KR102356959B1 - Polyester - Google Patents

Abstract

The polyester disclosed in the present invention is a polymer formed by an aromatic dicarboxylic acid or a derivative thereof and an aliphatic diol as a main component, and polyethylene glycol as a copolymerization component, and the number average molecular weight of the polyethylene glycol is 2000-30000 g/mol, , the copolymerization ratio is 25 to 55% by weight. The polyester of the present invention, the fibers produced through individual spinning by a conventional spinning method or composite spinning with other components, and the twisted filaments and fiber structures made of the polyester have excellent hygroscopicity. Therefore, the polyester of the present invention can be used in applications where comfort and quality are required.

Description

Polyester

The present invention relates to polyester having excellent hygroscopicity.

Polyester has various uses in the fields of fibers, films, and plastics due to its excellent properties. However, due to the regular structure and strong hydrophobicity of polyester, compared with natural fibers such as cotton or hemp, polyester fibers lack absorbency and hygroscopicity, and the use of polyester fibers in hygroscopic environments is greatly limited. . When textiles obtained from polyester fibers are used to fabricate clothing that adheres to the body, polyester fibers provide a feeling of sweltering heat due to lack of absorbency, so polyester fibers are particularly unsuitable for use in summer clothing.

In order to solve the problem of insufficient absorbency and hygroscopicity of polyester fibers, a number of methods have been tried by those skilled in the art. For example, the surface of the fiber is mainly modified to make the surface of the fiber porous, and then the hygroscopicity of the fiber is improved by the capillary principle. Further, the modification of the fiber surface can be achieved by methods such as electric discharge treatment, photograft modification and low-temperature plasma treatment. However, after the fibers obtained by these methods are made into fabrics, the effect of reducing the burning sensation in a sweating state or the like is not good, and there is no feeling of refreshing feeling like that of natural fibers such as cotton or hemp. In addition to these methods, there is a method of coating a hydrophilic film on the surface of the fiber, but this method often has problems of insufficient affinity between the fibers and the film and insufficient durability after washing.

In addition, by chemically grafting the polyester fibers, the moisture absorption properties of the fibers can be improved. For example, after graft copolymerization of acrylic acid and methacrylic acid to about 15% of polyethylene terephthalate (PET) fiber, sodium ion exchange treatment is performed to obtain a moisture absorption rate equivalent to that of cotton. However, the fiber absorbs moisture too slowly, and the basic properties of the polyester fiber are greatly impaired, so that it has no practical use value and has not yet been industrially produced.

Also, although high molecular weight polyether compounds are used to improve the hygroscopicity, the high molecular weight polyether compounds are not completely copolymerized with the polyester matrix, and most of them are present in the polyester in a phase-separated state, so that it may be kept molten. In this case, the polymer is coarsened to cause the formation of an unstable phase-separation structure, and the discharge from the spinneret during discharge and spinning is unstable after the polymerization reaction is completed, resulting in large fineness stains, dyeing stains, and fluff. In Japanese Patent Application Laid-Open No. 2007-70467, a specific copolymer of PEG and PET is used to improve the water absorption performance of PET. However, if the amount of PEG added is too small, high hygroscopicity is not obtained and a large amount of addition is required, as a result, the basic properties of the fiber after formation of the polyester fiber are lost, and heat resistance, hot water resistance and resistance to generation of oxidative heat are greatly increased. As it deteriorates, its usefulness becomes very low.

An object of the present invention is to provide a polyester having excellent hygroscopicity, and the fiber obtained by spinning the polyester has excellent resistance to hot water and oxidation heat generation.

The technical solution of the present invention is as follows:

A polyester as a polymer formed by an aromatic dicarboxylic acid or a derivative thereof as a main component and an aliphatic diol and polyethylene glycol as a copolymerization component, wherein the polyethylene glycol has a number average molecular weight of 2000 to 30000 g/mol, and a copolymerization ratio of 25 -55% by weight, wherein the polyester also includes a half hindered phenolic antioxidant as shown in Formula 1.

식 1

Equation 1

wherein R 1 is a group formed by one or a combination of hydrocarbon, oxygen and nitrogen; R2 is a group formed by one or a combination of hydrogen, hydrocarbon, oxygen and nitrogen.

The half-hindered phenolic antioxidant is preferably included in an amount of 1.0 to 8.0% by weight based on the total weight of the polyester.

The half hindered phenolic antioxidant is an antioxidant 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoylox as shown in formula 2 cy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, or the antioxidant 1,3,5-tris(4-tert-butyl-3-hydroxy- as shown in Formula 3) It is preferably 2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.

식 2

Equation 2

식 3

Equation 3

The copolymerization ratio of polyethylene glycol is preferably 35 to 55% by weight.

The aliphatic diol is preferably ethylene glycol or 1,4-butanediol; When it is preferred that the aliphatic diol is ethylene glycol, the number average molecular weight of the polyethylene glycol is preferably 4,000 to 30,000 g/mol.

In the polyester of the present invention, polyethylene glycol has a high copolymerization ratio, the polyester chip has excellent hygroscopicity, and the difference in moisture absorption rate before and after dyeing the polyester fiber is small. On the other hand, polyester has good heat resistance, excellent anti-yellowing properties, and high utility value.

