JPH04332755A - Hydrophilic polyester composition having excellent discoloration resistance - Google Patents

Abstract

PURPOSE:To provide a hydrophilic polyester composition extremely reduced in the discoloration when held under high temperatures. CONSTITUTION:The polyester composition is characterized by adding a specific phenolic stabilizer, a specific thiopropionate stabilizer and a specific phosphorous stabilizer in specified amounts, respectively, to a polyester composition comprising IC pts.wt. of an aromatic polyester and 0.2-30 pts.wt. of a polyoxyethylene polyether having an average mol.wt. of >=5000. Since the discoloration of the polyester composition is prevented under high temperatures, the polyester composition gives various products excellent in the initial whiteness and durability.

Description

Description: FIELD OF THE INVENTION This invention relates to improved hydrophilic polyester compositions. More specifically, discoloration occurs when the polyester composition is melt-molded, discoloration occurs when a molded product obtained by melt-molding the polyester composition is subjected to heat treatment and/or alkali treatment, and discoloration occurs when the molded product is exposed to a high-temperature oxygen atmosphere. The present invention relates to a hydrophilic polyester composition with excellent discoloration resistance and significantly reduced discoloration when held under the surface. [0002] Polyester has many excellent properties and is therefore widely used as a molding material for fibers, films, sheets, etc. However, since polyester is hydrophobic, its use in fields where hydrophilic properties such as antistatic properties, water absorption properties, and antifouling properties (soil release properties) are required is limited. [0003] Conventionally, in an attempt to impart hydrophilic properties such as antistatic properties, water absorption properties, and antifouling properties to polyester, there has been a method of blending polyoxyethylene polyethers such as polyoxyethylene glycol (for example, Japanese Patent Publication No. 39-197-1). 5214, JP-A-55-165917) Furthermore, a method of blending an ionic compound such as an organic sulfonic acid metal salt in combination with the above polyoxyethylene polyether (for example, JP-B-44-31828) It has been known. However, in these methods, the polyoxyethylene polyether used has poor heat resistance and antioxidant properties, so when melt-molding the polyester composition, the molded product obtained by melt-molding has a fine structure. The drawback is that when heat-treated to stabilize the molded product, and also when the molded product is held in a hot air atmosphere, for example for drying, significant coloring occurs. In an attempt to overcome these drawbacks, pentaerythrityl-tetrakis-[3-(3,5-di-t-
Methods using hindered phenol antioxidants such as butyl-4-hydroxyphenyl) propionate have been proposed (for example, JP-A No. 59-228018, JP-A No. 61-152822, JP-A No. 61-152822, 60-17
No. 117, JP-A-61-160476). However, in these methods, while the hindered phenol antioxidant has the effect of preventing the oxidative decomposition of polyoxyethylene polyether, it has the disadvantage that the antioxidant itself is oxidized and becomes significantly colored. As a result, it was found that the color fastness was not improved. Furthermore, according to the studies of the present inventors, when the polyester fiber finally obtained by this method is subjected to alkali weight loss processing, which is generally widely performed to improve the texture, depending on the processing conditions, It has been found that after weight reduction treatment, the product may turn yellow to such an extent that it cannot be used in the normal clothing field. As a result of detailed investigation of this process, we found that although the mechanism of action is still unclear, the above-mentioned yellowing was significantly It turned out to be. [0006] On the other hand, the present inventors have developed a method for producing water by specifically copolymerizing ethylene oxide with a specific higher olefin oxide instead of the above-mentioned water-soluble polyoxyethylene polyether such as polyoxyethylene glycol. It has been found that by using insolubilized non-randomly copolymerized polyoxyethylene-based polyether, durability, particularly in hydrophilicity, can be dramatically improved, and an application has already been filed (Japanese Patent Laid-Open No. 2-269762). In addition, we have filed a patent application for the discovery that phosphite-based antioxidants are effective for preventing such water-insoluble, non-randomly copolymerized polyoxyethylene-based polyethers from becoming water-soluble (Japanese Patent Application Laid-Open No.
-274758). Furthermore, the problem of yellowing caused by the alkali weight loss process described above is improved by using specific amounts of an antioxidant and a partially hindered phenol compound.
