TWI753033B - a polyester - Google Patents
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- TWI753033B TWI753033B TW106136344A TW106136344A TWI753033B TW I753033 B TWI753033 B TW I753033B TW 106136344 A TW106136344 A TW 106136344A TW 106136344 A TW106136344 A TW 106136344A TW I753033 B TWI753033 B TW I753033B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
本發明公開一種聚酯，所述聚酯是以芳香族二元羧酸或其衍生物與脂肪族二元醇為主要構成成分、聚乙二醇為共聚合成分形成的聚合物，其中聚乙二醇的數均分子量為2000~30000g/mol，共聚合率為25~55wt%。本發明的聚酯，通過常規紡絲方法單獨紡絲或與其他組分複合紡絲製得的纖維，及由其形成的假撚絲、纖維構造體的吸濕性優異。因此，可以用於要求舒適性及品質的用途。 The invention discloses a polyester. The polyester is a polymer formed by an aromatic dicarboxylic acid or a derivative thereof and an aliphatic diol as main constituents, and polyethylene glycol as a copolymerization constituent, wherein polyethylene glycol is used as a copolymer. The number-average molecular weight of the diol is 2000-30000 g/mol, and the copolymerization rate is 25-55 wt%. The polyester of the present invention is excellent in hygroscopicity of fibers obtained by spinning alone or in combination with other components by conventional spinning methods, as well as false twisted yarns and fiber structures formed therefrom. Therefore, it can be used for applications requiring comfort and quality.
Description
本發明係一種吸濕性優異的聚酯。 The present invention is a polyester with excellent hygroscopicity.
聚酯由於其優異的性能，在纖維、薄膜、塑料等領域有著廣泛的應用。但是由於聚酯的結構規整，疏水性較強，與棉或麻等天然纖維相比，聚酯纖維的吸水性、吸濕性較差，大大限制了聚酯纖維在要求吸濕性環境下的應用。由聚酯纖維得到的紡織品製成貼身衣物時，由於聚酯纖維的吸濕性差，會給人帶來悶熱感，因此聚酯纖維特別不適合應用於夏裝方面。 Due to its excellent properties, polyester has a wide range of applications in the fields of fibers, films, and plastics. However, due to the regular structure and strong hydrophobicity of polyester, compared with natural fibers such as cotton or hemp, polyester fibers have poor water absorption and hygroscopicity, which greatly limits the application of polyester fibers in environments requiring hygroscopicity. . When the textile obtained from polyester fiber is made into intimate clothing, because polyester fiber has poor hygroscopicity, it will give people a feeling of stuffiness, so polyester fiber is especially not suitable for summer clothing.
為了解決聚酯纖維吸水吸濕性差的問題，本領域技術人員嘗試了很多方法。例如對纖維表面進行改性，主要是使纖維表面多孔質化後利用毛細管原理提高纖維的吸濕性。也可以使用放電處理、光接枝改性、低溫等離子處理等方法實現纖維表面的改性。但是通過這些方法得到的纖維製成織物後，對於在出汗狀態下減少蒸熱感等方面沒有很好的效果，更不會有棉、麻等天然纖維的清涼感。在這些方法之外，還有在纖維表面包裹親水性膜的方法，但是這種方法往往存在纖維與膜之間親和性差、水洗後耐久性不佳的缺點。 In order to solve the problem of poor water absorption and hygroscopicity of polyester fibers, those skilled in the art have tried many methods. For example, the modification of the fiber surface is mainly to improve the hygroscopicity of the fiber by using the capillary principle after making the fiber surface porous. Modification of the fiber surface can also be achieved by methods such as electrical discharge treatment, photografting modification, and low temperature plasma treatment. However, after the fibers obtained by these methods are made into fabrics, they do not have a good effect on reducing the feeling of steaming and heat in the state of sweating, and they will not have the cooling feeling of natural fibers such as cotton and hemp. In addition to these methods, there is also a method of wrapping a hydrophilic film on the surface of the fiber, but this method often has the disadvantages of poor affinity between the fiber and the film, and poor durability after washing.
也可以通過對聚酯纖維進行化學接枝的方法來提高纖維的吸濕性能。例如：對聚對苯二甲酸乙二醇酯(PET)纖維進 行15%程度的丙烯酸及甲基丙烯酸的接枝共聚合後，進行鈉離子交換的處理，可以得到與棉同等的吸濕率。可是這種纖維的吸濕速度很慢，而且聚酯纖維的基本性能有很大損失，基本上沒有了應用價值，所以也一直沒有工業化生產。 The hygroscopic properties of fibers can also be improved by chemically grafting polyester fibers. For example, after graft copolymerization of about 15% of acrylic acid and methacrylic acid on polyethylene terephthalate (PET) fiber, and sodium ion exchange treatment, a moisture absorption rate equivalent to that of cotton can be obtained. However, the moisture absorption speed of this kind of fiber is very slow, and the basic properties of polyester fiber are greatly lost, which basically has no application value, so there has been no industrial production.
另外，也有使用高分子量的聚醚化合物來提高吸濕性的，但是高分子量的聚醚化合物與聚酯基體不完全進行共聚，大部分以分離相的狀態存在於聚酯中，這樣會導致聚合物熔融滯留時粗大化形成不穩定的相分離結構，聚合反應終了後吐出以及紡絲時口金部吐出不穩定，導致最終纖維的纖度斑、染斑大，以及毛羽的產生。日本專利特開2007-70467中使用特殊的PEG與PET共聚來改善PET的吸濕性能。但是PEG的添加量過少的話，不能帶來高的吸濕性，因此需要較高的添加量，其結果就是導致聚酯成纖後失去纖維的基本性能，而且耐熱性能、耐熱水性能以及耐氧化發熱性能大大變差，使用價值變得很低。 In addition, high molecular weight polyether compounds are also used to improve hygroscopicity, but high molecular weight polyether compounds are not completely copolymerized with the polyester matrix, and most of them exist in the polyester in the state of separate phases, which will lead to polymerization. When the material is melted and retained, it coarsens to form an unstable phase-separated structure, and the discharge after the polymerization reaction ends and the discharge of the gold part of the mouth during spinning is unstable, resulting in the final fiber size spot, large dye spot, and hairiness. Japanese Patent Laid-Open No. 2007-70467 uses special PEG to copolymerize with PET to improve the hygroscopic properties of PET. However, if the addition amount of PEG is too small, it cannot bring high hygroscopicity, so a higher addition amount is required. As a result, the basic properties of the fiber will be lost after the polyester fiber is formed, and the heat resistance, hot water resistance and oxidation resistance will be lost. The heating performance is greatly deteriorated, and the use value becomes very low.
本發明的目的在於提供一種吸濕性優異的聚酯，由該聚酯紡絲所得到的纖維具有優異的耐熱水性能以及耐氧化發熱性能。 The object of the present invention is to provide a polyester having excellent hygroscopicity, and the fibers obtained by spinning the polyester have excellent hot water resistance and oxidation heat generation resistance.
本發明的技術解決方案如下： The technical solution of the present invention is as follows:
一種聚酯，所述聚酯是以芳香族二元羧酸或其衍生物與脂肪族二元醇為主要構成成分、聚乙二醇為共聚合成分形成的聚合物，其中聚乙二醇的數均分子量為2000~30000g/mol，共聚合率為25~55wt%，並且聚酯中含有如式1所示的半受阻酚類抗氧化劑，
所述半受阻酚類抗氧化劑的含有量較佳佔聚酯總重量的1.0~8.0wt%。 The content of the semi-hindered phenolic antioxidant preferably accounts for 1.0-8.0 wt % of the total weight of the polyester.
所述半受阻酚類抗氧化劑較佳如式2所示的抗氧化劑3,9-雙[1,1-二甲基-2-[(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]乙基]-2,4,8,10-四氧雜螺[5.5]十一烷，或者如式3所示的1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三
所述聚乙二醇的共聚合率較佳35~55wt%。 The copolymerization rate of the polyethylene glycol is preferably 35 to 55 wt%.
所述脂肪族二元醇較佳乙二醇或1,4-丁二醇；當脂肪族二元醇較佳乙二醇時，所述聚乙二醇的數均分子量較佳4000~30000g/mol。 The aliphatic diol is preferably ethylene glycol or 1,4-butanediol; when the aliphatic diol is preferably ethylene glycol, the number average molecular weight of the polyethylene glycol is preferably 4000~30000g/ mol.
本發明所述聚酯中聚乙二醇的共聚合率高，聚酯切片 的吸濕性優異，且所述聚酯成纖後纖維染色前後的吸濕率差的差值小。同時，聚酯的耐熱性好，抗黃變性優良，應用價值高。 The copolymerization rate of polyethylene glycol in the polyester of the present invention is high, the hygroscopicity of polyester chips is excellent, and the difference between the difference in hygroscopicity before and after fiber dyeing of the polyester fiber is small. At the same time, polyester has good heat resistance, excellent yellowing resistance and high application value.
本發明所述聚酯是以芳香族二元羧酸或其衍生物、脂肪族二元醇為主要單體，聚乙二醇為共聚合成分共聚所得到的聚醚酯，具有良好的耐熱性及機械特性。 The polyester of the present invention is a polyether ester obtained by copolymerizing aromatic dicarboxylic acids or derivatives thereof, aliphatic diols as main monomers, and polyethylene glycol as copolymerization components, and has good heat resistance and mechanical properties.