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

Aromatic dicarboxylic acids or derivatives thereof include terephthalic acid, isophthalic acid, phthalic acid, sodium isophthalate-5-sulfonate, lithium isophthalate-5-sulfonate, 5-(tetraalkyl)-isophthalatesulfonate phosphorus compounds, Although 4,4'-biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, etc. can be illustrated concretely, It is not limited to these, Among these, terephthalic acid is preferable.

Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexanediol, cyclohexanehexanediol, diethylene glycol, hexamethyl glycol, neopentyl glycol, and the like. It is not limited. In particular, ethylene glycol, propylene glycol, and 1,4-butanediol are preferred for their accessibility in production and use. From the viewpoints of heat resistance and mechanical properties, ethylene glycol is more preferable; From the viewpoint of crystallinity, 1,4-butanediol is more preferable.

The number average molecular weight of polyethylene glycol, which is a copolymer component of the polyester of the present invention, may be appropriately selected within the range in which the polyester has crystallinity. The copolymerization ratio of polyethylene glycol in the polyester of this invention is 25 to 55 weight%. If the copolymerization ratio of polyethylene glycol is less than 25% by weight, the discharge characteristics of the polyester are poor; When the copolymerization ratio of polyethylene glycol exceeds 55% by weight, the physical properties of the fibers formed of the obtained polyester are deteriorated. When the copolymerization ratio of polyethylene glycol is between 25 and 35% by weight, the obtained polyester has normal discharge characteristics. It is preferable in the present invention that

The preferred range depends on the composition of the polyester. For example, when the aliphatic diol of the polyester component is ethylene glycol, if the molecular weight of the polyester is too low, the deterioration of polyethylene glycol due to the high polymerization temperature is extreme, and also the moisture absorption rate of the final polyester or even the formed fiber is low. can decrease. On the other hand, when the aliphatic diol, which is a component of the polyester, is 1,4-butanediol, the deterioration of polyethylene glycol is relatively less serious because of the lower polymerization temperature compared to the case where ethylene glycol is used. Accordingly, the hygroscopicity of the polyester and the hygroscopicity after fiber formation can also be improved.

When the aliphatic diol of the present invention is ethylene glycol, the number average molecular weight of polyethylene glycol is preferably 4,000 to 30,000 g/mol, and the copolymerization ratio of polyethylene glycol is preferably 35 to 55% by weight. When the number average molecular weight of polyethylene glycol is 4,000 g/mol or more, polyester has high hygroscopicity, and fibers excellent in hygroscopicity can be obtained by each spinning or composite spinning. On the other hand, since the lowering of the crystallinity of the polyester and the lowering of the extrapolated melting initiation temperature can be suppressed, and the filament breakage and the occurrence of fluff after spinning of the polyester are reduced, the process passability is excellent, such as woven or knitted fabrics In the case of forming a fiber structure, since the occurrence of dye stains and fluff is reduced, the quality is excellent. 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, so elution into hot water can be suppressed during hydrothermal treatment such as dyeing, so that hydrothermal treatment Hygroscopicity may be maintained afterward. The number average molecular weight of polyethylene glycol is preferably 25,000 g/mol or less, and more preferably 20,000 g/mol or less.

On the other hand, when the copolymerization ratio of polyethylene glycol is 35% by weight or more, polyester has high hygroscopicity, and fibers having excellent hygroscopicity can be obtained by individual spinning or composite spinning. On the other hand, when the copolymerization ratio of polyethylene glycol is 55% by weight or less, filament breakage and fluff after spinning of polyester are reduced, process passability is good, and when forming a fibrous structure such as a woven or knitted fabric, dyeing Since the occurrence of unevenness and fluff is reduced, the quality is excellent. On the other hand, the elution of polyethylene glycol can be suppressed during hydrothermal treatment such as dyeing, so that the hygroscopicity of the fiber after hydrothermal treatment can be maintained.

When the aliphatic diol of the present invention is 1,4-butanediol, the number average molecular weight of polyethylene glycol is preferably 2,000 to 30,000 g/mol, and the copolymerization ratio of polyethylene glycol is preferably 35 to 55% by weight. When the number average molecular weight of polyethylene glycol is 2,000 g/mol or more, the polyester has high hygroscopicity, and fibers excellent in hygroscopicity can be obtained by individual spinning or composite spinning. On the other hand, the reduction in crystallinity of the polyester can be suppressed. On the other hand, when the number average molecular weight of polyethylene glycol is 2,000 g/mol or more, a decrease in the crystallinity of the polyester and a decrease in the extrapolated melting initiation temperature can be suppressed, and the filament breakage and fluff generation during stretching and false twisting treatment are reduced As a result, the process passability is good, and when forming a fibrous structure such as a woven or knitted fabric, the occurrence of dye stains and fluff is reduced, thereby improving the quality. On the other hand, when the number average molecular weight of polyethylene glycol is 30,000 g/mol or less, polycondensation reactivity is high, unreacted polyethylene glycol is reduced, and thus elution to hot water can be suppressed during hydrothermal treatment such as dyeing, Hygroscopicity can be maintained after hydrothermal treatment. 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 20,000 g/mol or less. On the other hand, when the copolymerization ratio of polyethylene glycol is 35% by weight or more, polyester has high hygroscopicity, and fibers having excellent hygroscopicity can be obtained by individual spinning or composite spinning. On the other hand, when the copolymerization ratio of polyethylene glycol is 55% by weight or less, breakage of filaments and generation of fluff during stretching and false twisting treatment are reduced, process passability is good, and when forming a fibrous structure such as a woven or knitted fabric, The quality is excellent because the occurrence of dye stains and fluff is reduced. On the other hand, elution to hot water can be suppressed during hydrothermal treatment such as dyeing, so that hygroscopicity can be maintained after hydrothermal treatment.