Furthermore, it has been found that when a thiopropionate compound is contained in a specific amount ratio in addition to a partially hindered phenol compound, the two act synergistically to further dramatically improve the yellowing prevention effect described above. Filed (Patent Application No. 2-2752)
Publication No. 22). However, even with polyester compositions containing the water-insoluble polyoxyethylene polyether described above, yellowing occurs during melt molding, and the resulting molded product undergoes heat treatment and/or alkali weight loss treatment. None had a sufficiently excellent preventive effect against both discoloration during molding and discoloration when the molded product was held in a high-temperature oxygen-containing atmosphere. OBJECTS OF THE INVENTION In view of the above-mentioned current situation, the present invention addresses discoloration during melt molding, discoloration when the obtained molded product is subjected to heat treatment and/or alkali weight loss treatment, and the like. The object of the present invention is to provide a hydrophilic polyester composition that has an excellent effect of preventing discoloration when a molded article is held in a high-temperature oxygen-containing atmosphere. Such a composition is particularly useful in lingerie applications, foundation applications, etc., since it has both hydrophilicity and high whiteness when made into fibers, for example. [0009]Structure of the Invention In order to achieve the above object, the present inventors have made intensive studies focusing on antioxidants, and as a result, they have developed a specific phenol compound, a specific thiopropionate compound, and a specific phosphorus compound, respectively. It has been found that when used in a specific amount, these three act synergistically to provide particularly excellent color fastness. The present invention was completed as a result of further studies based on this knowledge. That is, the present invention has the following features: 1. (a) 100 parts by weight of aromatic polyester, (b)
0.2 to 30 parts by weight of a polyoxyethylene polyether with an average molecular weight of 5000 or more, (c) a phenol compound in an amount ranging from 1.0 to 30% by weight based on the polyoxyethylene polyether, ( d) a thiopropionate compound in an amount ranging from 0.2 to 5 times the weight of the phenol compound; and (e) an amount of 0.1 to 10% by weight based on the polyoxyethylene polyether. In the polyester composition comprising a phosphorus compound in an amount of 3,9-bis[2-{3
-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]
undecane and/or 1,3,5-tris(4-t
-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3
H,5H)-trione, and the thiopropionate compound is tetrakis[methylene-3-(dodecylthio)
propionate] methane and/or distearyl-
3,3'-thiodipropionate, and the phosphorus compound is 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite and/or tetrakis(2,4-di-t-butylphenyl); -butylphenyl)-4,4
A hydrophilic polyester composition with excellent discoloration resistance, characterized by being biphenylene phosphonite. 2. The polyoxyethylene polyether is represented by the following general formula (I) and has an average molecular weight of 5,000 to 16,000.
The hydrophilic polyester composition having excellent discoloration resistance according to claim 1, which is a water-insoluble non-random copolymerizable polyoxyethylene polyether. [0011] [0012] The aromatic polyester as used in the present invention is an aromatic polyester having an aromatic ring in the chain unit of the polymer, and is composed of a difunctional aromatic carboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. It is a polymer obtained by reaction with The difunctional aromatic carboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid,
, 5-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4
'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-diphenyl etherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,
4'-diphenylisopropylidenedicarboxylic acid, 1
, 2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-
anthracene dicarboxylic acid, 4,4'-p-terphenylene dicarboxylic acid, 2,5-pyridine dicarboxylic acid,
Examples include β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and terephthalic acid is particularly preferred. Two or more of these difunctional aromatic carboxylic acids may be used in combination. In addition, in small amounts, in addition to these difunctional aromatic carboxylic acids, difunctional aliphatic carboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and difunctional alicyclic carboxylic acids such as cyclohexanedicarboxylic acid can be used. Acid, 5-sodium sulfoisophthalic acid, etc. can be used alone or in combination of two or more. Further, as diol compounds, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2
Preferred examples include aliphatic diols such as -methyl-1,3-propanediol, diethylene glycol and trimethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof. Further, if the amount is small, polyoxyalkylene glycol whose both ends or one end are unblocked can be copolymerized with these diol compounds. Furthermore, polycarboxylic acids such as trimellitic acid and pyromellitic acid, polyols such as glycerin, trimethylolpropane, and pentaerythritol can be used as long as the polyester is substantially linear. Specific preferred aromatic polyesters include polyethylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyethylene-1,2-bis(phenoxy)ethane-4,4'.
