copolymerization component thereof, may be appropriately selected within the range in which the polyester has crystallinity. In the polyester of the present invention, the copolymerization rate of polyethylene glycol is 25 to 55 wt%. When the copolymerization rate of polyethylene glycol is less than 25 wt%, the ejection property of polyester is poor, and when the copolymerization rate of polyethylene glycol is larger than 55 wt%, the physical characteristics of the fibers formed from the obtained polyester are deteriorated. When the copolymerization rate of polyethylene glycol is 25 to 35 wt%, the ejectability of the obtained polyester is general. Therefore, in order to obtain a polyester having better ejection properties, it is preferable in the present invention. The copolymerization rate of polyethylene glycol is 35 to 55 wt%.

The preferred range depends on the composition of the polyester. For example, when the aliphatic diol which is a composition component of polyester is ethylene glycol, if the polyester molecular weight is too low, the polymerization temperature is too high, and the polyethylene glycol is seriously decomposed, resulting in polyester and thus produced. The moisture absorption rate of the fiber is reduced. Further, when the aliphatic diol which is a composition component of polyester is 1,4-butanediol, the polymerization temperature is lower than that when the above ethylene glycol is used, so that the decomposition of polyethylene glycol is relatively alleviated. As a result, the hygroscopicity of polyester and, by extension, the hygroscopicity after being produced into fibers are also improved.

When the aliphatic diol of the present invention is ethylene glycol, the number average molecular weight of polyethylene glycol is preferably 4000 to 30000 g / mol, and the copolymerization rate of polyethylene glycol is preferably 35 to 55 wt%. When the number average molecular weight of polyethylene glycol is 4000 g / mol or more, polyester has high hygroscopicity, and a fiber having excellent hygroscopicity can be obtained whether it is spun alone or in combination. In addition, the decrease in crystallinity of polyester and the decrease in the start temperature of external melting can be suppressed, and the occurrence of yarn breakage and fluffing after spinning is reduced, so that the process passability is good and a fiber structure such as a woven fabric or knitted fabric is formed. When it is used, the occurrence of stain spots and fluffing is reduced, and the quality is improved. On the other hand, when the number average molecular weight of polyethylene glycol is 30,000 g / mol or less, polycondensation reactivity is high and unreacted polyethylene glycol is reduced, thereby causing dissolution in hot water during hot water treatment such as dyeing. It can be suppressed and the moisture absorption characteristics after hot water treatment are maintained. The number average molecular weight of polyethylene glycol is preferably 25,000 g / mol or less, more preferably 20000 g / mol or less.

Further, when the copolymerization rate of polyethylene glycol is 35 wt% or more, polyester has high hygroscopicity, and fibers having excellent hygroscopicity can be obtained even if they are spun alone or in combination. On the other hand, when the copolymerization rate of polyethylene glycol is 55 wt% or less, after spinning polyester, the occurrence of yarn breakage and fluffing is reduced, so that the process passability is good and a fiber structure such as a woven fabric or knitted fabric is formed. When this is done, the occurrence of stain spots and fluffing is reduced, and the quality is improved. Further, it is possible to suppress the dissolution of polyethylene glycol during hot water treatment such as dyeing, and maintain the hygroscopicity of the fiber after hot water treatment.

When the aliphatic diol of the present invention is 1,4-butanediol, the number average molecular weight of polyethylene glycol is preferably 2000 to 30,000 g / mol, and the copolymerization rate of polyethylene glycol is preferably 35 to 35. It is 55 wt%. When the number average molecular weight of polyethylene glycol is 2000 g / mol or more, polyester has high hygroscopicity, and fibers having excellent hygroscopicity can be obtained even if they are spun alone or in combination. At the same time, it suppresses the decrease in crystallinity of polyester. At the same time, when the number average molecular weight of polyethylene glycol is 2000 g / mol or more, it is possible to suppress a decrease in the crystallinity of the polyester and a decrease in the external melting start temperature, and yarn breakage and fluffing occur in the drawing and false twisting steps. The number of dyed spots and fluffing is reduced when forming a fiber structure such as a woven fabric or a knitted fabric, and the quality is improved. On the other hand, when the number average molecular weight of polyethylene glycol is 30,000 g / mol or less, the polycondensation reactivity is high, unreacted polyethylene glycol is reduced, and dissolution in hot water during hot water treatment such as dyeing is suppressed. , Moisture absorption characteristics after hot water treatment can be maintained. The number average molecular weight of polyethylene glycol is preferably 27,000 g / mol or less, more preferably 25,000 g / mol or less, and most preferably 20000 g / mol or less. At the same time, when the copolymerization rate of polyethylene glycol is 35 wt% or more, the polyester has high hygroscopicity, and a fiber having excellent hygroscopicity can be obtained even if it is spun alone or in combination. On the other hand, when the copolymerization rate of polyethylene glycol is 55 wt% or less, the occurrence of yarn breakage and fluffing is reduced in the stretching and false twisting processes, so that the process passability is good and a fiber structure such as a woven fabric or a knitted fabric is formed. When this is done, the occurrence of stain spots and fluffing is reduced, and the quality is improved. At the same time, it is possible to suppress the dissolution of hot water during hot water treatment such as dyeing, and maintain the hygroscopicity after hot water treatment.