When a large amount of polyether compound is added to the polyester, the ether bond is oxidatively differentiated by heating, so that the hygroscopicity of the polyester is rapidly reduced after fiber formation. Therefore, in the synthesis of polyesters, hindered phenolic antioxidants are usually added. However, during the high-temperature dyeing process after fabricating the fibers from polyester, the oxidatively decomposed ether bond radicals attack the para position of the phenolic hydroxyl group of the hindered phenolic antioxidant to form a quinone yellow substance. By the same mechanism, a _{yellow material is formed after reaction with NO 2} , which makes the nitrogen-oxygen fastness of the fiber unsuitable, and affects the performance of the fiber. When the copolymerization ratio of polyethylene glycol is less than 25% by weight, the added amount of the hindered phenolic antioxidant is generally small, so that the yellowing problem does not occur; When the copolymerization ratio of polyethylene glycol exceeds 25% by weight, the yellowing problem is more serious. The present invention uses a half-hindered phenolic antioxidant as shown in Equation 1, despite the formation of ether bond radicals by thermal oxidative decomposition, wherein the ortho position of the phenolic hydroxyl groups of the half-hindered phenolic antioxidant This is because is a methyl group, and the steric hindrance effect is relatively small, so that the ether bond radical attacks the meta position of the phenolic hydroxyl group of the half hindered phenolic antioxidant, so that a yellow quinone material is not formed.

식 1

Equation 1

wherein R 1 is a group formed by one or a combination of hydrocarbon, oxygen and nitrogen; R2 is a group formed by one or a combination of hydrogen, hydrocarbon, oxygen and nitrogen.

The half hindered phenolic antioxidant of the present invention is 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethyl]- 2,4,8,10-tetraoxaspiro[5.5]undecane, or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5 -triazine-2,4,6-(1H,3H,5H)-trione is preferable. The amount to be added varies depending on the amount of polyethylene glycol, and the content of the half-hindered phenolic antioxidant in the final polyester is preferably 1.0 to 8.0% by weight. When the content of the half hindered phenolic antioxidant is too low, the oxidation resistance of the fiber formed by the polyester is insufficient, and the hygroscopicity of the polyester fiber is lowered due to the oxidative decomposition of polyethylene glycol; If the content of the half-hindered phenolic antioxidant is too high, the polyester fiber also turns yellow due to the decomposition of the antioxidant itself.

In the present invention, the polyester is a polyether ester compound, and the difference in water absorption (ΔMR) is 13.0% or more. The water absorption rate difference (ΔMR) in the present invention means a value measured by the method described in this specification. Polyesters can be spun individually by conventional spinning methods or composite spun together with other component polymers to obtain fibers with excellent hygroscopicity.

In the present invention, the fiber color L difference value of fibers obtained from polyester by conventional individual spinning or composite spinning methods is 6 or less, preferably 4, after hydrothermal treatment at 130° C. compared to non-hydrothermal treatment. On the other hand, the fiber after the nitrogen-oxygen fastness test has a fiber color yellowing difference value (ΔYI) of 10.0 or less, preferably 8.0 or less, more preferably 7.5 or less. When ΔYI is 7.5 or less, the nitrogen-oxygen fastness reaches grades 4-5, and when ΔYI is 7.5 or more, the nitrogen-oxygen fastness is grade 4.

In the polyester synthesis, a compound containing a titanium element or an antimony element may be added as a catalyst. Because of the high catalytic activity of the titanium-containing catalyst, side reactions are easily promoted, which affects the color tone stability of the final polyester fiber. Therefore, when a titanium-containing catalyst is selected, its addition amount is preferably adjusted within a range equivalent to 10 to 150 ppm of the polyester in terms of elemental titanium. When a compound of elemental antimony is used as the catalyst, its addition amount is preferably adjusted within a range equivalent to 150 to 300 ppm of the polyester in terms of elemental antimony.

In the polyester synthesis, various auxiliary modifiers may be added. As the auxiliary modifier, other types of antioxidants, commercial solvents, plasticizers, ultraviolet absorbers, optical brighteners, antibacterial agents, nucleating agents, heat stabilizers, antistatic agents, matting agents, defoamers, dyes, pigments, fragrances, etc. may be specifically exemplified , but not limited to these. The auxiliary additives may be used alone or in combination.

The extrapolated melting onset temperature of the polyester of the present invention is 180°C or higher. The extrapolated melting onset temperature of the polyester of the present invention means a value calculated according to the method described herein. If multiple melting peaks are observed, it is calculated from the melting peak with the lowest temperature. When the extrapolated melting initiation temperature of the polyester is 180 ° C. or higher, when the polyester is formed into fibers, filament breakage and fluff generation are reduced, so that the process passability is good, and when a fibrous structure such as a woven or knitted fabric is formed, dyeing stains And since the occurrence of fluff is reduced, the quality is excellent.