- In addition to dicarboxylate, copolymerized polyesters such as polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, polybutylene terephthalate/decanedicarboxylate, etc. can be mentioned. Among these, polyethylene terephthalate and polybutylene terephthalate, which have well-balanced mechanical properties, moldability, etc., are particularly preferred. [0018] Such an aromatic polyester can be synthesized by any method. For example, to explain polyethylene terephthalate, terephthalic acid and ethylene glycol are directly esterified, a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol are transesterified, or terephthalic acid and ethylene oxide are transesterified. The first stage reaction involves reacting the glycol esters of terephthalic acid and/or their low polymers, and the second stage involves heating the product under reduced pressure to undergo a polycondensation reaction until a desired degree of polymerization is achieved. It is easily produced by step reaction. In addition,
The polyester described above may contain other thermoplastic polymers such as polyamides such as nylon-6, polyolefins such as polyethylene and polystyrene, etc., to the extent that the inherent physical properties of the polyester are not impaired. The hydrophilic polyester composition of the present invention includes:
A polyoxyethylene polyether having an average molecular weight of 5000 or more is blended. Note that the combination here is
This means that the polyoxyethylene polyether does not substantially copolymerize with the above-mentioned polyester, and it is sufficient if the average molecular weight is 5,000 or more. Such polyoxyethylene-based polyethers include polyethylene glycol, a copolymer in which oxyethylene units are the main component (usually 50 mol% or more) and oxyalkylene units such as oxypropylene units are randomly or block copolymerized therewith. Polyether can be used. Further, the terminal of such polyoxyethylene polyether may be a hydroxyl group or may be blocked with a non-ester-forming organic group. Among them, water-insoluble water-insoluble compounds represented by the following general formula (I) having a polyoxyethylene block as the main chain and blocking the terminals of the polyoxyethylene molecular chain with a specific oxyalkylene component Polyoxyethylene polyether improves hydrophilic properties such as antistatic properties, water absorption properties, and antifouling properties of the final polyester composition molded product, as well as durability such as hot water resistance, alkali resistance, and washing resistance. It is preferred because it exhibits particularly improved discoloration resistance when combined with the antioxidant specified in the present invention. [0023] Water insolubility here means that 5 g of the sample was added to 100 g of pure water, stirred at 100°C for 60 minutes, allowed to cool at room temperature, and then subjected to natural filtration using JIS standard 5 type A filter paper. 90% by weight or more is filtered out. In the above formula (I), Z is a residue of an organic compound having 1 to 6 active hydrogen atoms and having a molecular weight of 300 or less,
methanol, propanol, butanol, phenol,
Residues of hydroxy group-containing compounds such as ethylene glycol, bisphenol A, propylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolpropane, triethanolamine, diglycerin, pentaerythritol, sorbitol, and ethylene diamine, hexamethylene diamine, Examples include residues of primary and secondary amines such as diethylenetriamine, among which hydroxyl group compounds with a molecular weight of 300 or less are preferred. R1 is an unsubstituted alkylene group or substituted alkylene group having 6 or more carbon atoms, preferably a substituted alkylene group having 6 to 50 carbon atoms, and more preferably an alkylethylene group having 6 to 50 carbon atoms. Preferred specific examples of R1 include cyclohexylene group, phenylethylene group, hexylethylene group, methyl-pentylethylene group, heptylethylene group, methyl-hexylethylene group, and alkylethylene group having 12 to 40 carbon atoms. be able to. Furthermore, R1 may be a mixture of two or more of the above. R2 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a monovalent acyl group having 2 to 40 carbon atoms, and the hydrocarbon group includes an alkyl group, an alkenyl group, a cyclo Preferred are alkyl, aryl, alkylaryl or hydroxyalkyl groups. In addition, the acyl group includes an alkanoyl group, an alkenoyl group,
A cycloalkylcarbonyl group, an arylcarbonyl group or an alkylarylcarbonyl group is preferred. k is Z
is an integer from 1 to 6 corresponding to the number of active hydrogen atoms possessed by the organic compound that is the basis of. n is preferably an integer such that k×n is 70 or more, and may be the same or different between or within molecules. When the value of k×n is less than 70, the polyester composition molded product finally obtained has hydrophilic alkali durability such as antistatic property, hot water durability,