所述芳香族二元羧酸或其衍生物，具體地可以列舉的有對苯二甲酸、間苯二甲酸、鄰苯二甲酸、間苯二甲酸-5-磺酸鈉、間苯二甲酸-5-磺酸鋰、5-(四烷基)-間苯二甲酸磺酸磷化合物、4,4’-聯苯二元羧酸、2,6-萘二甲酸等，但不限於以上物質，其中較佳對苯二甲酸。 Described aromatic dibasic carboxylic acid or its derivative, can specifically cite terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid-5-sodium sulfonate, isophthalic acid- 5-Lithium sulfonate, 5-(tetraalkyl)-isophthalic acid phosphorus compound, 4,4'-biphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, etc., but not limited to the above substances, Among them, terephthalic acid is preferred.
所述脂肪族二元醇，具體地可以列舉的有乙二醇、1,3-丙二醇、1,4-丁二醇、己二醇、環己烷己二醇、二乙二醇、六亞甲基乙二醇、新戊二醇等，但不限於以上物質。尤其，乙二醇、丙二醇、1,4-丁二醇製造以及使用時取用性良好而較佳。從耐熱性以及機械特性的角度來看，更佳乙二醇；從結晶性的角度來看，更佳1,4-丁二醇。 Specific examples of the aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, hexanediol, cyclohexanehexanediol, diethylene glycol, and hexaethylene glycol. Methyl glycol, neopentyl glycol, etc., but not limited to the above substances. In particular, ethylene glycol, propylene glycol, and 1,4-butanediol are preferable because they have good availability during production and use. From the viewpoint of heat resistance and mechanical properties, ethylene glycol is more preferable; from the viewpoint of crystallinity, 1,4-butanediol is more preferable.
本發明所述的聚酯，其共聚合成分聚乙二醇的數均分子量，可以在聚酯具有結晶性的範圍內進行適當選擇。本發明的聚酯中聚乙二醇的共聚合率為25~55wt%。當聚乙二醇的共聚合率小於25wt%時，聚酯的吐出性差；當聚乙二醇的共聚合率大於55wt%時，所得聚酯形成的纖維的物性下降。由於聚乙二醇的共聚合率在 25~35wt%之間時所得聚酯的吐出性一般，因此為了獲得更好吐出性的聚酯，本發明較佳聚乙二醇的共聚合率為35~55wt%。 In the polyester of the present invention, the number-average molecular weight of polyethylene glycol as a copolymerization component can be appropriately selected within the range where the polyester has crystallinity. The copolymerization ratio of polyethylene glycol in the polyester of the present invention is 25 to 55 wt %. When the copolymerization rate of polyethylene glycol is less than 25 wt %, the dischargeability of the polyester is poor; when the copolymerization rate of polyethylene glycol is greater than 55 wt %, the physical properties of the fibers formed by the obtained polyester decrease. When the copolymerization rate of polyethylene glycol is between 25 and 35wt%, the discharge property of the obtained polyester is general, so in order to obtain polyester with better discharge property, the preferred copolymerization rate of polyethylene glycol in the present invention is 35%. ~55wt%.
較佳的範圍根據聚酯的組成成分不同而不同。例如，在聚酯的組成成分脂肪族二元醇為乙二醇的場合下，聚酯分子量如果過低的話，由於聚合溫度過高，使得聚乙二醇降解嚴重，最終聚酯、甚至製成的纖維的吸濕率會下降。同時，當聚酯的構成成分脂肪族二元醇為1,4-丁二醇時，與上述使用乙二醇的場合相比，由於聚合溫度低，聚乙二醇降解相對不是很嚴重，從而聚酯的吸濕性、甚至製成纖維後的吸濕性也能得到提高。 The preferable range varies depending on the composition of the polyester. For example, in the case where the aliphatic diol of the polyester is ethylene glycol, if the molecular weight of the polyester is too low, the polyethylene glycol will be degraded seriously because the polymerization temperature is too high, and the final polyester, or even made into The moisture absorption rate of the fibers will decrease. At the same time, when the constituent aliphatic diol of the polyester is 1,4-butanediol, compared with the above-mentioned case of using ethylene glycol, the degradation of polyethylene glycol is relatively less serious due to the low polymerization temperature, so The hygroscopicity of polyester, even after being made into fibers, can be improved.
本發明所述脂肪族二元醇為乙二醇的場合，聚乙二醇的數均分子量較佳4000~30000g/mol，聚乙二醇的共聚合率較佳35~55wt%。聚乙二醇的數均分子量在4000g/mol以上的話，聚酯的吸濕性高，單獨紡絲或複合紡絲，都能得到吸濕性優異的纖維。同時，能夠抑制聚酯的結晶性的下降及外推熔融起始溫度的降低，由於聚酯紡絲後斷絲以及毛羽的發生變少，加工性良好，形成織物和編物等纖維構造體時染斑及毛羽的產生變少，品質優異。另一方面，聚乙二醇的數均分子量在30000g/mol以下的話，縮聚反應性高，未反應的聚乙二醇減少，能夠抑制染色等熱水處理時在熱水中的溶出，熱水處理後的吸濕性能夠被維持。聚乙二醇的數均分子量較佳25000g/mol以下，更佳為20000g/mol以下。 When the aliphatic diol of the present invention is ethylene glycol, the number average molecular weight of polyethylene glycol is preferably 4000-30000 g/mol, and the copolymerization rate of polyethylene glycol is preferably 35-55 wt%. When the number-average molecular weight of polyethylene glycol is 4000 g/mol or more, polyester has high hygroscopicity, and fibers excellent in hygroscopicity can be obtained by single spinning or combined spinning. At the same time, the decrease of the crystallinity of polyester and the decrease of the extrapolated melting initiation temperature can be suppressed. Since the occurrence of yarn breakage and hairiness after polyester spinning is reduced, the processability is good, and it is dyed when forming fiber structures such as woven fabrics and knitted fabrics. The occurrence of spots and hairiness is reduced, and 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, unreacted polyethylene glycol is reduced, elution in hot water during hot water treatment such as dyeing can be suppressed, and hot water Hygroscopicity after treatment can be maintained. The number average molecular weight of polyethylene glycol is preferably 25,000 g/mol or less, more preferably 20,000 g/mol or less.
同時，聚乙二醇的共聚合率在35wt%以上的話，聚酯的吸濕性高，單獨紡絲或複合紡絲都能得到吸濕性優異的纖維。另一方面，聚乙二醇的共聚合率在55wt%以下的話，聚酯紡絲後，斷絲以及毛羽的發生變少，加工性良好，形成織物和編物等纖維構造 體時染斑及毛羽的產生變少，品質優異。同時，能夠抑制染色等熱水處理時聚乙二醇的溶出，熱水處理後能夠維持纖維的吸濕性。 At the same time, when the copolymerization ratio of polyethylene glycol is 35 wt% or more, polyester has high hygroscopicity, and fibers excellent in hygroscopicity can be obtained by single spinning or combined spinning. On the other hand, when the copolymerization ratio of polyethylene glycol is 55 wt% or less, the occurrence of yarn breakage and hairiness after polyester spinning is reduced, the processability is good, and dye spots and hairiness are formed when fiber structures such as woven fabrics and knitted fabrics are formed. The production is less and the quality is excellent. At the same time, the elution of polyethylene glycol during hot water treatment such as dyeing can be suppressed, and the hygroscopicity of the fiber can be maintained after the hot water treatment.
本發明所述脂肪族二元醇為1,4-丁二醇的場合，聚乙二醇的數均分子量較佳2000~30000g/mol，聚乙二醇的共聚合率較佳35~55wt%。聚乙二醇的數均分子量在2000g/mol以上的話，聚酯的吸濕性高，單獨紡絲或複合紡絲都能得到吸濕性優異的纖維。同時，能夠抑制聚酯的結晶性下降。同時，聚乙二醇的數均分子量在2000g/mol以上的話，能夠抑制聚酯的結晶性的下降以及外推熔融起始溫度的降低，由於延伸以及假撚工程中斷絲以及毛羽的發生變少，加工性良好，形成織物和編物等纖維構造體時染斑及毛羽的產生變少，品質優異。另一方面，聚乙二醇的數均分子量在30000g/mol以下的話，縮聚反應性高，未反應的聚乙二醇減少，能夠抑制染色等熱水處理時在熱水中的溶出，熱水處理後的吸濕性能夠維持。聚乙二醇的數均分子量較佳27000g/mol以下，更佳25000g/mol以下，最佳20000g/mol以下。同時，聚乙二醇的共聚合率在35wt%以上的話，聚酯的吸濕性高，單獨紡絲或複合紡絲都能得到吸濕性優異的纖維。另一方面，聚乙二醇的共聚合率在55wt%以下時，由於延伸以及假撚工程中斷絲以及毛羽的發生變少，加工性良好，形成織物和編物等纖維構造體時染斑及毛羽的產生變少，品質優異。同時，能夠抑制染色等熱水處理時在熱水中的溶出，熱水處理後的吸濕性能夠維持。 When the aliphatic diol of the present invention is 1,4-butanediol, the number-average molecular weight of polyethylene glycol is preferably 2000-30,000 g/mol, and the copolymerization rate of polyethylene glycol is preferably 35-55 wt% . When the number-average molecular weight of polyethylene glycol is 2,000 g/mol or more, polyester has high hygroscopicity, and fibers excellent in hygroscopicity can be obtained by single spinning or combined spinning. At the same time, the decrease in the crystallinity of the polyester can be suppressed. At the same time, if the number average molecular weight of polyethylene glycol is 2000 g/mol or more, the decrease of the crystallinity of polyester and the decrease of the extrapolated melting start temperature can be suppressed, and the occurrence of yarn breakage and hairiness due to drawing and false twisting process can be reduced. , The processability is good, the generation of dye spots and hairiness is reduced when forming fiber structures such as fabrics and knitted fabrics, and 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, unreacted polyethylene glycol is reduced, elution in hot water during hot water treatment such as dyeing can be suppressed, and hot water The hygroscopicity after the 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 20,000 g/mol or less. At the same time, when the copolymerization ratio of polyethylene glycol is 35 wt% or more, polyester has high hygroscopicity, and fibers excellent in hygroscopicity can be obtained by single spinning or combined spinning. On the other hand, when the copolymerization ratio of polyethylene glycol is 55 wt% or less, the occurrence of yarn breakage and hairiness due to drawing and false twisting process is reduced, and the workability is good, and dye spots and hairiness are formed when fiber structures such as woven fabrics and knitted fabrics are formed. The production is less and the quality is excellent. At the same time, elution in hot water during hot water treatment such as dyeing can be suppressed, and hygroscopicity after hot water treatment can be maintained.