The fibers obtained from the polyester of the present invention are individually spun according to a conventional spinning method or fibers obtained by composite spinning with other components, and the twisted filaments or fiber structures made of the fibers have excellent hygroscopicity. Therefore, it may be used for applications requiring comfort and quality, for example, general-purpose clothing use, sports clothing use, bedding use, interior decoration use, material use, etc., but is not limited thereto.

Hereinafter, the present invention will be described in detail with reference to specific examples. In addition, each characteristic value in an Example was tested by the following method.

A. Difference in water absorption between polyester and fiber (ΔMR)

Using polyester and fiber as samples, dried in hot air at 60° C. for 30 minutes, and then, in order to specify the weight of the polymer (W1), in a thermo-hygrostat LHU-123 made by ESPEC at a temperature of 20° C. and a humidity of 65% RH for 24 hours. left unattended; Then, in a thermo-hygrostat, at a temperature of 30°C and a humidity of 90% RH for 24 hours, the weight of the polymer was measured as (W2). Then, it was dried with hot air at 105 DEG C for 2 hours, and the weight of the polymer after absolute drying was measured as (W3). According to the following general formula, the moisture absorption rate MR1 (%) after standing for 24 hours in an atmosphere of 20 ° C. and a humidity of 65% RH from an absolute dry state is calculated from the weight (W1) and weight (W3) of the polymer, and also the following general formula According to the method, after standing for 24 hours in an atmosphere of 30° C. and 90% RH in an atmosphere from an absolute dry state, the moisture absorption rate MR2 (%) was calculated from the weight (W2) and weight (W3) of the polymer, and then according to the following general formula The water absorption rate difference (ΔMR) was calculated. Moreover, 5 measurements were performed with respect to one sample, and the average value was made into the water absorption rate difference ((DELTA)MR).

MR1(%) = {(W1-W3)/W3} × 100,

MR2(%) = {(W2-W3)/W3} × 100,

Water absorption rate difference (ΔMR) (%) = MR2-MR1.

B. Hydrothermal yellowing performance of fibers

The polyester obtained in Examples was individually spun or composite spun with other components in a conventional manner to form fibers, the fibers were hydrothermally treated at 130° C. for 20 minutes, and the obtained sample was placed in a color difference meter (USTC-datacolor). . The L value after the hydrothermal treatment was measured and referred to as L2, the L value before the hydrothermal treatment was measured and set as L1, and L2-L1 was the hydrothermal treatment yellowing value.

C. Testing of Fiber Yellowing Value

The polyesters obtained in Examples were spun individually or compositely spun with other components in a conventional manner to form fibers as test samples. NO _x gas generating agent (85% phosphoric acid and 2% nitric acid aqueous solution) was placed in an airtight container, and then the sample and blue standard dye were placed in the container. When the color of the blue standard cloth faded to the standard gray board No.3, the blue standard dyed cloth was replaced. When the color reached the standard gray board No. 3 again, the sample was taken out, washed twice and dried. Yellowing values were measured with a Datacolor 650 spectrophotometer.

D. Polyethylene glycol copolymerization ratio

Polyethylene glycol copolymerization ratio: (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 / ether bond Number of H in * * molecular weight of structural unit of polyether compound) + (peak area of H in isophthalic acid containing sodium sulfonate/3 * molecular weight of ester formed by isophthalic acid containing sodium sulfate ) + peak area of H in PTA / 4 * molecular weight of PET + peak area of H in EG unit structure in polyester / 4 * molecular weight of EG unit structure].

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

50 g of the sample was weighed in the flask, sealed with 1 mL of aqueous ammonia, and heated at 120 degreeC for 3 hours. After cooling, the sample was ground and heated at 120° C. for an additional 2 hours. After cooling, 1 mL of distilled water and 1.5 mL of 6 M hydrochloric acid were added, and the volume was adjusted using a 5 mL volumetric flask. After centrifugation (3,500 rpm x 10 minutes), filtration was performed using a 0.45 µm filter, and the obtained filtrate was subjected to a GPC test. This sample was subjected to a GPC test (Alliance 2690 manufactured by Waters) under the following conditions. Those having a molecular weight of 1800 or less could not be separated from impurities, and those of other number average molecular weights were measured:

Detector: TOSOH with a sensitivity of 128x, RI-8020 made in Japan

Column: TOSOH, Japan TSKgelG3000PWXL I

Solvent: 0.1M sodium chloride aqueous solution

Injection amount: 200㎛

Column temperature: 40°C

Standard substance: polyethylene glycol (Mn 106 to 101000 g/mol, manufactured by AMR Co., Ltd.).

F. Content of Half Hindered Phenolic Antioxidant and Hindered Phenolic Antioxidant

Pretreatment: 8 g of polyester was cycled with 150 mL of solvent toluene for 35 minutes; After treatment, cooled to 100° C. and then poured into centrifuge tubes; Then centrifugation was performed, and the supernatant was filtered through a 0.45 μm filter; Then diluted with methanol and centrifuged to obtain a supernatant; Finally an internal standard was added thereto, filtered through a 0.45 μm filter and measured by HPLC.