Washing durability etc. decreases. In addition, as the value of k×n increases, the hydrophilicity and its durability improve, but when this value exceeds 300, it becomes difficult to recognize a significant improvement in the hydrophilicity and its durability, and on the contrary, the polyoxyethylene Since it tends to be difficult to make the polyether insoluble in water, n is preferably an integer such that the value of k×n is 300 or less. A more preferable range of k×n is 80
~200 range. m is an integer of 1 or more, and may be the same or different between or within molecules, but it is preferable that all m in the k branches bonded to Z be integers of 1 or more. . When a branch in which m is 0 exists, the hydrophilic durability of the finally obtained polyester composition tends to decrease. The arrangement of the CH2 CH2 O units and R1 O units constituting this polyoxyethylene polyether is such that a polyoxyethylene block consisting of CH2 CH2 O units constitutes the main chain, and an R1 O unit is located at the end of the polyoxyethylene molecular chain. It is more desirable to have an arrangement in which the particles are localized by forming a block of one unit or two or more units. By adopting such a specific structure, it is possible to make the polyoxyethylene polyether highly water insolubilizable and highly improve its hygroscopicity with the introduction of a small amount of R1 O units, and it is possible to achieve a high degree of hydrophilicity and its durability. sexual achievement becomes possible. When CH2 CH2 O units and R1 O units are arranged randomly, hydrophilicity and durability thereof are reduced. The above water-insoluble polyoxyethylene polyether preferably has a molecular weight of 5,000 to 1,600.
The range is 0. When the molecular weight is less than 5,000, water insolubility and hygroscopicity cannot be achieved at the same time even if the R1 O unit is changed, and the hydrophilicity and durability of the final polyester composition molded product are reduced. Both decrease. On the other hand, when the molecular weight exceeds 16,000, the thermal stability of the water-insoluble polyoxyethylene-based polyether deteriorates rapidly, and for example, when melt-molded, the polyoxyethylene-based polyether may thermally decompose. This tends to cause disadvantages such as loss of water insolubility, poor compatibility with aromatic polyesters and insufficient hydrophilic durability, or deterioration of moldability and mechanical properties of molded articles. For example, when fiberized and subjected to alkali weight loss treatment of 20% by weight or more, not only the hydrophilic durability becomes insufficient, but also the alkali weight loss rate becomes excessive, the visual infection color property decreases, and it becomes insufficient. Even if a certain amount of dye is applied, the visual density is low (it looks whitish) and the abrasion resistance is also poor (the fibers become fibrillated due to friction, causing the dyed fabric to turn white). Among these, the preferred molecular weight range of the polyoxyethylene polyether is 5,500 to 14,000. Such a polyoxyethylene polyether can be produced by a first stage reaction in which an active hydrogen compound is reacted with ethylene oxide, then a second stage reaction in which the product is reacted with an olefin oxide having 6 or more carbon atoms, and, if necessary, It can be synthesized by a third step reaction in which the hydroxyl terminal group of the product is capped with a hydrocarbon group or an acyl group. Such olefin oxides include nonene oxide, cyclohexene oxide,
α-olefin oxides having 12 to 40 carbon atoms are particularly preferred. Particularly preferred examples of the above water-insoluble polyoxyethylene glycol polyether are shown in the table below. [Table 1] [Table 2] Specific examples of R2 other than H in the compounds shown in Table 1 include R2 = -CH3, -C6 H5, -CH2
C6 H5 , -C12H25, -C18H37, -
C18H35, C11H23CO-, C17H33CO