眾所周知，聚酯中大量添加聚醚類化合物時，由於醚鍵受熱氧化分解，導致聚酯形成纖維後吸濕性大幅度下降。故在聚酯的合成過程中，一般會添加受阻酚類抗氧化劑，但是，聚酯製成 纖維後，在高溫染色過程中，被氧化分解的醚鍵自由基進攻受阻酚類抗氧化劑酚羥基的對位，生成醌類黃色物質。同樣的機轉，與NO2作用後也會生成黃色物質，使得纖維氮氧堅牢度不合格，影響了纖維的使用性能。當聚乙二醇的共聚率低於25wt%時，添加的受阻酚類抗氧劑量一般比較少，因而不會產生上述黃變問題；但是，當聚乙二醇的共聚率高於25wt%時，黃變問題就會比較嚴重。本發明使用如式1所示的半受阻酚類抗氧化劑，即使存在被熱氧化分解後形成的醚鍵自由基，由於半受阻酚類抗氧化劑酚羥基鄰位上是甲基，位阻效應比較小，醚鍵自由基將進攻半受阻酚類抗氧劑酚羥基的間位，將不會生成黃色醌類物質，
其中，R1為由碳氫、氧、氮中的一或多種結合形成的基團；R2為由氫、碳氫、氧、氮中的一或多種結合形成的基團。 Wherein, R1 is a group formed by the combination of one or more of hydrocarbon, oxygen and nitrogen; R2 is a group formed by the combination of one or more of hydrogen, hydrocarbon, oxygen and nitrogen.
本發明所述半受阻酚類抗氧化劑，較佳3,9-雙[1,1-二甲基-2-[(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]乙基]-2,4,8,10-四氧雜螺[5.5]十一烷，或者1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三
本發明中，所述聚酯為吸濕率 In the present invention, the polyester is the moisture absorption rate
差(△MR)13.0wt%以上的聚醚酯化合物。本發明所述的吸濕率差(△MR)是指按照說明書中所記載的方法測定的值。該聚酯通過常規紡絲方法單獨紡絲，或者與其他組分聚合物進行複合紡絲，均能得到吸濕性優異的纖維。 A polyetherester compound with a difference (ΔMR) of 13.0 wt% or more. The difference in moisture absorption rate (ΔMR) in the present invention refers to a value measured by the method described in the specification. The polyester can be spun by conventional spinning methods alone or combined with other component polymers to obtain fibers with excellent hygroscopicity.
本發明中，所述聚酯通過常規單獨或者複合紡絲的方法製得的纖維，在130℃熱水處理後，與未熱水處理相比，纖維色調L值的變化為6以下，較佳4以下。另一方面，纖維經過氮氧堅牢度測試後，色調黃變值△YI為10.0以下，較佳8.0以下，更佳7.5以下。當△YI為7.5以下時，氮氧堅牢度達到4~5級，△YI為7.5以上時，氮氧堅牢度為4級。 In the present invention, the fiber obtained by the conventional single or composite spinning method of the polyester, after being treated with hot water at 130°C, compared with the non-hot water treatment, the change of the color tone L value of the fiber is less than 6, preferably 4 or less. On the other hand, after the fiber has been tested for nitroxide fastness, the hue yellowing value ΔYI is 10.0 or less, preferably 8.0 or less, more preferably 7.5 or less. When △YI is below 7.5, the fastness to nitrogen and oxygen reaches grade 4-5, and when △YI is above 7.5, the fastness to nitrogen and oxygen is grade 4.
在上述聚酯合成時，可以添加含鈦元素或銻元素的化合物作為催化劑。由於含鈦催化劑的催化活性高，容易促進副反應，影響最終聚酯纖維的色調穩定性，因此選用含鈦催化劑時其添加量最好控制在以鈦元素計相當於聚酯的10~150ppm的範圍之內。以銻元素的化合物作為催化劑時，其添加量為以銻元素計相當於聚酯150~300ppm範圍內。 In the synthesis of the above polyester, a compound containing a titanium element or an antimony element may be added as a catalyst. Due to the high catalytic activity of titanium-containing catalysts, it is easy to promote side reactions and affect the color stability of the final polyester fiber. Therefore, when selecting titanium-containing catalysts, the addition amount should preferably be controlled at 10-150ppm equivalent to polyester in terms of titanium element. within the range. When the compound of antimony element is used as a catalyst, the addition amount is in the range of 150-300 ppm equivalent to polyester in terms of antimony element.
在上述聚酯合成時，還可以添加各種各樣的輔助改性劑。輔助改性劑，具體地可以列舉的有其他類型的抗氧化、相溶劑、可塑劑、紫外線吸收劑、螢光增白劑、抗菌劑、成核劑、熱穩定劑、帶電防止劑、消光劑、消泡劑、染料、顏料、香料等，但不限於上述物質。上述輔助添加劑可以單獨使用，也可以混合使用。 In the above polyester synthesis, various auxiliary modifiers can also be added. Auxiliary modifiers, specifically, other types of antioxidants, compatibilizers, plasticizers, ultraviolet absorbers, optical brighteners, antibacterial agents, nucleating agents, heat stabilizers, anti-charge agents, and matting agents can be listed , defoamer, dyes, pigments, fragrances, etc., but not limited to the above substances. The above-mentioned auxiliary additives may be used alone or in combination.
本發明的聚酯的外推熔融起始溫度在180℃以上。本發明的聚酯的外推熔融起始溫度，是指按照說明書中記載的方法算 出的值。在觀測到多個熔融峰的場合，從溫度最低的融解峰開始算出。聚酯的外推熔融起始溫度在180℃以上的話，聚酯形成纖維後，斷絲以及毛羽的發生變少，加工性良好，形成織物和編物等纖維構造體時染斑及毛羽產生變少，品質優異。 The extrapolated melting onset temperature of the polyester of the present invention is above 180°C. The extrapolated melting onset temperature of the polyester of the present invention means a value calculated according to the method described in the specification. When a plurality of melting peaks are observed, calculation is performed from the melting peak with the lowest temperature. When the extrapolated melting start temperature of polyester is 180°C or higher, the occurrence of yarn breakage and hairiness after polyester is formed into fibers is reduced, the processability is good, and the occurrence of dye spots and hairiness when forming fiber structures such as woven fabrics and knitted fabrics is reduced. , excellent quality.
本發明的聚酯，通過常規紡絲方法單獨紡絲或與其他組分複合紡絲製得的纖維，及由其形成的假撚絲、纖維構造體的吸濕性優異。因此，可以用於要求舒適性及品質的用途。例如，一般衣料用途、運動衣料用途、寢具用途、室內裝飾用途、資材用途等，但並不限於上述列舉。 The polyester of the present invention is excellent in hygroscopicity of fibers obtained by spinning alone or in combination with other components by conventional spinning methods, as well as false twisted yarns and fiber structures formed therefrom. Therefore, it can be used for applications requiring comfort and quality. For example, general clothing application, sports clothing application, bedding application, interior decoration application, material application, etc. are not limited to the above-mentioned ones.
下面，通過具體實施例對本發明作詳細地說明。同時，實施例中的各特性值通過以下的方法測試。 Hereinafter, the present invention will be described in detail through specific embodiments. Meanwhile, each characteristic value in the examples was tested by the following methods.