HPLC analysis: mobile phase A/B: methanol/water (12%); flow rate: 1.3 ml/min; column temperature: 40°C; UV wavelength: 284 nm; Time: 15 minutes.

G. Extrapolated Melting Onset Temperature

The polymer as the core component and the polymer as the sheath component, and the fibers obtained in Examples were used as samples, and the extrapolated melting onset temperature was measured using a Q2000 type differential scanning calorimeter (DSC) manufactured by TA Instruments. First, 5 mg of the sample was heated from 0° C. to 280° C. at a temperature increase rate of 50° C./min in a nitrogen atmosphere, and held at 280° C. for 5 minutes to remove the thermal history. The mixture was then quenched from 280°C to 0°C and further heated from 0°C to 280°C at a rate of 3°C/min. The set temperature was changed within a range of ±1°C, and a temperature change cycle was performed for 60 seconds, and then the temperature was increased to measure TMDSC. The extrapolated melting onset temperature was calculated from the melting point peak observed during the second temperature raising process according to the standard of JIS K7121:1987 (Method for measuring transition temperature of plastics) 9.1. Three measurements were made for one sample, and the average value was used as the extrapolated melting onset temperature. In addition, when a plurality of melting peaks are observed, the extrapolated melting initiation temperature is calculated from the melting peak on the lowest temperature side.

Example 1

10.9 kg of terephthalic acid and 4.7 kg of ethylene glycol were placed in an esterification kettle, and the mixture was heated to 230° C. while stirring to perform an esterification reaction, and then transferred to a polycondensation kettle. Polyethylene glycol 8300 (polyethylene glycol having a number average molecular weight of 8300 g/mol, abbreviated as PEG 8300) in an amount of 35% by weight based on the total amount of the final polyester, antimony trioxide as a polymerization catalyst, antimony with respect to the total amount of the final polyester In terms of elemental content of 250 ppm, trimethyl phosphate as a stabilizer was added in an amount of 250 ppm with respect to the total amount of the final polyester. After 5 minutes, the temperature was raised under reduced pressure to reach a final temperature of 285° C., and when the final pressure was reached, 1,3,5-tris(4-tert-butyl-3, a half-hindered phenolic antioxidant, in the reaction system) -Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (CN1790) was added in an amount of 1.0% by weight based on the total amount of the final polyester was added in the amount of After stirring for 10 minutes, nitrogen gas was introduced into the reaction system to return to atmospheric pressure, and the polycondensation reaction was terminated to obtain copolyester.

The obtained polyester chips were melt-spun at a spinning speed of 3 Km/min to obtain pre-oriented filaments. Then, the obtained pre-oriented filament was subjected to false twist treatment under the following conditions to obtain a polyester fiber with high hygroscopicity: the first heater temperature was 180° C., the second heater temperature was room temperature, and the draw ratio was 1.7. The specific properties of the polyester and fibers are shown in Table 1.

Example 2

PEG 8300 was added in an amount of 40% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.1% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 3

PEG 11000 (number average molecular weight 11,000 g/mol) was added in an amount of 35% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.0% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 4

PEG 20000 (number average molecular weight 20,000 g/mol) was added in an amount of 35% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.0% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 5

PEG 30000 (number average molecular weight 30,000 g/mol) was added in an amount of 35% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.0% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 6

PEG 8300 was added in an amount of 35% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 3.0% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 7

PEG 8300 was added in an amount of 35% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 5.0% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 8

PEG 8300 was added in an amount of 35% by weight, and the half hindered phenolic antioxidant 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propanoyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO80) was added in an amount of 1.6% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 9

PEG 8300 was added in an amount of 35% by weight, and half hindered phenolic antioxidant AO80 was added in an amount of 4.7% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 10

PEG 8300 was added in an amount of 35% by weight, and a half hindered phenolic antioxidant AO80 was added in an amount of 8.0% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 11

PEG 8300 was added in an amount of 30% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.0% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 12

PEG 8300 was added in an amount of 27% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 10.0% by weight. The rest was the same as in Example 1. See Table 1 for details.

Example 13

10.9 kg of terephthalic acid and 11.8 kg of 1,4-butanediol were placed in an esterification kettle, tetrabutyl titanate as a catalyst was added in an amount of 450 ppm based on the total amount of the final polyester, and the mixture was heated to 230° C. while stirring to ester After carrying out the polymerization reaction, it was transferred to a polycondensation kettle. Polyethylene glycol 3400 (polyethylene glycol having a number average molecular weight of 3400 g/mol, abbreviated as PEG 3400) in an amount of 45 wt% with respect to the total amount of the final polyester, tetrabutyl titanate as a catalyst, 900 ppm with respect to the total amount of the final polyester In addition, trimethylphosphate as a stabilizer was added in an amount of 250 ppm with respect to the total amount of the final polyester. After 5 minutes, the temperature was raised under reduced pressure to reach a final temperature of 285° C., and when the final pressure was reached, 1,3,5-tris(4-tert-butyl-3, a half-hindered phenolic antioxidant, in the reaction system) -Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (CN1790) 1.3 wt% based on the total amount of the final polyester was added in the amount of After stirring for 10 minutes, nitrogen gas was introduced into the reaction system to return to atmospheric pressure, and the polycondensation reaction was terminated to obtain copolyester.