As is well known, when a large amount of a polyether compound is added to a polyester, the ether bond is heated and oxidatively decomposed, and the hygroscopicity of the fiber formed from the polyester is significantly reduced. Therefore, in the process of synthesizing polyester, a hindered phenol-based antioxidant is generally added, but after producing fibers from polyester, the free radical of the ether bond that has been oxidatively decomposed in the high-temperature dyeing process is based on hindered phenol. It attacks the para-position of the phenolic hydroxyl group of the antioxidant to produce quinones yellow substances. By the same mechanism, a _{yellow substance is produced even when it acts on NO 2} , which deteriorates the nitrogen oxide fastness of the fiber and adversely affects the use performance of the fiber. When the copolymerization rate of polyethylene glycol is less than 25 wt%, the amount of the added hindered phenolic antioxidant is generally small, so that the above-mentioned yellowing problem does not occur, while the copolymerization of polyethylene glycol is performed. If the rate is higher than 25 wt%, the problem of yellowing is relatively serious. In the present invention, since the half-hindered phenol-based antioxidant represented by the formula 1 is used, the half-hindered phenol-based antioxidant is present even when a free radical of an ether bond generated by oxidative decomposition by heating is present. Since it has a methyl group at the ortho position of the phenolic hydroxyl group of the antioxidant, the steric damage effect is small, and the free radical of the ether bond attacks the meta position of the phenolic hydroxyl group of the half-hindered phenolic antioxidant, which is why. , Does not produce yellow quinones.

(In the formula, R1 is a group to which one or more of hydrocarbons, oxygen and nitrogen are bonded, and R2 is a group to which one or more of hydrogen, hydrocarbons, oxygen and nitrogen are bonded. Is the basis.)

The half-hindered phenolic antioxidant of the present invention is preferably 3.9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propanoyl). Oxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, or 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)- It is 1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, the amount of which is added depends on the amount of polyethylene glycol, and finally the half-hindered phenolic antioxidant in polyester. The content of is preferably 1.0 to 8.0 wt%. If the content of the half-hindered phenolic antioxidant is too low, the oxidation resistance of the fiber formed from polyester deteriorates, and the oxidative decomposition of polyethylene glycol lowers the hygroscopicity of the polyester fiber, resulting in half-hindered phenol. If the content of the system antioxidant is too high, the polyester fiber will turn yellow due to the decomposition of the antioxidant itself.

In the present invention, the polyester is a polyether ester compound having a hygroscopicity difference (ΔMR) of 13.0 wt% or more. The hygroscopicity difference (ΔMR) of the present invention is a value measured by the method described in the specification. The polyester can be spun alone by a usual spinning method or spun in combination with other component polymers to obtain fibers having excellent hygroscopicity.

In the present invention, the fiber produced by the usual single or composite spinning method using the polyester has a change in the color tone L value of the fiber after being treated with hot water at 130 ° C. as compared with the treatment with unheated water. Hereinafter, it is preferably 4 or less. On the other hand, when the nitrogen oxide fastness test was performed on the fiber, the color tone yellowing value ΔYI was 10.0 or less, preferably 8.0 or less, and more preferably 7.5 or less. When ΔYI is 7.5 or less, the nitrogen oxide fastness is grade 4 to 5, and when ΔYI is 7.5 or more, the nitrogen oxide fastness is grade 4.

When synthesizing the polyester, a compound containing a titanium element or an antimony element may be added as a catalyst. Since the catalytic activity of the titanium-containing catalyst is high, it promotes side reactions and tends to adversely affect the color stability of the final polyester fiber. Therefore, when a titanium-containing catalyst is used, the addition amount of the polyester is based on the titanium element. It is preferably controlled in the range of 10 to 150 ppm. When an antimony element compound is used as a catalyst, the addition amount is in the range of 150 to 300 ppm of polyester based on the antimony element standard.

Various secondary additives may be added when synthesizing the polyester. As secondary additives, specifically, other types of antioxidants, phase solvents, plasticizers, ultraviolet absorbers, optical brighteners, antibacterial agents, nucleating agents, heat stabilizers, antistatic agents, etc. Examples include, but are not limited to, quenchers, defoamers, dyes, pigments, fragrances and the like. The above additive aids may be used alone or in combination.