A.聚酯以及纖維的吸濕率差(△MR) A. Difference in moisture absorption between polyester and fiber (△MR)
將聚酯以及纖維作為樣品，先在60℃下熱風乾燥30分鐘後，在溫度20℃、濕度65%RH的ESPEC公司製恒溫恒濕機LHU-123內靜置24小時，測定聚合物的重量(W1)；接著在溫度30℃、濕度90%RH的恒溫恒濕機內靜置24小時，測定聚合物的重量為(W2)。然後，在105℃下熱風乾燥2小時，測定絕乾後的聚合物重量為(W3)。根據下記公式用聚合物的重量W1、W3計算出從絕乾狀態到20℃、濕度65%RH環境下靜置24小時後的吸濕率MR1(%)，根據下記公式用聚合物的重量W2、W3計算出絕乾狀態到30℃、濕度90%RH環境下靜置24小時後的吸濕率MR2(%)，然後根據下記公式算出吸濕率差(△MR)。並且，1個樣品測定5回，取平均值作為吸濕率差(△MR)，MR1(%)={(W1-W3)/W3}×100， MR2(%)={(W2-W3)/W3}×100，吸濕率差(△MR)(%)=MR2-MR1。 The polyester and fiber were used as samples, and after drying with hot air at 60°C for 30 minutes, they were left standing for 24 hours in a constant temperature and humidity machine LHU-123 manufactured by ESPEC at a temperature of 20°C and a humidity of 65% RH, and the weight of the polymer was measured. (W1); Next, it was left to stand in a constant temperature and humidity machine with a temperature of 30° C. and a humidity of 90% RH for 24 hours, and the weight of the polymer was measured as (W2). Then, it was hot-air-dried at 105 degreeC for 2 hours, and the polymer weight after absolute drying was measured as (W3). Calculate the moisture absorption rate MR1 (%) after standing for 24 hours from a dry state to a 20°C, humidity 65%RH environment using the weights W1 and W3 of the polymers according to the following formula, and use the weight W2 of the polymer according to the following formula , W3 Calculate the moisture absorption rate MR2 (%) after standing for 24 hours in a dry state to 30 ℃, humidity 90%RH environment, and then calculate the moisture absorption rate difference (△MR) according to the following formula. In addition, one sample is measured 5 times, and the average value is taken as the difference in moisture absorption rate (ΔMR), MR1(%)={(W1-W3)/W3}×100, MR2(%)={(W2-W3) /W3}×100, moisture absorption difference (△MR) (%)=MR2-MR1.
B.纖維的熱水黃變性能 B. Hot water yellowing properties of fibers
實施例所製得的聚酯，通過常規方法單獨紡絲或與其他組分複合紡絲後形成的纖維，在130℃×20分鐘的條件下進行熱水處理，得到的樣品用色差計(USTC-datacolor)進行L值測定為L2，熱水處理前的L值測定為L1，L2-L1為熱水處理黃變值。 The polyesters prepared in the examples, the fibers formed by spinning alone or in combination with other components by conventional methods, were subjected to hot water treatment under the condition of 130 ° C × 20 minutes, and the obtained samples were measured with a color difference meter (USTC). -datacolor) L value was measured as L2, L value before hot water treatment was measured as L1, and L2-L1 was the yellowing value of hot water treatment.
C.纖維的黃變值測試 C. Fiber yellowing value test
實施例所製得的聚酯，通過常規方法單獨紡絲或與其他組分複合紡絲後形成的纖維作為測試樣品，在密閉容器中放入NOx氣體發生劑(85%磷酸及2%的亞硝酸水溶液)，然後將試樣及藍色標準染色佈置於容器內，當藍色標準布顏色褪為標準灰度板3號時，更換藍色標準染色布，當顏色再次達到標準灰度板3號時，將試樣取出，並清洗2次，晾乾。通過Datacolor 650分光光度儀對黃變值進行測定。 The polyesters obtained in the examples were used as test samples after spinning alone or in combination with other components by conventional methods. NOx gas generating agent (85% phosphoric acid and 2% nitrous oxide) was placed in a closed container. Nitric acid aqueous solution), then arrange the sample and blue standard dyeing in the container, when the color of the blue standard cloth fades to the standard grayscale plate No. 3, replace the blue standard dyeing cloth, when the color reaches the standard grayscale plate 3 again No., take out the sample, wash it twice, and dry it. Yellowing values were determined by a Datacolor 650 spectrophotometer.
D.聚乙二醇的共聚合率 D. Copolymerization rate of polyethylene glycol
聚乙二醇的共聚合率：(醚鍵中H的峰面積/醚鍵中H的個數×聚醚化合物的結構單元分子量)/[(醚鍵中H的峰面積/醚鍵中H的個數×聚醚化合物的結構單元分子量)+(含磺酸鈉的間苯二甲酸中H的峰面積/3×含磺酸鈉的間苯二甲酸形成的酯的分子量)+PTA中H的峰面積/4×PET的分子量+聚酯中EG單元結構的H的峰面積/4×EG單元結構的分子量]。 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 Number × 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 sulfonate) + H in PTA Peak area/4 x molecular weight of PET + peak area of H of EG unit structure in polyester/4 x molecular weight of EG unit structure].
E.所含聚乙二醇的數均分子量(Mn) E. Number average molecular weight (Mn) of polyethylene glycol contained
用瓶子稱取50mg試樣，加入1mL氨水密封，溫度 120℃下加熱3小時。冷卻後，試樣經粉碎後在120℃下再加熱2小時。冷卻後，添加蒸餾水1Ml、6M鹽酸1.5mL，用5ML的容量瓶進行定容。遠心分離(3500rpm×10分)後，用0.45μm的濾網進行過濾，得到的濾液進行GPC測試。該試樣，用以下的條件進行GPC測試(Waters製Alliance2690)。分子量低於1800的與不純物不能進行分離，除此之外求出數均分子量； Weigh 50 mg of sample with a bottle, add 1 mL of ammonia water to seal, and heat at 120°C for 3 hours. After cooling, the samples were pulverized and heated at 120°C for a further 2 hours. After cooling, 1Ml of distilled water and 1.5mL of 6M hydrochloric acid were added, and the volume was adjusted with a 5ML volumetric flask. After telecentric separation (3500 rpm×10 minutes), it was filtered with a 0.45 μm mesh, and the obtained filtrate was subjected to GPC test. This sample was subjected to a GPC test (Alliance 2690 manufactured by Waters) under the following conditions. Impurities with a molecular weight lower than 1800 cannot be separated, and the number average molecular weight is obtained in addition to that;
檢出器：日本「Tosoh」製造的RI-8020、感度128x Detector: RI-8020 made by Japan "Tosoh", sensitivity 128x
管柱：日本「Tosoh」製造的TSKgelG3000PWXL I Column: TSKgelG3000PWXL I manufactured by Japan "Tosoh"
溶劑：0.1M氯化鈉水溶液 Solvent: 0.1M aqueous sodium chloride solution
注入量：200μm Injection volume: 200μm
管柱溫度：40℃ Column temperature: 40℃
標準物質：聚乙二醇(「AMR股份有限公司」製Mn106~101000g/mol)。 Standard substance: polyethylene glycol (Mn106~101000g/mol manufactured by "AMR Co., Ltd.").
F.半受阻酚類抗氧化劑、受阻酚類抗氧化劑的含有量 F. Content of semi-hindered phenolic antioxidants and hindered phenolic antioxidants
前處理：取聚酯8g，用溶劑甲苯150ml進行環流處理35分鐘；處理後冷卻至100度，然後倒入遠心分離管；接下來進行遠心分離，取上層液體用0.45μm的過濾器進行過濾；然後用甲醇進行稀釋，遠心分離取上層液體；最後添加內標，用0.45μm的過濾器進行過濾後用HPLC進行測定。 Pre-treatment: take 8g of polyester, and use 150ml of solvent toluene for circulation treatment for 35 minutes; after treatment, cool it to 100 degrees, and then pour it into a telecentric separation tube; then carry out telecentric separation, take the upper layer of liquid and filter it with a 0.45μm filter; Then, it was diluted with methanol, and the supernatant liquid was collected by centrifugation; finally, the internal standard was added, filtered through a 0.45 μm filter, and then measured by HPLC.
HPLC測定：流動相A/B：甲醇/水(12%)；流速：1.3ml/min；柱溫：40度；紫外線波長：284nm；時間：15min。 HPLC determination: mobile phase A/B: methanol/water (12%); flow rate: 1.3 ml/min; column temperature: 40 degrees; ultraviolet wavelength: 284 nm; time: 15 min.
G.外推熔融起始溫度 G. Extrapolated melting onset temperature
取芯成分、鞘成分的聚合物以及通過實施例得到的纖維作為試樣，採用TA Instruments公司製的Q2000型差示掃描量熱 儀(DSC)，測定外推熔融起始溫度。首先，在氮氣環境下將5mg的試樣以50℃/分的升溫速度從0℃升溫至280℃，在280℃的狀態下保持5分鐘消除熱歷史。然後，從280℃驟冷至0℃，再次以3℃/分的速度從0℃升溫至280℃，溫度變調幅度為±1℃，溫度變調週期60秒後進行升溫，進行TMDSC的測定。根據JISK7121：1987(塑料的轉變溫度的測定方法)9.1的標準，根據第2回升溫過程中觀測到的融解峰算出外推熔融起始溫度。1個樣品測定3回，其平均值作為外推熔融起始溫度。並且，觀測到多個融解峰的場合，根據最低溫側的融解峰算出外推熔融起始溫度。 The polymer of the core component, the sheath component, and the fibers obtained in the examples were taken as samples, and the extrapolated melting onset temperature was measured using a Q2000 differential scanning calorimeter (DSC) manufactured by TA Instruments. First, a 5 mg sample was heated from 0°C to 280°C at a temperature increase rate of 50°C/min in a nitrogen atmosphere, and kept at 280°C for 5 minutes to eliminate thermal history. Then, it was quenched from 280°C to 0°C, and then heated again from 0°C to 280°C at a rate of 3°C/min. The temperature adjustment range was ±1°C, and the temperature was adjusted after a period of 60 seconds, and then the temperature was increased to perform TMDSC measurement. The extrapolated melting onset temperature was calculated from the melting peak observed in the second heating process in accordance with the standards of JISK7121:1987 (Method for Measuring Transition Temperature of Plastics) 9.1. One sample was measured three times, 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 onset temperature is calculated from the melting peak on the lowest temperature side.