The obtained polyester chips were melt-spun at a spinning speed of 3 Km/min to obtain pre-oriented filaments. Then, the obtained pre-oriented filament was subjected to false twist treatment under the following conditions to obtain a polyester fiber with high hygroscopicity: the first heater temperature was 180° C., the second heater temperature was room temperature, and the draw ratio was 1.7. The specific properties of the polyester and fibers are shown in Table 2.

Example 14

PEG 3400 was added in an amount of 55% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.4% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 15

PEG 3400 was added in an amount of 58% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.8% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 16

PEG 11000 was added in an amount of 55% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.4% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 17

PEG 20000 was added in an amount of 55% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.4% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 18

PEG 3400 was added in an amount of 55% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 4.2% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 19

PEG 3400 was added in an amount of 55% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 8.0% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 20

PEG 3400 was added in an amount of 55% by weight, and the half hindered phenolic antioxidant 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) propanoyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO80) was added in an amount of 2.2% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 21

PEG 3400 was added in an amount of 55% by weight, and half hindered phenolic antioxidant AO80 was added in an amount of 6.6% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 22

PEG 3400 was added in an amount of 55% by weight, and half hindered phenolic antioxidant AO80 was added in an amount of 8.0% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 23

PEG 3400 was added in an amount of 50% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 10.0% by weight. The rest was the same as in Example 13. See Table 2 for details.

Example 24

10.9 kg of terephthalic acid and 4.7 kg of ethylene glycol were placed in an esterification kettle, and the mixture was heated to 230° C. while stirring to perform an esterification reaction, and then transferred to a polycondensation kettle. Polyethylene glycol 8300 (polyethylene glycol having a number average molecular weight of 8300 g/mol, abbreviated as PEG 8300) in an amount of 50% by weight based on the total amount of the final polyester, antimony trioxide as a polymerization catalyst, antimony with respect to the total amount of the final polyester In terms of elemental content of 250 ppm, trimethyl phosphate as a stabilizer was added in an amount of 250 ppm based on the total amount of the final polyester. After 5 minutes, the temperature was raised under reduced pressure to reach a final temperature of 285° C., and when the final pressure was reached, 1,3,5-tris(4-tert-butyl-3, a half hindered phenolic antioxidant, in the reaction system) -Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (CN1790) was added in an amount of 1.0% by weight based on the total amount of the final polyester was added in the amount of After stirring for 10 minutes, nitrogen gas was introduced into the reaction system to return to atmospheric pressure, and the polycondensation reaction was terminated to obtain copolyester.

The polyester as an island component and polyethylene terephthalate (IV=0.66) as a sea component were individually vacuum-dried at 150° C. for 12 hours, and these were screw-type in a ratio of 20% by weight to 80% by weight of the sea component. It was fed to a composite spinning machine and melted. Using a sea-island composite spinneret (24 islands in one discharge port), spun yarn was obtained under the conditions of a spinning temperature of 285°C and a discharge amount of 36 g/min. The spun yarn is cooled under cooling wind at a wind temperature of 20° C. and a wind speed of 20 m/min, and then coalesced by supplying oil by an oil supply device, drawn to the first segment of the roller at 2500 m/min, and the same speed as the first segment of the roller It was wound around the second segment of the furnace roller to obtain an undrawn filament of 144dtex-36f. Then, using a stretching and twisting device (twisted portion: friction disk type, heater portion: contact type), the obtained undrawn filament was false-twisted at a heater temperature of 170° C. and a ratio of 1.7, followed by false stretching of 84 dtex-36f. Filament was obtained.

Table 3 shows the evaluation results of fiber properties, fabric properties, and process passability of the obtained fibers. The number of filament breakage during false twisting was zero, so the process passability was very good. On the other hand, the hygroscopicity after the hydrothermal treatment did not substantially decrease, and the hygroscopicity after the hydrothermal treatment was also good. Also, the leveling properties and quality had reached a suitable level. See Table 3 for details.

Example 25

A half hindered phenolic antioxidant CN1790 was added in an amount of 3.0% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 26

A half hindered phenolic antioxidant CN1790 was added in an amount of 5.0% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 27

PEG 8300 was added in an amount of 45% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 5.0% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 28

PEG 8300 was added in an amount of 55% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 5.0% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 29

A half hindered phenolic antioxidant AO80 was added in an amount of 1.6% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 30

A half hindered phenolic antioxidant AO80 was added in an amount of 4.7% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 31

A half hindered phenolic antioxidant AO80 was added in an amount of 8.0% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 32

A half hindered phenolic antioxidant CN1790 was added in an amount of 2.0% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 33

A half hindered phenolic antioxidant AO80 was added in an amount of 4.0% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 34

A half hindered phenolic antioxidant AO80 was added in an amount of 6.0%, and the remainder was the same as in Example 24. See Table 3 for details.

Example 35

A half hindered phenolic antioxidant CN1790 was added in an amount of 9.0% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 36

A half hindered phenolic antioxidant CN1790 was added in an amount of 0.9% by weight, and the remainder was the same as in Example 24. See Table 3 for details.