-, C17H35CO-, etc. are preferred. Such polyoxyethylene polyethers may be used alone or in combination of two or more. The polyoxyethylene polyether used in the polyester composition of the present invention is blended in an amount of 0.2 to 30 parts by weight based on 100 parts by weight of the aromatic polyester. If this amount is less than 0.2 parts by weight, the hydrophilicity of the resulting molded product will be insufficient and it will not be possible to exhibit sufficient antistatic properties, sweat absorption properties, and antifouling properties. In addition, even if the blending amount is greater than 30 parts by weight, no further improvement in the antistatic properties, sweat absorption properties, and antifouling properties of the resulting molded product is observed, and the mechanical properties of the resulting molded product are adversely affected. Heat resistance and light resistance will be impaired. [0034] In order to improve the antistatic properties of the polyester composition of the present invention, it is preferable to blend an organic or inorganic ionic compound, and it is particularly preferable to blend an organic ionic compound. The organic ionic compound is preferably an organic sulfonate that is substantially non-reactive with the aromatic polyester. As such an organic sulfonate, all organic sulfonate salts that are non-reactive with the aromatic polyester, such as organic sulfonic acid metal salts and organic sulfonic acid quaternary phosphonium salts, can be used, but among them, the following general Formula (II) ~
Examples include compounds represented by (V). embedded image In the above formula, R represents an alkyl group having 3 to 30 carbon atoms, an aryl group or alkylaryl group having 7 to 40 carbon atoms, and M represents an alkali metal. When R is an alkyl group, R may be linear or may have a branched side chain. M is an alkali metal such as Na, K, or Li, with Li, Na, or K being particularly preferred. R1, R2
, R3 and R4 are an alkyl group or an aryl group, and a lower alkyl group, a phenyl group or a benzyl group is particularly preferred. R5 represents a monovalent hydrocarbon group, preferably an alkyl group, a cycloalkyl group, an aryl group or an alkylaryl group. R6 is an alkylene group,
Usually 2 to 4 alkylene groups are preferred. Specific examples include ethylene group, propylene group, and tetramethylene group. It may also be a mixture of two or more types, for example a copolymer having an ethylene group and a propylene group. Among these, an ethylene group is particularly preferred. q is a positive integer indicating the degree of polymerization, preferably in the range of 1 to 100, especially 2
A range of 30 to 30 is particularly preferred. p is an integer from 2 to 4. Preferred specific examples of the compound represented by the above formula (II) include sodium stearylsulfonate, sodium octylsulfonate, a mixture of sodium alkylsulfonates having an average number of carbon atoms of 14, and t-
Lithium butylbenzenesulfonate, lithium dibutylbenzenesulfonate, sodium dodecylbenzenesulfonate (hard type, soft type), lithium dodecylbenzenesulfonate (hard type, soft type), potassium dodecylbenzenesulfonate (hard type, soft type) , sodium dibutylnaphthalene sulfonate, lithium dibutylnaphthalene sulfonate, and the like. Preferred specific examples of the compound represented by the above formula (III) include tetrabutylphosphonium alkylsulfonate having an average number of carbon atoms of 14, and tetraphenylphosphonium alkylsulfonate having an average number of carbon atoms of 14. , butyltriphenylphosphonium alkylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate (with an average number of carbon atoms of 14)
(hard type, soft type), tetraphenylphosphonium dodecylbenzenesulfonate (hard type, soft type), benzyltriphenylphosphonium dodecylbenzenesulfonate (hard type, soft type), and the like. Preferred specific examples of the compound represented by the above formula (IV) include the following. Preferred specific examples of the compound represented by the above formula (V) include metal salts in preferred specific examples of the compound represented by the above formula (IV), such as tetra-n-butylphosphonium salt, tetraphenylphosphonium salt, n −
Examples include compounds substituted with butyltriphenylphosphonium salt or phenyltri-n-butylphosphonium salt. The organic sulfonate salts of formulas (II) to (V) above may be used alone or in combination of two or more. Examples of inorganic ionic compounds include potassium iodide, sodium chloride, calcium chloride, sodium thiocyanate, potassium thiocyanate, lithium thiocyanate, and cesium thiocyanate. [0043] The above organic or inorganic ionic compound is
Only one type thereof may be used, or two or more types thereof may be used in combination. The amount of the aromatic polyester is 1
It is preferably within the range of 0.05 to 10 parts by weight relative to 0.00 parts by weight. If the amount is less than 0.05 parts by weight, the effect of improving antistatic properties on the resulting composition will be small, and if it exceeds 10 parts by weight, the mechanical properties of the composition will be impaired. The polyester composition of the present invention contains, as essential components, a specific phenol compound, a specific thiopropionate compound, and a specific thiopropionate compound, along with the above polyoxyethylene polyether and optionally an organic or inorganic ionic compound. It is important that specific amounts of each of the phosphorus compounds are included. The above phenol compound is 3,9-bis[2