[實施例1] [Example 1]
將對苯二甲酸10.9Kg與乙二醇4.7Kg投入酯化釜中，攪拌升溫至230℃進行酯化反應後移至縮聚釜，加入相對於最終聚酯總量為35wt%的聚乙二醇8300(數均分子量為8300g/mol的聚乙二醇，簡寫PEG8300)，以銻元素計相對於最終聚酯總量含量為250ppm的三氧化二銻作為聚合催化劑，以及添加相對於最終聚酯總量的穩定劑磷酸三甲酯250ppm，5分鐘後開始減壓升溫，達到最終溫度285℃、最終壓力後，向反應體系添加相對於最終聚酯總量為1.0wt%的半受阻酚類抗氧化劑1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三
將上述所得到的聚酯切片進行熔融紡絲，紡絲速度為3Km/min得到預取向絲。然後將得到的預取向絲經過假撚加工，加工條件：第一熱箱溫度為180℃，第二熱箱的溫度為常溫，延伸倍 率為1.7，製得高吸濕性聚酯纖維。聚酯以及纖維的具體物性見表1。 The polyester chips obtained above were melt-spun at a spinning speed of 3 Km/min to obtain pre-oriented yarns. Then, the obtained pre-oriented yarn is subjected to false twisting processing, processing conditions: the temperature of the first hot box is 180°C, the temperature of the second hot box is normal temperature, and the stretching ratio is 1.7 to obtain a highly hygroscopic polyester fiber. The specific physical properties of polyester and fibers are shown in Table 1.
[實施例2] [Example 2]
PEG8300的添加量為40wt%，半受阻酚類抗氧化劑CN1790的添加量為1.1wt%。其餘同實施例1。具體見表1。 The addition amount of PEG8300 was 40wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 was 1.1wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例3] [Example 3]
PEG11000(數均分子量11000g/mol)的添加量為35wt%，半受阻酚類抗氧化劑CN1790的添加量為1.0wt%。其餘同實施例1。具體見表1。 The addition amount of PEG11000 (number average molecular weight 11000g/mol) was 35wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 was 1.0wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例4] [Example 4]
PEG20000(數均分子量20000g/mol)的添加量為35wt%，半受阻酚類抗氧化劑CN1790的添加量為1.0wt%。其餘同實施例1。具體見表1。 The addition amount of PEG20000 (number average molecular weight 20000g/mol) is 35wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 is 1.0wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例5] [Example 5]
PEG30000(數均分子量30000g/mol)的添加量為35wt%，半受阻酚類抗氧化劑CN1790的添加量為1.0wt%。其餘同實施例1。具體見表1。 The addition amount of PEG30000 (number average molecular weight 30000g/mol) is 35wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 is 1.0wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例6] [Example 6]
PEG8300的添加量為35wt%，半受阻酚類抗氧化劑CN1790的添加量為3.0wt%。其餘同實施例1。具體見表1。 The addition amount of PEG8300 is 35wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 is 3.0wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例7] [Example 7]
PEG8300的添加量為35wt%，半受阻酚類抗氧化劑CN1790的添加量為5.0wt%。其餘同實施例1。具體見表1。 The addition amount of PEG8300 was 35wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 was 5.0wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例8] [Example 8]
PEG8300的添加量為35wt%，半受阻酚類抗氧化劑半 受阻酚類抗氧化劑3,9-雙[1,1-二甲基-2-[(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]乙基]-2,4,8,10-四氧雜螺[5.5]十一烷(AO80)的添加量為1.6wt%。其餘同實施例1。具體見表1。 The addition amount of PEG8300 is 35wt%, the semi-hindered phenolic antioxidant, the semi-hindered phenolic antioxidant, 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5 -Methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO80) was added in an amount of 1.6 wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例9] [Example 9]
PEG8300的添加量為35wt%，半受阻酚類抗氧化劑AO80的添加量為4.7wt%。其餘同實施例1。具體見表1。 The addition amount of PEG8300 was 35wt%, and the addition amount of semi-hindered phenolic antioxidant AO80 was 4.7wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例10] [Example 10]
PEG8300的添加量為35wt%，半受阻酚類抗氧化劑AO80的添加量為8.0wt%。其餘同實施例1。具體見表1。 The addition amount of PEG8300 was 35wt%, and the addition amount of semi-hindered phenolic antioxidant AO80 was 8.0wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例11] [Example 11]
PEG8300的添加量為30wt%，半受阻酚類抗氧化劑CN1790的添加量為1.0wt%。其餘同實施例1。具體見表1。 The addition amount of PEG8300 is 30wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 is 1.0wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例12] [Example 12]
PEG8300的添加量為27wt%，半受阻酚類抗氧化劑CN1790的添加量為10.0wt%。其餘同實施例1。具體見表1。 The addition amount of PEG8300 was 27wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 was 10.0wt%. The rest are the same as in Example 1. See Table 1 for details.
[實施例13] [Example 13]
將對苯二甲酸10.9Kg與1,4-丁二醇11.8Kg投入酯化釜中，加入相對於最終聚酯總量的鈦酸四丁酯催化劑450ppm，攪拌升溫至230℃進行酯化反應後移至縮聚釜，加入相對於最終聚酯總量為45wt%的聚乙二醇3400(數均分子量為3400g/mol的聚乙二醇，簡寫PEG3400)，添加相對於最終聚酯總量的鈦酸四丁酯催化劑900ppm，以及添加相對於最終聚酯總量的穩定劑磷酸三甲酯250ppm，5分鐘後開始減壓升溫，達到最終溫度250℃、最終壓力後，向反應體系添加相對於最終聚酯總量為1.3wt%的半受阻酚類 抗氧化劑1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三
將上述所得到的聚酯切片進行熔融紡絲，紡絲速度為3Km/min得到預取向絲。然後將得到的預取向絲經過假撚加工，加工條件：第一熱箱溫度為180℃，第二熱箱的溫度為常溫，延伸倍率為1.7，製得高吸濕性聚酯纖維。聚酯以及纖維的具體物性見表2。 The polyester chips obtained above were melt-spun at a spinning speed of 3 Km/min to obtain pre-oriented yarns. Then, the obtained pre-oriented yarn is subjected to false twisting processing. The processing conditions are as follows: the temperature of the first hot box is 180°C, the temperature of the second hot box is normal temperature, and the elongation ratio is 1.7 to obtain a highly hygroscopic polyester fiber. The specific physical properties of polyester and fibers are shown in Table 2.
[實施例14] [Example 14]
PEG3400的添加量為55wt%，半受阻酚類抗氧化劑CN1790的添加量為1.4wt%。其餘同實施例13。具體見表2。 The addition amount of PEG3400 was 55wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 was 1.4wt%. The rest are the same as in Example 13. See Table 2 for details.
[實施例15] [Example 15]
PEG3400的添加量為58wt%，半受阻酚類抗氧化劑CN1790的添加量為1.8wt%。其餘同實施例13。具體見表2。 The addition amount of PEG3400 was 58wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 was 1.8wt%. The rest are the same as in Example 13. See Table 2 for details.
[實施例16] [Example 16]
PEG11000的添加量為55wt%，抗氧化劑CN1790的添加量為1.4wt%。其餘同實施例13。具體見表2。 The addition amount of PEG11000 was 55wt%, and the addition amount of antioxidant CN1790 was 1.4wt%. The rest are the same as in Example 13. See Table 2 for details.
[實施例17] [Example 17]
PEG20000的添加量為55wt%，半受阻酚類抗氧化劑CN1790的添加量為1.4wt%。其餘同實施例13。具體見表2。 The addition amount of PEG20000 was 55wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 was 1.4wt%. The rest are the same as in Example 13. See Table 2 for details.
[實施例18] [Example 18]
PEG3400的添加量為55wt%，半受阻酚類抗氧化劑CN1790的添加量為4.2wt%，其餘同實施例13。具體見表2。 The addition amount of PEG3400 is 55wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 4.2wt%, and the rest are the same as in Example 13. See Table 2 for details.
[實施例19] [Example 19]
PEG3400的添加量為55wt%，半受阻酚類抗氧化劑 CN1790的添加量為8.0wt%，其餘同實施例13。具體見表2。 The addition amount of PEG3400 was 55wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 was 8.0wt%, and the rest were the same as in Example 13. See Table 2 for details.