The extrapolation melting start temperature of the polyester of the present invention is 180 ° C. or higher. The extrapolation melting start temperature of the polyester of the present invention is a value calculated by the method described in the specification. When multiple melting peaks are detected, it is calculated from the melting peak with the lowest temperature. When the external melting start temperature of polyester is 180 ° C or higher, after fibers are formed from polyester, yarn breakage and fluffing are less likely to occur, so that the process passability is good, and fiber structures such as woven fabrics and knitted fabrics. The occurrence of stain spots and fluffing is reduced and the quality is improved.

The fibers produced by spinning alone or in combination with other components by a normal spinning method using the polyester of the present invention, and the false plying and fiber structures formed from the fibers are excellent in moisture absorption. .. Therefore, it can be applied to applications that require comfort and high quality. For example, general clothing use, sports clothing use, bedding use, interior decoration use, material use and the like can be mentioned, but the present invention is not limited thereto.

Hereinafter, the present invention will be described in detail with specific examples. At the same time, the values of each characteristic in the examples are tested by the following method.

A. Difference in hygroscopicity between polyester and fiber (△ MR)

Using polyester and fibers as samples, first, they were dried with hot air at 60 ° C. for 30 minutes, and then allowed to stand in an ESPEC constant temperature and humidity chamber LHU-123 at a temperature of 20 ° C. and a humidity of 65% RH for 24 hours to obtain a polymer. The weight (W1) of the polymer is measured, and then the polymer is allowed to stand in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 90% RH for 24 hours, and the weight of the polymer (W2) is measured. Next, the polymer is dried with hot air at 105 ° C. for 2 hours, and the weight (W3) of the absolutely dried polymer is measured. Using the weights W1 and W3 of the polymer according to the following formula, the hygroscopicity MR1 (%) after standing for 24 hours in an atmosphere of 20 ° C. and 65% humidity RH from an absolute dry state is calculated, and the weight is calculated by the following formula. Using the combined weights W2 and W3, calculate the hygroscopicity MR2 (%) after standing for 24 hours in an atmosphere of 30 ° C. and 90% humidity RH from an absolute dry state, and then calculate the hygroscopicity difference by the following formula. (ΔMR) is calculated. However, each sample is measured 5 times, and the average value is taken as the hygroscopicity difference (ΔMR).
MR1 (%) = {(W1-W3) / W3} x 100,
MR2 (%) = {(W2-W3) / W3} x 100,
Hygroscopicity difference (ΔMR) (%) = MR2-MR1.

B. Hot water yellowing characteristics of fibers

The fibers formed by spinning the polyester produced in the examples alone or in combination with other components by a usual method are subjected to hot water treatment under the conditions of 130 ° C. × 20 minutes, and obtained. The L value of the sample was measured with a color difference meter (USTC-datacolor) and used as L2, the L value before hot water treatment was measured as L1, and L2-L1 was used as the hot water treatment yellowing value.

C. Fiber yellowing test

NOx gas generator (85% phosphoric acid and 85% phosphoric acid and (2% nitrite aqueous solution) is put in, then the test piece and the blue standard dyed cloth are put in the container, and when the color of the blue standard cloth fades to become standard gray board No. 3, the blue standard dyed cloth is put on. When the color is replaced and the color becomes standard gray board No. 3 again, the test piece is taken out, washed twice and dried. The yellowing value is measured with a Datacolor 650 spectrophotometer.

D. Copolymerization rate of polyethylene glycol

Copolymerization rate of polyethylene glycol: (Peak area of H in ether bond / Number of H in ether bond * Molecular weight of structural unit of polyether compound) / [(Peak area of H in ether bond / Number of H in ether bond * Molecular weight of structural unit of polyether compound) + (Peak area of H in isophthalic acid containing sodium sulfonate / 3 * Molecular weight of ester formed from isophthalic acid containing sodium sulfonate) + Peak area of H in PTA / 4 * PET molecular weight + H peak area of EG unit structure in polyester / 4 * Molecular weight of EG unit structure].

E. Number average molecular weight (Mn) of polyethylene glycol contained

Weigh 50 mg of the test piece in a flask, add 1 mL of aqueous ammonia to seal, and heat at a temperature of 120 ° C. for 3 hours. After cooling, the test piece is pulverized and then heated at 120 ° C. for 2 hours. After cooling, 1 ML of distilled water and 1.5 mL of 6 M hydrochloric acid are added, and the volume is adjusted in a 5 ML volumetric flask. After centrifugation (3500 rpm × 10 minutes), the filtrate is filtered through a 0.45 μm filtration filter, and the obtained filtrate is subjected to a GPC test. The test piece is subjected to a GPC test (Alliance 2690 manufactured by Waters) under the following conditions. If the molecular weight is less than 1800, it cannot be separated from impurities, and except for this case, the number average molecular weight is obtained.