-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethyl]-2,4,8,10-tetraoxaspiro[5.5]
Undecane [0046] and/or 1,3,5-tris(4-t-butyl-
3-hydroxy-2,6-dimethylbenzyl)-1,3
,5-triazine-2,4,6-(1H,3H,5H)
-trione [Chemical 7] and the above thiopropionate compound is tetrakis[methylene-3-(dodecylthio)propionate]methane [Chemical 8] and/or distearyl-3,3' - thiodipropionate [Chemical 9] and the phosphorus compound is 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite [Chemical 10] and/ or tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenephosphonite 0
[051] The amount of the phenol compound blended is in the range of 1.0 to 30% by weight based on the polyoxyethylene polyether, and the amount of the thiopropionate compound blended is 0.0% by weight based on the phenol compound. The amount of the phosphorus compound should be 2 to 5 times the amount by weight, and the amount of the phosphorus compound added should be 0.1 to 10% by weight based on the polyoxyethylene polyether. By using the above-mentioned specific phenol compound, specific thiopropionate compound, and specific phosphorus compound in the above-mentioned ranges, an amazing synergistic effect that could not be predicted from the conventional combination technology of antioxidants. occurs, discoloration occurs when the resulting polyester composition is melt-molded, discoloration occurs when the obtained molded product is subjected to heat treatment and/or alkali weight loss treatment, and when the molded product is held in a high-temperature oxygen-containing atmosphere. A significantly improved prevention effect is achieved against all types of discoloration. If even one of these essential antioxidant components is missing, or if even one of the amounts of each of the essential antioxidant components is out of the above range, the above-mentioned excellent resistance may be lost. No color change is obtained. The reason why such a special synergistic effect is produced is not clear, but based on the numerous experimental results of the present inventors, water-insoluble polyoxyethylene is more effective than water-soluble polyoxyethylene-based polyether as mentioned above. Since improved effects can be obtained with polyether-based polyethers, and among the many known antioxidants, the above-mentioned effects cannot be obtained with compounds other than those specified in the present invention, etc. It is presumed that some kind of interaction (for example, the antioxidant has a high solubility in the polyether) is at work between the ethylene polyether and the above-mentioned specific antioxidant. In order to produce the composition of the present invention, the aromatic polyester is combined with a polyoxyethylene polyether, optionally organic and inorganic ionic compounds, the above phenol compound, the above thiopropionate compound and the above phosphorus. To incorporate the compounds, the above components can be incorporated into the aromatic polyester simultaneously or in any order by any method. That is, at any stage until the completion of molding of the aromatic polyester, for example, before the start of the polycondensation reaction of the aromatic polyester, during the polycondensation reaction, at the end of the polycondensation reaction when it is still in a molten state, or in a powdered state. ,
Alternatively, in the molding step or the like, the additive components may be melt-mixed in advance and then added once or in two or more portions, or each of the additive components may be added separately. When added before the middle stage of the polycondensation reaction, it may be added after being dissolved or dispersed in a solvent such as glycol. Furthermore, it is particularly preferable to add the above-mentioned phosphorus compound at any stage of the manufacturing process of the polyoxyethylene polyether because its effect will be increased. [0054] The composition of the present invention may also contain a conventional ultraviolet absorber, and it is preferable to do so. In addition, flame retardants, optical brighteners, matting agents, colorants, and other additives may be added as necessary. When producing fibers from the polyester composition of the present invention, any spinning conditions can be used without any problem. For example, a method of melt spinning at a speed of 500 to 2,500 m/min, stretching, and heat treatment;