[實施例20] [Example 20]
PEG3400的添加量為55wt%，半受阻酚類抗氧化劑3,9-雙[1,1-二甲基-2-[(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]乙基]-2,4,8,10-四氧雜螺[5.5]十一烷(AO80)的添加量為2.2wt%。其餘同實施例13。具體見表2。 The addition amount of PEG3400 is 55wt%, the semi-hindered phenolic antioxidant 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl) The addition amount of propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (AO80) was 2.2 wt%. The rest are the same as in Example 13. See Table 2 for details.
[實施例21] [Example 21]
PEG3400的添加量為55wt%，半受阻酚類抗氧化劑AO80的添加量為6.6wt%。其餘同實施例13。具體見表2。 The addition amount of PEG3400 was 55wt%, and the addition amount of semi-hindered phenolic antioxidant AO80 was 6.6wt%. The rest are the same as in Example 13. See Table 2 for details.
[實施例22] [Example 22]
PEG3400的添加量為55wt%，半受阻酚類抗氧化劑AO-80的添加量為8.0wt%。其餘同實施例13。具體見表2。 The addition amount of PEG3400 was 55wt%, and the addition amount of semi-hindered phenolic antioxidant AO-80 was 8.0wt%. The rest are the same as in Example 13. See Table 2 for details.
[實施例23] [Example 23]
PEG3400的添加量為50wt%，半受阻酚類抗氧化劑CN1790的添加量為10.0wt%。其餘同實施例13。具體見表2。 The addition amount of PEG3400 is 50wt%, and the addition amount of semi-hindered phenolic antioxidant CN1790 is 10.0wt%. The rest are the same as in Example 13. See Table 2 for details.
[實施例24] [Example 24]
將對苯二甲酸10.9Kg與乙二醇4.7Kg投入酯化釜中，攪拌升溫至230℃進行酯化反應後移至縮聚釜，加入相對於最終聚酯總量為35wt%的聚乙二醇8300(數均分子量為8300g/mol的聚乙二醇，簡寫PEG8300)，以銻元素計相對於最終聚酯總量含量為250ppm的三氧化二銻作為聚合催化劑，以及添加相對於最終聚酯總量的穩定劑磷酸三甲酯250ppm，5分鐘後開始減壓升溫，達到最終溫度285℃、最終壓力後，向反應體系添加相對於最終聚酯總量為1.0wt%的半受阻酚類抗氧化劑1,3,5-三(4-第三丁基-3-羥基 -2,6-二甲基苄基)-1,3,5-三
將上述聚酯作為島成分，以聚對苯二甲酸乙二醇酯(IV=0.66)作為海成分，分別在150℃條件下真空乾燥12小時後，按島成分20wt%、海成分80wt%的配比向螺桿型複合紡絲機內供給分別進行熔融，在紡絲溫度285℃、吐出量為36g/分下用海島型複合用紡絲口金(一個吐出孔有24個島)，紡出絲條。紡出的絲條在風溫20℃、風速20m/分的冷風下進行冷卻，通過給油裝置進行給油收束，2500m/分回轉的第1段羅拉進行拉伸，通過與第一段羅拉同樣的回轉速度的第2段羅拉卷取，得到144dtex-36f的未延伸絲。然後，採用延伸假撚機(加撚部：摩擦磁盤式、加熱器部：接觸式)，將得到的未延伸絲在加熱器溫度170℃、倍率1.7倍的條件下進行延伸假撚，得到84dtex-36f的假撚絲。 The above polyester was used as the island component, and polyethylene terephthalate (IV=0.66) was used as the sea component. After vacuum drying at 150 ° C for 12 hours, the island component was 20wt% and the sea component was 80wt%. The mixing ratio is supplied to the screw type composite spinning machine for melting separately, and the spinning temperature is 285°C and the discharge rate is 36g/min. strip. The spun yarn is cooled under cold air with a wind temperature of 20°C and a wind speed of 20m/min, and is fed with oil by the oil feeder. The 2nd stage roller of the rotation speed was taken up to obtain an undrawn filament of 144dtex-36f. Then, the obtained undrawn yarn was drawn and false-twisted at a heater temperature of 170° C. and a magnification of 1.7 times using a draw-false-twist machine (twisting part: friction disk type, heater part: contact type) to obtain 84 dtex -36f false twisted silk.
得到的纖維的纖維特性、布帛特性以及加工性的評價結果如表3所示。假撚時的斷絲回數為0回，加工性極其良好。同時，熱水處理後吸濕性基本沒有降低，熱水處理後吸濕性也良好。並且，但是均染性、品質都達到合格水平。具體見表3。 Table 3 shows the evaluation results of the fiber properties, fabric properties, and processability of the obtained fibers. The number of times of yarn breakage during false twisting was 0, and the workability was extremely good. At the same time, the hygroscopicity was not substantially reduced after the hot water treatment, and the hygroscopicity was also good after the hot water treatment. And, but the leveling, quality have reached the qualified level. See Table 3 for details.
[實施例25] [Example 25]
半受阻酚類抗氧化劑CN1790的添加量為3.0wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant CN1790 is 3.0 wt %, and the rest are the same as those in Example 24. See Table 3 for details.
[實施例26] [Example 26]
半受阻酚類抗氧化劑CN1790的添加量為5.0wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant CN1790 was 5.0 wt %, and the rest were the same as those in Example 24. See Table 3 for details.
[實施例27] [Example 27]
PEG8300的添加量為45wt%，半受阻酚類抗氧化劑CN1790的添加量為5.0wt%，其餘同實施例24。具體見表3。 The addition amount of PEG8300 is 45wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 5.0wt%, and the rest are the same as in Example 24. See Table 3 for details.
[實施例28] [Example 28]
PEG8300的添加量為55wt%，半受阻酚類抗氧化劑CN1790的添加量為5.0wt%，其餘同實施例24。具體見表3。 The addition amount of PEG8300 is 55 wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 5.0 wt%, and the rest are the same as in Example 24. See Table 3 for details.
[實施例29] [Example 29]
半受阻酚類抗氧化劑AO80的添加量為1.6wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant AO80 was 1.6 wt %, and the rest were the same as those in Example 24. See Table 3 for details.
[實施例30] [Example 30]
半受阻酚類抗氧化劑AO80的添加量為4.7wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant AO80 is 4.7 wt %, and the rest are the same as those in Example 24. See Table 3 for details.
[實施例31] [Example 31]
半受阻酚類抗氧化劑AO80的添加量為8.0wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant AO80 is 8.0 wt%, and the rest are the same as those in Example 24. See Table 3 for details.
[實施例32] [Example 32]
半受阻酚類抗氧化劑CN1790的添加量為2.0wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant CN1790 is 2.0 wt %, and the rest are the same as those in Example 24. See Table 3 for details.
[實施例33] [Example 33]
半受阻酚類抗氧化劑AO80的添加量為4.0wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant AO80 is 4.0 wt %, and the rest are the same as those in Example 24. See Table 3 for details.
[實施例34] [Example 34]
半受阻酚類抗氧化劑AO80的添加量為6.0wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant AO80 is 6.0 wt %, and the rest are the same as those in Example 24. See Table 3 for details.
[實施例35] [Example 35]
半受阻酚類抗氧化劑CN1790的添加量為9.0wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant CN1790 is 9.0 wt%, and the rest are the same as those in Example 24. See Table 3 for details.
[實施例36] [Example 36]
半受阻酚類抗氧化劑CN1790的添加量為0.9wt%，其餘同實施例24。具體見表3。 The addition amount of the semi-hindered phenolic antioxidant CN1790 was 0.9 wt %, and the rest were the same as those in Example 24. See Table 3 for details.
[實施例37] [Example 37]
將對苯二甲酸10.9Kg與1,4-丁二醇11.8Kg投入酯化釜中，加入相對於最終聚酯總量的鈦酸四丁酯催化劑450ppm，攪拌升溫至230℃進行酯化反應後移至縮聚釜，加入相對於最終聚酯總量為50wt%的聚乙二醇8300(數均分子量為8300g/mol的聚乙二醇，簡寫PEG8300)，添加相對於最終聚酯總量的鈦酸四丁酯催化劑900ppm，以及添加相對於最終聚酯總量的穩定劑磷酸三甲酯250ppm，5分鐘後開始減壓升溫，達到最終溫度250℃、最終壓力後，向反應體系添加相對於最終聚酯總量為1.3wt%的半受阻酚類抗氧化劑1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)-1,3,5-三
[實施例38] [Example 38]
半受阻酚類抗氧化劑CN1790的添加量為2.4wt%，其餘同實施例37。具體見表4。 The addition amount of the semi-hindered phenolic antioxidant CN1790 is 2.4 wt %, and the rest are the same as those in Example 37. See Table 4 for details.
[實施例39] [Example 39]
半受阻酚類抗氧化劑CN1790的添加量為4.2wt%，其 餘同實施例37。具體見表4。 The addition amount of the semi-hindered phenolic antioxidant CN1790 is 4.2wt%, and the rest are the same as in Example 37. See Table 4 for details.
[實施例40] [Example 40]
半受阻酚類抗氧化劑CN1790的添加量為8.0wt%，其餘同實施例37。具體見表4。 The addition amount of the semi-hindered phenolic antioxidant CN1790 is 8.0 wt %, and the rest are the same as those in Example 37. See Table 4 for details.