Detector: RI-8020 made by Japan "Tosoh", sensitivity 128x

Column: TSKge1G3000PWXL I made by Japan "Tosoh"

Solvent: 0.1M sodium chloride aqueous solution

Injection amount: 200 μm

Column temperature: 40 ° C

Standard substance: Polyethylene glycol (Mn106-101000 g / mol manufactured by "AMAL Co., Ltd.").

F. Content of half-hindered phenolic antioxidants and hindered phenolic antioxidants

Pretreatment: 8 g of polyester is refluxed with 150 ml of solvent toluene for 35 minutes, cooled to 100 ° C., then placed in a centrifuge tube, then centrifuged to eliminate the upper liquid. Filter through a .45 μm filter, then dilute with methanol and centrifuge to obtain a superficial liquid, finally add an internal standard, filter through a 0.45 μm filter and measure by HPLC. ..

HPLC measurement: mobile phase A / B: methanol / water (12%); flow velocity: 1.3 ml / min; column temperature: 40 degrees; ultraviolet wavelength: 284 nm; time: 15 min.

G. Extrapolation melting start temperature

Using the polymer as the core component and the sheath component and the fibers obtained in the examples as test pieces, the extrapolation melting start temperature is measured using a Q2000 type differential scanning calorimeter (DSC) manufactured by TA Instruments. First, in an atmosphere of nitrogen gas, 5 mg of the test piece is heated from 0 ° C. to 280 ° C. at a heating rate of 50 ° C./min and held at 280 ° C. for 5 minutes to eliminate the heat history. Next, the temperature is rapidly cooled from 280 ° C. to 0 ° C., then the temperature is raised from 0 ° C. to 280 ° C. at a rate of 3 ° C./min, the temperature modulation width is set to ± 1 ° C., and the temperature is raised after 60 seconds of the temperature modulation cycle. Then, TMDSC is measured. JIS K7121: 1987 (Measurement method of transition temperature of plastic) 9.1 The extrapolation melting start temperature is calculated based on the melting peak observed in the second heating process according to the standard. Measure 3 times for each sample, and use the average value as the extrapolation melting start temperature. When a plurality of melting peaks are observed, the extrapolated melting start temperature is calculated based on the melting peak on the lowest temperature side.

Example 1

10.9 kg of terephthalic acid and 4.7 kg of ethylene glycol were put into an esterification kettle, heated to 230 ° C. with stirring to carry out an esterification reaction, and then transferred to a polycondensation kettle, and the final total amount of polyester was obtained. 35 wt% polyethylene glycol 8300 (polyester glycol having a number average molecular weight of 8300 g / mol, abbreviation PEG8300) was added to polymerize 250 ppm of antimonate trioxide with respect to the total content of the final polyester based on the antimony element. As a catalyst, 250 ppm of trimethyl phosphate as a stabilizer was added to the total amount of the final polyester, and after 5 minutes, the pressure was reduced to raise the temperature, and the final temperature was 285 ° C. and the final pressure was reached, and then the reaction system was charged. 1,3,5-Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-which is a half-hindered phenolic antioxidant of 1.0 wt% of the total amount of the final polyester. Add 1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (CN1790), stir for 10 minutes, introduce nitrogen gas into the reaction system to make it normal pressure, and polycondensate. The reaction was stopped to obtain a copolymerized polyester.

The obtained polyester chips were melt-spun at a spinning speed of 3 Km / min to obtain semi-drawn yarns. Next, the partially oriented yarn obtained was subjected to false twisting under processing conditions where the temperature of the first heater was 180 ° C., the temperature of the second heater was normal temperature, and the draw ratio was 1.7, and high hygroscopicity was obtained. Polyester fibers were obtained. The specific physical characteristics of polyester and fiber are shown in Table 1.

Example 2

It was the same as in Example 1 except that the addition amount of PEG8300 was 40 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.1 wt%. Specifically, it is shown in Table 1.

Example 3

It was the same as in Example 1 except that the addition amount of PEG11000 (number average molecular weight 11000 g / mol) was 35 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.0 wt%. Specifically, it is shown in Table 1.

Example 4

It was the same as in Example 1 except that the addition amount of PEG20000 (number average molecular weight 20000 g / mol) was 35 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.0 wt%. Specifically, it is shown in Table 1.

Example 5

It was the same as in Example 1 except that the addition amount of PEG30000 (number average molecular weight 30,000 g / mol) was 35 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.0 wt%. Specifically, it is shown in Table 1.

Example 6

It was the same as in Example 1 except that the addition amount of PEG8300 was 35 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 3.0 wt%. Specifically, it is shown in Table 1.

Example 7

It was the same as in Example 1 except that the addition amount of PEG8300 was 35 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 5.0 wt%. Specifically, it is shown in Table 1.

Example 8

The amount of PEG8300 added is 35 wt%, and it is a half-hindered phenolic antioxidant, 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propa. It was the same as in Example 1 except that the amount of noyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (AO80) was set to 1.6 wt%. Specifically, it is shown in Table 1.