Example 37

10.9 kg of terephthalic acid and 11.8 kg of 1,4-butanediol were placed in an esterification kettle, tetrabutyl titanate as a catalyst was added in an amount of 450 ppm based on the total amount of the final polyester, and the mixture was heated to 230 ° C. while stirring to ester After carrying out the polymerization reaction, it was transferred to a polycondensation kettle. Polyethylene glycol 8300 (polyethylene glycol having a number average molecular weight of 8300 g/mol, abbreviated as PEG 8300) in an amount of 50% by weight based on the total amount of the final polyester, and tetrabutyl titanate as a catalyst 900ppm with respect to the total amount of the final polyester In addition, trimethylphosphate as a stabilizer was added in an amount of 250 ppm with respect to the total amount of the final polyester. After 5 minutes, the temperature was raised under reduced pressure to reach a final temperature of 250° C., and when the final pressure was reached, 1,3,5-tris(4-tert-butyl-3, a half hindered phenolic antioxidant, in the reaction system) -Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (CN1790) was added to the total amount of the final polyester by 1.3 weight % was added. After stirring for 10 minutes, nitrogen gas was introduced into the reaction system to return to atmospheric pressure, and the polycondensation reaction was terminated to obtain copolyester. The rest was the same as in Example 24. See Table 4 for details.

Example 38

Half hindered phenolic antioxidant CN1790 was added in an amount of 2.4% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 39

A half hindered phenolic antioxidant CN1790 was added in an amount of 4.2% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 40

A half hindered phenolic antioxidant CN1790 was added in an amount of 8.0% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 41

A half hindered phenolic antioxidant AO80 was added in an amount of 2.2% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 42

A half hindered phenolic antioxidant AO80 was added in an amount of 6.6% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 43

PEG 8300 was added in an amount of 45% by weight, and a half hindered phenolic antioxidant AO80 was added in an amount of 6.6% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 44

PEG 8300 was added in an amount of 55% by weight, and a half hindered phenolic antioxidant AO80 was added in an amount of 6.6% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 45

PEG 8300 was added in an amount of 50% by weight, and a half hindered phenolic antioxidant AO80 was added in an amount of 8.0% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 46

PEG 8300 was added in an amount of 50% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 2.0% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 47

PEG 8300 was added in an amount of 50% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 3.0% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 48

PEG 8300 was added in an amount of 50% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 5.0% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 49

PEG 8300 was added in an amount of 50% by weight, and a half hindered phenolic antioxidant AO80 was added in an amount of 4.0% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 50

PEG 8300 was added in an amount of 50% by weight, and a half hindered phenolic antioxidant AO80 was added in an amount of 6.0% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Example 51

PEG 8300 was added in an amount of 50% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 9.0% by weight, and the remainder was the same as in Example 37. See Table 4 for details.

Comparative Example 1

PEG 8300 was added in an amount of 12% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.0% by weight, and the remainder was the same as in Example 1. See Table 5 for details. Since PEG was added in relatively small amounts, a high moisture absorption effect was not achieved.

Comparative Example 2

PEG 8300 was added in an amount of 20% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.0% by weight, and the remainder was the same as in Example 1. See Table 5 for details. Since PEG was added in relatively small amounts, a high moisture absorption effect was not achieved.

Comparative Example 3

PEG 100000 (number average molecular weight 100000 g/mol) was added in an amount of 30% by weight, and a half hindered phenolic antioxidant CN1790 was added in an amount of 2.0% by weight, and the remainder was the same as in Example 1. See Table 5 for details. Since PEG of ultra-high molecular weight was added, swelling occurred during ejection, which made ejection difficult.

Comparative Example 4

PEG 3400 was added in an amount of 12% by weight, and a half hindered phenolic antioxidant CN1790 was added in an amount of 0.8% by weight, and the remainder was the same as in Example 13. See Table 5 for details. Since PEG was added in relatively small amounts, a high moisture absorption effect was not achieved.

Comparative Example 5

PEG 3400 was added in an amount of 70% by weight, and a half hindered phenolic antioxidant CN1790 was added in an amount of 4.6% by weight, and the remainder was the same as in Example 13. See Table 5 for details. The extrapolated melting onset temperature of the final polyester was lowered by adding too much PEG 3400. When a fiber was produced from this polyester, filament breakage and fluff were further generated, and process passability deteriorated. When fibrous structures such as woven or knitted fabrics were formed, dye stains and fluff increased, resulting in poor quality.

Comparative Example 6

PEG 600 (number average molecular weight 600 g/mol) was added in an amount of 50% by weight, and a half hindered phenolic antioxidant CN1790 was added in an amount of 3.3% by weight, and the remainder was the same as in Example 13. See Table 5 for details. Since the molecular weight of PEG was low, a large amount of scattering occurred during polymerization. Even when added in a large amount, the obtained polyester had poor hygroscopicity.

Comparative Example 7

PEG 100000 was added in an amount of 50% by weight, and a half hindered phenolic antioxidant CN1790 was added in an amount of 3.3% by weight, and the remainder was the same as in Example 13. See Table 5 for details. Because PEG of ultra-high molecular weight was added, swelling occurred during ejection and the ejection deteriorated.