[實施例41] [Example 41]
半受阻酚類抗氧化劑AO80的添加量為2.2wt%，其餘同實施例37。具體見表4。 The addition amount of the semi-hindered phenolic antioxidant AO80 was 2.2 wt%, and the rest were the same as those in Example 37. See Table 4 for details.
[實施例42] [Example 42]
半受阻酚類抗氧化劑AO80的添加量為6.6wt%，其餘同實施例37。具體見表4。 The addition amount of the semi-hindered phenolic antioxidant AO80 is 6.6 wt %, and the rest are the same as those in Example 37. See Table 4 for details.
[實施例43] [Example 43]
PEG8300的添加量為45wt%，半受阻酚類抗氧化劑AO80的添加量為6.6wt%，其餘同實施例37。具體見表4。 The addition amount of PEG8300 is 45wt%, the addition amount of semi-hindered phenolic antioxidant AO80 is 6.6wt%, and the rest are the same as in Example 37. See Table 4 for details.
[實施例44] [Example 44]
PEG8300的添加量為55wt%，半受阻酚類抗氧化劑AO80的添加量為6.6wt%，其餘同實施例37。具體見表4。 The addition amount of PEG8300 is 55wt%, the addition amount of semi-hindered phenolic antioxidant AO80 is 6.6wt%, and the rest are the same as in Example 37. See Table 4 for details.
[實施例45] [Example 45]
PEG8300的添加量為50wt%，半受阻酚類抗氧化劑AO80的添加量為8.0wt%，其餘同實施例37。具體見表4。 The addition amount of PEG8300 is 50wt%, the addition amount of semi-hindered phenolic antioxidant AO80 is 8.0wt%, and the rest are the same as in Example 37. See Table 4 for details.
[實施例46] [Example 46]
PEG8300的添加量為50wt%，半受阻酚類抗氧化劑CN1790的添加量為2.0wt%，其餘同實施例37。具體見表4。 The addition amount of PEG8300 is 50wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 2.0wt%, and the rest are the same as in Example 37. See Table 4 for details.
[實施例47] [Example 47]
PEG8300的添加量為50wt%，半受阻酚類抗氧化劑 CN1790的添加量為3.0wt%，其餘同實施例37。具體見表4。 The addition amount of PEG8300 is 50wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 3.0wt%, and the rest are the same as in Example 37. See Table 4 for details.
[實施例48] [Example 48]
PEG8300的添加量為50wt%，半受阻酚類抗氧化劑CN1790的添加量為5.0wt%，其餘同實施例37。具體見表4。 The addition amount of PEG8300 is 50wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 5.0wt%, and the rest are the same as in Example 37. See Table 4 for details.
[實施例49] [Example 49]
PEG8300的添加量為50wt%，半受阻酚類抗氧化劑AO80的添加量為4.0wt%，其餘同實施例37。具體見表4。 The addition amount of PEG8300 is 50wt%, the addition amount of semi-hindered phenolic antioxidant AO80 is 4.0wt%, and the rest are the same as in Example 37. See Table 4 for details.
[實施例50] [Example 50]
PEG8300的添加量為50wt%，半受阻酚類抗氧化劑AO80的添加量為6.0wt%，其餘同實施例37。具體見表4。 The addition amount of PEG8300 is 50wt%, the addition amount of semi-hindered phenolic antioxidant AO80 is 6.0wt%, and the rest are the same as in Example 37. See Table 4 for details.
[實施例51] [Example 51]
PEG8300的添加量為50wt%，半受阻酚類抗氧化劑CN1790的添加量為9.0wt%，其餘同實施例37。具體見表4。 The addition amount of PEG8300 is 50wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 9.0wt%, and the rest are the same as in Example 37. See Table 4 for details.
[比較例1] [Comparative Example 1]
PEG8300的添加量為12wt%，半受阻酚類抗氧化劑CN1790的添加量為1.0wt%，其餘同實施例1。具體見表5。由於PEG的添加量比較少，達不到高吸濕性效果。 The addition amount of PEG8300 is 12wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 1.0wt%, and the rest are the same as in Example 1. See Table 5 for details. Due to the relatively small amount of PEG added, the effect of high hygroscopicity cannot be achieved.
[比較例2] [Comparative Example 2]
PEG8300的添加量為20wt%，半受阻酚類抗氧化劑CN1790的添加量為1.0wt%，其餘同實施例1。具體見表5。由於PEG的添加量比較少，達不到高吸濕性效果。 The addition amount of PEG8300 is 20wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 1.0wt%, and the rest are the same as in Example 1. See Table 5 for details. Due to the relatively small amount of PEG added, the effect of high hygroscopicity cannot be achieved.
[比較例3] [Comparative Example 3]
PEG100000(數均分子量100000g/mol)的添加量為30wt%，半受阻酚類抗氧化劑CN1790的添加量為2.0wt%，其餘同 實施例1。具體見表5。由於添加了超高分子量PEG，發生吐出漲大，不易吐出。 The addition of PEG100000 (number-average molecular weight 100000g/mol) is 30wt%, and the addition of semi-hindered phenolic antioxidant CN1790 is 2.0wt%, and all the other are the same as in Example 1. See Table 5 for details. Due to the addition of ultra-high molecular weight PEG, spit swelling occurs, and it is difficult to spit out.
[比較例4] [Comparative Example 4]
PEG3400的添加量為12wt%，半受阻酚類抗氧化劑CN1790的添加量為0.8wt%，其餘同實施例13。具體見表5。由於PEG的添加量比較少，達不到高吸濕性效果。 The addition amount of PEG3400 was 12 wt %, the addition amount of semi-hindered phenolic antioxidant CN1790 was 0.8 wt %, and the rest were the same as in Example 13. See Table 5 for details. Due to the relatively small amount of PEG added, the effect of high hygroscopicity cannot be achieved.
[比較例5] [Comparative Example 5]
PEG3400的添加量為70wt%，半受阻酚類抗氧化劑CN1790的添加量為4.6wt%，其餘同實施例13。具體見表5。PEG3400的添加量過高，導致最終聚酯的外推熔融起始溫度偏低，聚酯形成纖維後，斷絲以及毛羽的發生變多，加工性變差，形成織物和編物等纖維構造體時染斑及毛羽產生變多，品質不佳。 The addition amount of PEG3400 is 70wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 4.6wt%, and the rest are the same as in Example 13. See Table 5 for details. If the amount of PEG3400 added is too high, the extrapolated melting starting temperature of the final polyester is low. After the polyester is formed into fibers, the occurrence of broken filaments and hairiness increases, and the processability becomes poor. When forming fiber structures such as fabrics and knitting Dyed spots and hairiness increased, and the quality was poor.
[比較例6] [Comparative Example 6]
PEG600(數均分子量600g/mol)的添加量為50wt%，半受阻酚類抗氧化劑CN1790的添加量為3.3wt%，其餘同實施例13。具體見表5。PEG的分子量偏低，聚合過程中大量飛散，即使大量添加，所得聚酯的吸濕性差。 The addition amount of PEG600 (number-average molecular weight 600 g/mol) is 50 wt %, the addition amount of semi-hindered phenolic antioxidant CN1790 is 3.3 wt %, and the rest are the same as in Example 13. See Table 5 for details. The molecular weight of PEG is relatively low, and a large amount of PEG is scattered during the polymerization process. Even if a large amount of PEG is added, the obtained polyester has poor hygroscopicity.
[比較例7] [Comparative Example 7]
PEG100000的添加量為50wt%，半受阻酚類抗氧化劑CN1790的添加量為3.3wt%，其餘同實施例13。具體見表5。由於添加了超高分子量PEG，發生吐出漲大，不易吐出。 The addition amount of PEG100000 is 50wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 3.3wt%, and the rest are the same as in Example 13. See Table 5 for details. Due to the addition of ultra-high molecular weight PEG, spit swelling occurs, and it is difficult to spit out.
[比較例8] [Comparative Example 8]
PEG3400的添加量為20wt%，半受阻酚類抗氧化劑CN1790的添加量為1.0wt%，其餘同實施例13。具體見表5。由於 PEG的添加量比較少，達不到高吸濕性效果。 The addition amount of PEG3400 is 20wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 1.0wt%, and the rest are the same as in Example 13. See Table 5 for details. Due to the relatively small amount of PEG added, the effect of high hygroscopicity cannot be achieved.
[比較例9] [Comparative Example 9]
PEG8300的添加量為20wt%，受阻酚類抗氧化劑......(IR1010)的添加量為0.5wt%，其餘同實施例1。具體見表5。與受阻酚類抗氧化劑相比，受阻酚類抗氧化劑容易導致聚酯黃變。在PEG添加量少的情況下，雖然只需要添加少量的受阻酚類抗氧化劑四[β-(3,5-二第三丁基-4-羥基苯基)丙酸]新戊四醇酯IR1010，聚酯黃變指數也在可接受範圍之內，但是聚酯的抗氧化效果降低，染色前後聚酯纖維的吸濕率差的差值大，說明染色後聚酯纖維的吸濕性下降明顯。 The addition amount of PEG8300 is 20wt%, the addition amount of hindered phenolic antioxidant...(IR1010) is 0.5wt%, and the rest are the same as in Example 1. See Table 5 for details. Compared with hindered phenolic antioxidants, hindered phenolic antioxidants tend to cause polyester yellowing. In the case of a small amount of PEG, although only a small amount of hindered phenolic antioxidant tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] neopentaerythritol ester IR1010 , the yellowing index of polyester is also within the acceptable range, but the antioxidant effect of polyester is reduced, and the difference between the difference in moisture absorption rate of polyester fiber before and after dyeing is large, indicating that the moisture absorption of polyester fiber after dyeing is significantly reduced .