Example 9

It was the same as in Example 1 except that the addition amount of PEG8300 was 35 wt% and the addition amount of the half-hindered phenolic antioxidant AO80 was 4.7 wt%. Specifically, it is shown in Table 1.

Example 10

It was the same as in Example 1 except that the addition amount of PEG8300 was 35 wt% and the addition amount of the half-hindered phenolic antioxidant AO80 was 8.0 wt%. Specifically, it is shown in Table 1.

Example 11

It was the same as in Example 1 except that the addition amount of PEG8300 was 30 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.0 wt%. Specifically, it is shown in Table 1.

Example 12

It was the same as in Example 1 except that the addition amount of PEG8300 was 27 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 10.0 wt%. Specifically, it is shown in Table 1.

Example 13

10.9 kg of terephthalic acid and 11.8 kg of 1,4-butanediol were put into an esterification kettle, 450 ppm of a tetrabutyl titanate catalyst was added to the total amount of the final polyester, and the temperature was raised to 230 ° C. with stirring. After the esterification reaction, the mixture is transferred to a polycondensation kettle, and 45 wt% polyethylene glycol 3400 (polyester glycol having a number average molecular weight of 3400 g / mol, abbreviation PEG3400) is added to the total amount of the final polyester to make the final polyester. To the total amount of polyester, 900 ppm of tetrabutyl titanate catalyst and 250 ppm of trimethyl phosphate, which is a stabilizer, were added to the total amount of final polyester, and after 5 minutes, the pressure was reduced to raise the temperature, and the final temperature was 250 ° C. After reaching the final pressure, 1,3,5-tris (4-tert-butyl-3), a half-hindered phenolic antioxidant, is 1.3 wt% of the total amount of final polyester in the reaction system. -Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trion (CN1790) was added, and after stirring for 10 minutes, nitrogen was added to the reaction system. A gas was introduced to bring the pressure to normal, and the polycondensation reaction was stopped to obtain a copolymerized polyester.

The obtained polyester chips were melt-spun at a spinning speed of 3 Km / min to obtain semi-drawn yarns. Next, the semi-drawn yarn obtained was subjected to false twisting under processing conditions where the temperature of the first heater was 180 ° C., the temperature of the second heater was normal temperature, and the draw ratio was 1.7, and high hygroscopicity was obtained. Polyester fibers were obtained. Table 2 shows the specific physical characteristics of polyester and fiber.

Example 14

It was the same as in Example 13 except that the addition amount of PEG3400 was 55 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.4 wt%. Specifically, it is shown in Table 2.

Example 15

It was the same as in Example 13 except that the addition amount of PEG3400 was 58 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.8 wt%. Specifically, it is shown in Table 2.

Example 16

It was the same as in Example 13 except that the addition amount of PEG11000 was 55 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.4 wt%. Specifically, it is shown in Table 2.

Example 17

It was the same as in Example 13 except that the addition amount of PEG20000 was 55 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.4 wt%. Specifically, it is shown in Table 2.

Example 18

It was the same as in Example 13 except that the addition amount of PEG3400 was 55 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 4.2 wt%. Specifically, it is shown in Table 2.

Example 19

It was the same as in Example 13 except that the addition amount of PEG3400 was 55 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 8.0 wt%. Specifically, it is shown in Table 2.

Example 20

The amount of PEG3400 added is 55 wt%, and it is a half-hindered phenolic antioxidant, 3,9-bis [1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propa. It was the same as in Example 13 except that the amount of noyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (AO80) was set to 2.2 wt%. Specifically, it is shown in Table 2.

Example 21

It was the same as in Example 13 except that the addition amount of PEG3400 was 55 wt% and the addition amount of the half-hindered phenolic antioxidant AO80 was 6.6 wt%. Specifically, it is shown in Table 2.

Example 22

It was the same as in Example 13 except that the addition amount of PEG3400 was 55 wt% and the addition amount of the half-hindered phenolic antioxidant AO-80 was 8.0 wt%. Specifically, it is shown in Table 2.

Example 23

It was the same as in Example 13 except that the addition amount of PEG3400 was 50 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 10.0 wt%. Specifically, it is shown in Table 2.

Example 24

10.9 kg of terephthalic acid and 4.7 kg of ethylene glycol were put into an esterification kettle, heated to 230 ° C. with stirring to carry out an esterification reaction, and then transferred to a polycondensation kettle, and the final total amount of polyester was obtained. Add 50 wt% polyethylene glycol 8300 (polyethylene glycol with a number average molecular weight of 8300 g / mol, abbreviation PEG8300) to add 250 ppm of antimonate trioxide to the final total polyester content based on the antimony element. As a polymerization catalyst, 250 ppm of trimethyl phosphate as a stabilizer was added to the total amount of the final polyester, and after 5 minutes, the pressure was reduced to raise the temperature, and the final temperature reached 285 ° C. and the final pressure was reached. 1,3,5-Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-which is a half-hindered phenolic antioxidant with 1.0 wt% of the total amount of the final polyester. Add 1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (CN1790), stir for 10 minutes, introduce nitrogen gas into the reaction system to make it normal pressure, and polycondensate. The reaction was stopped to obtain a copolymerized polyester.