A method of melt spinning at a speed of 5000 m/min and performing drawing and false twisting simultaneously or successively, a method of melt spinning at a high speed of 5000 m/min or more and omitting the drawing step depending on the application, etc. conditions may be adopted. The fibers obtained in this manner may be solid fibers having no hollow portions, or may be hollow fibers having hollow portions. Further, the outer shape and the shape of the hollow portion in the fiber cross section may be circular or irregular. Furthermore, even if it is a core-sheath type composite fiber having the polyester composition of the present invention as a core component and a normal polyester as a sheath component, it may also be a core-sheath type composite fiber having the polyester composition of the present invention as a sheath component and a normal polyester as a core component. It may be a core-sheath type conjugate fiber, or it may be a multilayer conjugate fiber with two or more layers side-by-side consisting of a layer made of the composition of the present invention and a layer made of ordinary polyester. You can. [0056] Such polyester fibers may be subjected to appropriate post-hydrophilic processing, if necessary, and it is preferable to do so. This post-hydrophilic treatment includes, for example, treating the polyester fibers with an aqueous dispersion of a polyester polyether block copolymer consisting of terephthalic acid and/or isophthalic acid or their lower alkyl esters, lower alkylene glycol, and polyalkylene glycol. A method of treating with a liquid, a method of graft polymerizing a hydrophilic monomer such as acrylic acid or methacrylic acid, and then converting this into a sodium salt can be preferably employed. The composition of the present invention can also be used for producing films and sheets. Furthermore, any molding conditions can be adopted in this molding process without any problems. For example, a method of manufacturing an anisotropic film by applying tension in only one direction after film formation, a method of stretching the film in two directions simultaneously or in an arbitrary order, and a method of multi-stage stretching of the film in two or more stages. , etc. can be adopted under any conditions. Furthermore, the composition of the present invention can also be used as a masterbatch. This masterbatch can also be diluted with a conventional polyester resin that does not contain polyether polymers, and the mixture can be melt-molded into final molded articles such as fibers, films, sheets, etc. Effects of the Invention: Molded articles such as fibers obtained from the polyester composition of the present invention have excellent antistatic properties, water absorption properties, and stain resistance (
In addition to having hydrophilic properties such as soil release properties and durability (hot water resistance, alkali resistance, and washing resistance), when melt-molding the polyester composition, the molded product obtained by melt-molding has a fine structure. During heat treatment for stabilization, and when the molded product is held in a high-temperature air atmosphere for drying, for example, after washing, coloration is significantly suppressed, which improves initial whiteness and its maintenance properties. An extremely superior product can be obtained. Furthermore, fibers made of the composition of the present invention can be subjected to alkali weight loss treatment even if the conventionally widely used hanging kneading or batch dipping method using a liquid bath dyeing machine is adopted. Even if continuous processing methods such as the pad-dry method and pad-steam method, which are used to improve texture, are used, yellowing problems do not occur during weight reduction processing, resulting in high whiteness and excellent texture. You can get fabric. [0061] Therefore, the fibers made of the composition of the present invention are
It can be used for all kinds of textile products that require anti-static properties, water absorption, and stain resistance, such as lingerie, foundations, innerwear, dust-free clothing, uniforms, and linings. In addition, when the composition of the present invention is made into a film or sheet, it has particularly excellent whiteness, as well as extremely excellent antistatic properties, water absorption, printability, adhesion, etc. in terms of water resistance. It is extremely useful. [Examples] The present invention will be explained in more detail with reference to specific examples, but the present invention is not limited to these examples. Note that the whiteness index, frictional charging voltage, etc. that appear in the examples were measured by the following methods. (1) Whiteness index Lightness index L* and chromaticness index b* specified in JIS Z8722 and JIS Z8727
The whiteness index W was determined according to the following formula. W
=L* -b* (2) Frictional charging voltage Using a rotary static tester (Kyoto University, Kaken type), JIS L-1094 8.2B method was followed. (3) Washing method: According to JIS L-1018-77 6.36H method. [Example 1 and Comparative Examples 1 to 9] 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, 0.06 part of calcium acetate monohydrate (0.06 parts based on dimethyl terephthalate).