[比較例10] [Comparative Example 10]
PEG8300的添加量為50wt%，受阻酚類抗氧化劑IR1010的添加量為3.0wt%，其餘同實施例1。具體見表5。受阻酚類抗氧化劑大量添加的場合，雖然抗氧化效果優異，但是纖維容易發生黃變。 The addition amount of PEG8300 is 50wt%, the addition amount of hindered phenolic antioxidant IR1010 is 3.0wt%, and the rest are the same as in Example 1. See Table 5 for details. When a large amount of hindered phenolic antioxidant is added, although the antioxidant effect is excellent, the fiber tends to be yellowed.
[比較例11] [Comparative Example 11]
PEG8300的添加量為50wt%，受阻酚類抗氧化劑IR1010的添加量為0.5wt%，其餘同實施例1。具體見表5。受阻酚類抗氧化劑少量添加的場合，雖然可以抑制纖維的黃變，但是抗氧化效果降低。 The addition amount of PEG8300 is 50wt%, the addition amount of hindered phenolic antioxidant IR1010 is 0.5wt%, and the rest are the same as in Example 1. See Table 5 for details. When a hindered phenolic antioxidant is added in a small amount, the yellowing of fibers can be suppressed, but the antioxidant effect is reduced.
[比較例12] [Comparative Example 12]
PEG3400的添加量為20wt%，受阻酚類抗氧化劑IR1010的添加量為0.5wt%，其餘同實施例13。具體見表5。與受阻酚類抗氧化劑相比，受阻酚類抗氧化劑容易導致聚酯黃變。在 PEG添加量少的情況下，雖然只需要添加少量的受阻酚類抗氧化劑IR1010，聚酯黃變指數也在可接受範圍之內，但是聚酯的抗氧化效果降低，染色前後聚酯纖維的吸濕率差的差值大，說明染色後聚酯纖維的吸濕性下降明顯。 The addition amount of PEG3400 is 20wt%, the addition amount of hindered phenolic antioxidant IR1010 is 0.5wt%, and the rest are the same as Example 13. See Table 5 for details. Compared with hindered phenolic antioxidants, hindered phenolic antioxidants tend to cause polyester yellowing. In the case of a small amount of PEG added, although only a small amount of hindered phenolic antioxidant IR1010 needs to be added, the yellowing index of polyester is also within the acceptable range, but the antioxidant effect of polyester is reduced, and the polyester fiber before and after dyeing. The difference of the difference in the moisture absorption rate is large, indicating that the moisture absorption of the polyester fiber after dyeing is significantly reduced.
[比較例13] [Comparative Example 13]
PEG3400的添加量為50wt%，受阻酚類抗氧化劑IR1010的添加量為3.0wt%，其餘同實施例13。具體見表5。受阻酚類抗氧化劑大量添加的場合，雖然抗氧化效果優異，但是纖維容易發生黃變。 The addition amount of PEG3400 is 50wt%, the addition amount of hindered phenolic antioxidant IR1010 is 3.0wt%, and the rest are the same as Example 13. See Table 5 for details. When a large amount of hindered phenolic antioxidant is added, although the antioxidant effect is excellent, the fiber tends to be yellowed.
[比較例14] [Comparative Example 14]
PEG3400的添加量為50wt%，受阻酚類抗氧化劑IR1010的添加量為0.5wt%，其餘同實施例13。具體見表5。受阻酚類抗氧化劑少量添加的場合，雖然可以抑制纖維的黃變，但是抗氧化效果降低。 The addition amount of PEG3400 is 50wt%, the addition amount of hindered phenolic antioxidant IR1010 is 0.5wt%, and the rest are the same as in Example 13. See Table 5 for details. When the hindered phenolic antioxidant is added in a small amount, the yellowing of the fiber can be suppressed, but the antioxidant effect is reduced.
[實施例15] [Example 15]
PEG8300的添加量為22wt%，半受阻酚類抗氧化劑CN1790的添加量為1.0wt%，其餘同實施例1。具體見表5。PEG8300的添加量不合適，導致吐出性變差。 The addition amount of PEG8300 is 22wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 1.0wt%, and the rest are the same as in Example 1. See Table 5 for details. The amount of PEG8300 added was inappropriate, resulting in poor discharge properties.
[實施例16] [Example 16]
PEG8300的添加量為25wt%，半受阻酚類抗氧化劑CN1790的添加量為1.0wt%，其餘同實施例1。具體見表5。PEG8300的添加量不合適，導致吐出性變差。 The addition amount of PEG8300 is 25wt%, the addition amount of semi-hindered phenolic antioxidant CN1790 is 1.0wt%, and the rest are the same as in Example 1. See Table 5 for details. The amount of PEG8300 added was inappropriate, resulting in poor discharge properties.
[比較例17] [Comparative Example 17]
PEG8300的添加量為50wt%，受阻酚類抗氧化劑 IR1010的添加量為3.0wt%，其餘同實施例24。具體見表6。複合紡絲的場合，受阻酚類抗氧化劑大量添加時，雖然抗氧化效果優異，但是纖維容易發生黃變。 The addition of PEG8300 is 50wt%, the addition of hindered phenolic antioxidant IR1010 is 3.0wt%, and the rest are 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 is added, although the antioxidant effect is excellent, the fiber tends to be yellowed.
[比較例18] [Comparative Example 18]
PEG8300的添加量為50wt%，受阻酚類抗氧化劑IR1010的添加量為0.8wt%，其餘同實施例24。具體見表6。複合紡絲的場合，受阻酚類抗氧化劑少量添加時，雖然可以抑制纖維的黃變，但是抗氧化效果降低。 The addition amount of PEG8300 is 50wt%, the addition amount of hindered phenolic antioxidant IR1010 is 0.8wt%, and the rest are 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 is added, the yellowing of the fiber can be suppressed, but the antioxidant effect is reduced.
[比較例19] [Comparative Example 19]
PEG8300的添加量為50wt%，不添加抗氧化劑，其餘同實施例24。具體見表6。由於沒有添加抗氧化劑，纖維不會發生黃變，但是不具有抗氧化效果。 The addition amount of PEG8300 is 50wt%, and no antioxidant is added, and the rest are the same as in Example 24. See Table 6 for details. Since no antioxidants are added, the fiber does not yellow, but it does not have an antioxidant effect.
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| CN109097858A (en) * | 2018-09-05 | 2018-12-28 | 安徽泛博纺织科技有限公司 | A kind of polyester filament and preparation method thereof of high regain |
| CN110205692A (en) * | 2019-06-24 | 2019-09-06 | 绍兴诚邦高新纤维科技有限公司 | A kind of processing method of the double-colored superfine composite polyester fiber of same plate |
| JP7363232B2 (en) * | 2019-09-10 | 2023-10-18 | 東レ株式会社 | Method for producing polyester composition with excellent hygroscopicity |
| CN115260473A (en) * | 2022-07-12 | 2022-11-01 | 日华化学（中国）有限公司 | Polyester polyether resin washable moisture absorption quick-drying agent for polyester fiber and blended fabric thereof and application method |
| CN115821418B (en) * | 2022-10-18 | 2024-04-05 | 浙江恒逸石化研究院有限公司 | Method for preparing high-sulfonate-content antibacterial flame-retardant cationic dye-dyeable polyester fiber based on autocatalysis |
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| DE102012016444A1 (en) * | 2012-08-18 | 2014-02-20 | Clariant International Ltd. | polyester |
| CN104711695B (en) * | 2013-12-13 | 2018-03-16 | 东丽纤维研究所（中国）有限公司 | A kind of fiber and its production and use |
| CN105986330A (en) * | 2015-02-13 | 2016-10-05 | 东丽纤维研究所（中国）有限公司 | Antistatic polyester fiber, preparation method of polyester composition, and method for preparing fiber |
-
2016
- 2016-10-25 CN CN201610934835.3A patent/CN107973903A/en active Pending
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2017
- 2017-10-23 CN CN201780050617.6A patent/CN109563257B/en active Active
- 2017-10-23 WO PCT/CN2017/107220 patent/WO2018077126A1/en active Application Filing
- 2017-10-23 JP JP2019521413A patent/JP6988891B2/en active Active
- 2017-10-23 KR KR1020197011786A patent/KR102356959B1/en active IP Right Grant
- 2017-10-23 TW TW106136344A patent/TWI753033B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009235242A (en) * | 2008-03-27 | 2009-10-15 | Teijin Fibers Ltd | Copolyester and polyester fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190073388A (en) | 2019-06-26 |
| TW201819457A (en) | 2018-06-01 |
| CN109563257B (en) | 2020-12-25 |
| CN109563257A (en) | 2019-04-02 |
| CN107973903A (en) | 2018-05-01 |
| JP2019531395A (en) | 2019-10-31 |
| KR102356959B1 (en) | 2022-01-28 |
| WO2018077126A1 (en) | 2018-05-03 |
| JP6988891B2 (en) | 2022-01-05 |
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