The above polyester is used as an island component and polyethylene terephthalate (IV = 0.66) is used as a sea component. After vacuum drying at 150 ° C. for 12 hours, screw type composite spinning is performed at a blending ratio of 20 wt% for the island component and 80 wt% for the sea component. The yarn was supplied into the machine and melted, and the yarn was spun using a sea-island type composite spinneret (having 24 islands for each discharge hole) at a spinning temperature of 285 ° C. and a discharge rate of 36 g / min. The spun yarn is cooled by cold air at an air temperature of 20 ° C. and a wind speed of 20 m / min, refueled by a refueling device, focused, and stretched by a first stage roller rotating at 2500 m / min. The undrawn yarn of 144dtex-36f was obtained by winding with a second stage roller having the same rotation speed as the first stage roller. Next, using a draw false twisting machine (twisting part: friction disc type, heater part: contact type), the obtained undrawn yarn is stretched under the conditions of a heater temperature of 170 ° C. and a magnification of 1.7 times. It was twisted to obtain a false twisted yarn of 84 dtex-36f.

Table 3 shows the evaluation results of the fiber characteristics, fabric characteristics and process passability of the obtained fibers. The number of yarn breaks during false twisting was 0, and the process passability was extremely good. In addition, the hygroscopicity after the hot water treatment is almost not lowered, and the hygroscopicity after the hot water treatment is also excellent. Moreover, both the leveling property and the quality have reached the passing level. Specifically, it is shown in Table 3.

Example 25

It was the same as in Example 24 except that the amount of the half-hindered phenolic antioxidant CN1790 added was 3.0 wt%. Specifically, it is shown in Table 3.

Example 26

It was the same as in Example 24 except that the addition amount of the half-hindered phenolic antioxidant CN1790 was 5.0 wt%. Specifically, it is shown in Table 3.

Example 27

It was the same as in Example 24 except that the addition amount of PEG8300 was 45 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 5.0 wt%. Specifically, it is shown in Table 3.

Example 28

It was the same as in Example 24 except that the addition amount of PEG8300 was 55 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 5.0 wt%. Specifically, it is shown in Table 3.

Example 29

It was the same as in Example 24 except that the amount of the half-hindered phenolic antioxidant AO80 added was 1.6 wt%. Specifically, it is shown in Table 3.

Example 30

It was the same as in Example 24 except that the addition amount of the half-hindered phenolic antioxidant AO80 was 4.7 wt%. Specifically, it is shown in Table 3.

Example 31

It was the same as in Example 24 except that the addition amount of the half-hindered phenolic antioxidant AO80 was 8.0 wt%. Specifically, it is shown in Table 3.

Example 32

It was the same as in Example 24 except that the addition amount of the half-hindered phenolic antioxidant CN1790 was 2.0 wt%. Specifically, it is shown in Table 3.

Example 33

It was the same as in Example 24 except that the addition amount of the half-hindered phenolic antioxidant AO80 was 4.0 wt%. Specifically, it is shown in Table 3.

Example 34

It was the same as in Example 24 except that the addition amount of the half-hindered phenolic antioxidant AO80 was 6.0 wt%. Specifically, it is shown in Table 3.

Example 35

It was the same as in Example 24 except that the amount of the half-hindered phenolic antioxidant CN1790 added was 9.0 wt%. Specifically, it is shown in Table 3.

Example 36

It was the same as in Example 24 except that the addition amount of the half-hindered phenolic antioxidant CN1790 was 0.9 wt%. Specifically, it is shown in Table 3.

Example 37

10.9 kg of terephthalic acid and 11.8 kg of 1,4-butanediol were put into an esterification kettle, 450 ppm of a tetrabutyl titanate catalyst was added to the total amount of the final polyester, and the temperature was raised to 230 ° C. with stirring. After the esterification reaction, the mixture is transferred to a polycondensation kettle, and 50 wt% polyethylene glycol 8300 (polyester glycol having a number average molecular weight of 8300 g / mol, abbreviation PEG8300) is added to the total amount of the final polyester. 900 ppm of tetrabutyl titanate catalyst was added to the total amount of polyester, and 250 ppm of trimethyl phosphate, which is a stabilizer, was added to the total amount of final polyester. After reaching the final pressure, 1,3,5-tris (4-tert-butyl-3), a half-hindered phenolic antioxidant, is 1.3 wt% of the total amount of final polyester in the reaction system. -Hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trion (CN1790) was added, and after stirring for 10 minutes, nitrogen was added to the reaction system. A gas was introduced to bring the pressure to normal, and the polycondensation reaction was stopped to obtain a copolymerized polyester. The rest was the same as in Example 24. Specifically, it is shown in Table 4.