Comparative Example 8

PEG 3400 was added in an amount of 20% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.0% by weight, and the remainder was the same as in Example 13. See Table 5 for details. Since PEG was added in relatively small amounts, a high moisture absorption effect was not achieved.

Comparative Example 9

PEG 8300 was added in an amount of 20% by weight, and hindered phenolic antioxidant (IR1010) was added in an amount of 0.5% by weight, and the remainder was the same as in Example 1. See Table 5 for details. Compared to half hindered phenolic antioxidants, hindered phenolic antioxidants tend to cause yellowing of the polyester. When a small amount of PEG is added, only a small amount of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester (IR1010), a hindered phenolic antioxidant, is required. Although the following, the yellowing index of the polyester is within an acceptable range, but the effect of the antioxidant of the polyester is low, and the difference in water absorption rate between before and after dyeing of the polyester fiber is large, so this is the polyester fiber after dyeing indicates that the hygroscopicity of the

Comparative Example 10

PEG 8300 was added in an amount of 50% by weight, and a hindered phenolic antioxidant IR1010 was added in an amount of 3.0% by weight, and the remainder was the same as in Example 1. See Table 5 for details. When the hindered phenolic antioxidant was added in a large amount, the oxidizing agent effect was excellent, but the fibers were prone to yellowing.

Comparative Example 11

PEG 8300 was added in an amount of 50% by weight, and a hindered phenolic antioxidant IR1010 was added in an amount of 0.5% by weight, and the remainder was the same as in Example 1. See Table 5 for details. When a small amount of hindered phenolic antioxidant was added, yellowing of the fibers could be suppressed, but the effect of the oxidizing agent was low.

Comparative Example 12

PEG 3400 was added in an amount of 20% by weight, and a hindered phenolic antioxidant IR1010 was added in an amount of 0.5% by weight, and the remainder was the same as in Example 13. See Table 5 for details. Compared to half hindered phenolic antioxidants, hindered phenolic antioxidants tend to cause yellowing of the polyester. Although only a small amount of hindered phenolic antioxidant IR1010 is required when a small amount of PEG is added, the yellowing index of the polyester is within an acceptable range, but the effect of the antioxidant of the polyester is low, and the Since the value of the difference in moisture absorption between before and after dyeing was large, this indicates that the hygroscopicity of the polyester fiber after dyeing was significantly lowered.

Comparative Example 13

PEG 3400 was added in an amount of 50% by weight, and hindered phenolic antioxidant IR1010 was added in an amount of 3.0% by weight, and the remainder was the same as in Example 13. See Table 5 for details. When the hindered phenolic antioxidant was added in a large amount, the oxidizing agent effect was excellent, but the fibers were prone to yellowing.

Comparative Example 14

PEG 3400 was added in an amount of 50% by weight, and a hindered phenolic antioxidant IR1010 was added in an amount of 0.5% by weight, and the remainder was the same as in Example 13. See Table 5 for details. When a small amount of hindered phenolic antioxidant was added, yellowing of the fibers could be suppressed, but the effect of the oxidizing agent was low.

Comparative Example 15

PEG 8300 was added in an amount of 22 wt%, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.0 wt%, and the remainder was the same as in Example 1. See Table 5 for details. PEG 8300 was added in an unsuitable amount, resulting in poor ejection properties.

Comparative Example 16

PEG 8300 was added in an amount of 25% by weight, and half hindered phenolic antioxidant CN1790 was added in an amount of 1.0% by weight, and the remainder was the same as in Example 1. See Table 5 for details. PEG 8300 was added in an unsuitable amount, resulting in poor ejection properties.

Comparative Example 17

PEG 8300 was added in an amount of 50% by weight, and hindered phenolic antioxidant IR1010 was added in an amount of 3.0% by weight, and the remainder was the same as in Example 24. See Table 6 for details. In the case of composite spinning, when a large amount of hindered phenolic antioxidant was added, the oxidizing agent effect was excellent, but the fibers were prone to yellowing.

Comparative Example 18

PEG 8300 was added in an amount of 50% by weight, and a hindered phenolic antioxidant IR1010 was added in an amount of 0.8% by weight, and the remainder was the same as in Example 24. See Table 6 for details. In the case of composite spinning, when a small amount of hindered phenolic antioxidant was added, yellowing of the fibers could be suppressed, but the effect of the oxidizing agent was low.

Comparative Example 19

PEG 8300 was added in an amount of 50% by weight, no antioxidant was added, and the remainder was the same as in Example 24. See Table 6 for details. Since no antioxidant was added, the fibers did not yellow, but had no oxidizing effect either.

Claims (6)

A polyester, which is a polymer formed by aromatic dicarboxylic acid or a derivative thereof as a main component and 1,4-butanediol as a main component, and polyethylene glycol as a copolymerization component,
The number average molecular weight of the polyethylene glycol is 2000-30000 g/mol, the copolymerization ratio is 25-55 wt%, and the polyester contains 3.82-8.0 wt% of a half-hindered phenolic antioxidant as shown in Formula 2 polyester.

Equation 2 The method of claim 1,
The copolymerization ratio of the polyethylene glycol is 35 to 55% by weight of polyester. delete delete delete delete