Example 38

It was the same as in Example 37 except that the amount of the half-hindered phenolic antioxidant CN1790 added was 2.4 wt%. Specifically, it is shown in Table 4.

Example 39

It was the same as in Example 37 except that the addition amount of the half-hindered phenolic antioxidant CN1790 was 4.2 wt%. Specifically, it is shown in Table 4.

Example 40

It was the same as in Example 37 except that the amount of the half-hindered phenolic antioxidant CN1790 added was 8.0 wt%. Specifically, it is shown in Table 4.

Example 41

It was the same as in Example 37 except that the addition amount of the half-hindered phenolic antioxidant AO80 was 2.2 wt%. Specifically, it is shown in Table 4.

Example 42

It was the same as in Example 37 except that the amount of the half-hindered phenolic antioxidant AO80 added was 6.6 wt%. Specifically, it is shown in Table 4.

Example 43

It was the same as in Example 37 except that the addition amount of PEG8300 was 45 wt% and the addition amount of the half-hindered phenolic antioxidant AO80 was 6.6 wt%. Specifically, it is shown in Table 4.

Example 44

It was the same as in Example 37 except that the addition amount of PEG8300 was 55 wt% and the addition amount of the half-hindered phenolic antioxidant AO80 was 6.6 wt%. Specifically, it is shown in Table 4.

Example 45

It was the same as in Example 37 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the half-hindered phenolic antioxidant AO80 was 8.0 wt%. Specifically, it is shown in Table 4.

Example 46

It was the same as in Example 37 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 2.0 wt%. Specifically, it is shown in Table 4.

Example 47

It was the same as in Example 37 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 3.0 wt%. Specifically, it is shown in Table 4.

Example 48

It was the same as in Example 37 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 5.0 wt%. Specifically, it is shown in Table 4.

Example 49

It was the same as in Example 37 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the half-hindered phenolic antioxidant AO80 was 4.0 wt%. Specifically, it is shown in Table 4.

Example 50

It was the same as in Example 37 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the half-hindered phenolic antioxidant AO80 was 6.0 wt%. Specifically, it is shown in Table 4.

Example 51

It was the same as in Example 37 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 9.0 wt%. Specifically, it is shown in Table 4.

Comparative Example 1

It was the same as in Example 1 except that the addition amount of PEG8300 was 12 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.0 wt%. Specifically, it is shown in Table 5. Due to the small amount of PEG added, a high hygroscopic effect could not be realized.

Comparative Example 2

It was the same as in Example 1 except that the addition amount of PEG8300 was 20 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.0 wt%. Specifically, it is shown in Table 5. Due to the small amount of PEG added, a high hygroscopic effect could not be realized.

Comparative Example 3

It was the same as in Example 1 except that the addition amount of PEG100,000 (number average molecular weight 100,000 g / mol) was 30 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 2.0 wt%. Specifically, it is shown in Table 5. Since ultra-high molecular weight PEG was added, it expanded after ejection, making it difficult to eject.

Comparative Example 4

It was the same as in Example 13 except that the addition amount of PEG3400 was 12 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 0.8 wt%. Specifically, it is shown in Table 5. Due to the small amount of PEG added, a high hygroscopic effect could not be realized.

Comparative Example 5

It was the same as in Example 13 except that the addition amount of PEG3400 was 70 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 4.6 wt%. Specifically, it is shown in Table 5. Since the amount of PEG3400 added is too high, the final external melting start temperature of the polyester is excessively lowered, and the fibers formed from the polyester are prone to yarn breakage and fluffing, resulting in deterioration of process passability. As a result, when a fiber structure such as a woven fabric or a knitted fabric is formed, the occurrence of dyeing spots and fluffing increases, and the quality deteriorates.

Comparative Example 6

It was the same as in Example 13 except that the addition amount of PEG600 (number average molecular weight 600 g / mol) was 50 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 3.3 wt%. Specifically, it is shown in Table 5. Since the molecular weight of PEG was too low, it was scattered in a large amount during the polymerization process, and even if it was added in a large amount, the hygroscopicity of the obtained polyester was poor.

Comparative Example 7

It was the same as in Example 13 except that the addition amount of PEG100000 was 50 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 3.3 wt%. Specifically, it is shown in Table 5. Since ultra-high molecular weight PEG was added, it expanded after ejection, making it difficult to eject.

Comparative Example 8

It was the same as in Example 13 except that the addition amount of PEG3400 was 20 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.0 wt%. Specifically, it is shown in Table 5. Due to the small amount of PEG added, a high hygroscopic effect could not be realized.

Comparative Example 9

It was the same as in Example 1 except that the addition amount of PEG8300 was 20 wt% and the addition amount of the hindered phenolic antioxidant (IR1010) was 0.5 wt%. Specifically, it is shown in Table 5. Compared with half- hindered phenolic antioxidants, hindered phenolic antioxidants were more likely to cause yellowing of polyester. When the amount of PEG added is small, even if a small amount of tetrakis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol IR1010, which is a hindered phenolic antioxidant, is added, polyester Although the yellowing index of the polyester is within an acceptable range, the antioxidant effect of the polyester is reduced, and the difference in the moisture absorption rate of the polyester fiber before and after dyeing is large. It was shown to decrease significantly.

Comparative Example 10

It was the same as in Example 1 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the hindered phenolic antioxidant IR1010 was 3.0 wt%. Specifically, it is shown in Table 5. When a large amount of hindered phenolic antioxidant was added, the antioxidant effect was high, but yellowing was likely to occur in the fibers.

Comparative Example 11

It was the same as in Example 1 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the hindered phenolic antioxidant IR1010 was 0.5 wt%. Specifically, it is shown in Table 5. When a small amount of a hindered phenolic antioxidant was added, the yellowing of the fibers could be suppressed, but the antioxidant effect was reduced.

Comparative Example 12

It was the same as in Example 13 except that the addition amount of PEG3400 was 20 wt% and the addition amount of the hindered phenolic antioxidant IR1010 was 0.5 wt%. Specifically, it is shown in Table 5. Compared with half-hindered phenolic antioxidants, hindered phenolic antioxidants were more likely to cause yellowing of polyester. When the amount of PEG added is small, even if a small amount of the hindered phenolic antioxidant IR1010 is added, the yellowing index of the polyester is within an acceptable range, but the antioxidant effect of the polyester is reduced, and the polyester before and after dyeing. The difference in the hygroscopicity of the fibers was large, indicating that the hygroscopicity of the dyed polyester fibers was significantly reduced.

Comparative Example 13

It was the same as in Example 13 except that the addition amount of PEG3400 was 50 wt% and the addition amount of the hindered phenolic antioxidant IR1010 was 3.0 wt%. Specifically, it is shown in Table 5. When a large amount of hindered phenolic antioxidant was added, the antioxidant effect was high, but yellowing was likely to occur in the fibers.

Comparative Example 14

It was the same as in Example 13 except that the addition amount of PEG3400 was 50 wt% and the addition amount of the hindered phenolic antioxidant IR1010 was 0.5 wt%. Specifically, it is shown in Table 5. When a small amount of a hindered phenolic antioxidant was added, the yellowing of the fibers could be suppressed, but the antioxidant effect was reduced.

Comparative Example 15

It was the same as in Example 1 except that the addition amount of PEG8300 was 22 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.0 wt%. Specifically, it is shown in Table 5. Due to the inappropriate addition amount of PEG8300, the ejection property was poor.

Comparative Example 16

It was the same as in Example 1 except that the addition amount of PEG8300 was 25 wt% and the addition amount of the half-hindered phenolic antioxidant CN1790 was 1.0 wt%. Specifically, it is shown in Table 5. Due to the inappropriate addition amount of PEG8300, the ejection property was poor.

Comparative Example 17

It was the same as in Example 24 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the hindered phenolic antioxidant IR1010 was 3.0 wt%. Specifically, it is shown in Table 6. In the case of compound spinning, when a large amount of hindered phenolic antioxidant was added, the antioxidant effect was high, but yellowing was likely to occur in the fibers.

Comparative Example 18

It was the same as in Example 24 except that the addition amount of PEG8300 was 50 wt% and the addition amount of the hindered phenolic antioxidant IR1010 was 0.8 wt%. Specifically, it is shown in Table 6. In the case of compound spinning, when a small amount of a hindered phenolic antioxidant was added, yellowing of the fibers could be suppressed, but the antioxidant effect was reduced.

Comparative Example 19

It was the same as in Example 24 except that the amount of PEG8300 added was 50 wt% and no antioxidant was added. Specifically, it is shown in Table 6. Since no antioxidant is added, the fibers do not yellow, but they do not have an antioxidant effect.

Claims (3)

It ’s polyester,
It is a polymer formed with an aromatic dicarboxylic acid or a derivative thereof and 1,4-butanediol as a main composition component and polyethylene glycol as a copolymerization component, and the number average molecular weight of polyethylene glycol is 2000 to 30,000 g / mol. A polyester having a polymerization rate of 25 to 55 wt% and containing 5.21 to 8.0 wt% of a half-hindered phenolic antioxidant represented by the formula 2 in the polyester.

The polyester according to claim 1, wherein the polyethylene glycol has a copolymerization rate of 35 to 55 wt%. Polyesters of the aromatic dicarboxylic acid or derivative thereof according to請Motomeko 2 Ru derivatives der terephthalic acid or terephthalic acid.