066 mol%) and 0.009 part of cobalt acetate tetrahydrate as a coloring agent (0.00 part relative to dimethyl terephthalate)
7 mol %) was charged into a transesterification tank, and the temperature was raised from 140° C. to 220° C. over 4 hours under a nitrogen gas atmosphere, and the transesterification reaction was carried out while distilling the generated methanol out of the system. After the transesterification reaction was completed, 0.058 part of trimethyl phosphate (0.080 mol % based on dimethyl terephthalate) as a stabilizer and 0.024 part of dimethylpolysiloxane as an antifoaming agent were added. Then, 10 minutes later, 0.04 part of antimony trioxide (0.027 mol % based on dimethyl terephthalate) was added, the temperature was raised to 240°C while simultaneously expelling excess ethylene glycol, and the mixture was transferred to a polymerization vessel. Then 760mmHg over 1 hour
The pressure was reduced from 1 to 1 mmHg, and at the same time the temperature was raised from 240°C to 285°C over 1 hour and 30 minutes. Two hours after the start of decompression, the following chemical formula: [Chemical formula 12] Two parts of water-insoluble polyoxyethylene polyether having a molecular weight of 7106 were added in a molten state under reduced pressure. Subsequently, polymerization was continued for 1 hour under a reduced pressure of 1 mmHg or less with stirring, and then the phenol compound, thiopropionate compound, and phosphorus compound listed in Table 2 were added in the amounts listed in Table 2, and the polymerization was continued for another 20 minutes to reach the ultimate limit. Viscosity 0.6
A polymer having a softening point of 36-0.662°C and a softening point of 261.8-262.5°C was obtained. This polymer was made into chips using a conventional method. The obtained chips were dried in a conventional manner and melted at 285° C. using an extrusion spinning machine equipped with a spinneret having 24 circular spinning holes with a hole diameter of 0.3 mm, and the take-up speed was 1500 m/min. It was spun with Next, a drawn yarn of 50 denier/24 filaments was obtained by drawing heat treatment using a heating roller at 90° C. and a drawing heater at 170° C. at a drawing ratio such that the elongation of the obtained drawn yarn was 35%. The obtained drawn yarn was made into a knitted fabric and processed under the following processing conditions in the order of scouring → presetting → alkali weight loss. Scouring: Score roll #900 0.
5g/liter, Na2 CO3 0.5g/liter, 70℃ x 20 minutes Preset: Dry heat heat set at 190℃ x 1 minute Alkali weight loss: <Padding conditions> Using NaOH 200g/liter aqueous solution, mangle pressure 3kg /cm2 to obtain a pickup rate of 90%. <Steaming conditions> The knitted fabric padded with NaOH aqueous solution under the above conditions is immediately steamed with saturated steam (100°C).
The material was steamed in a vacuum chamber until the weight loss rate reached 20%, and then dried at 100° C. for 5 minutes. Whiteness index after scouring, after presetting, after alkali treatment and after holding the scoured fabric in a hot air dryer at 170° C. for 20 hours, friction zone of the alkali weight loss fabric without washing (referred to as L0) The voltage and the frictional charging voltage after washing 30 times (referred to as L30) were measured, and the results are shown in Table 2. Examples 2 to 9 The same operations as in Example 1 were carried out. however,
0.4 part of sodium dodecylbenzenesulfonate was added together with water-insoluble polyoxyethylene polyether. The results are shown in Table 2. Example 10 The same operation as in Example 2 was carried out. However, the phosphorus compound used together with the phenol compound and the thiopropionate compound was previously added to the polyoxyethylene polyether in the process of producing the polyoxyethylene polyether. The results were as shown in Table 2. [Comparative Examples 10 and 11] The same operation as in Example 2 was carried out. However, the type of phosphorus compound used together with the phenol compound and thiopropionate compound was changed to the compounds listed in Table 2. The results are shown in Table 2. [Comparative Example 12] The same operation as in Example 2 was carried out. However, the thiopropionate compound was not used, the type and amount of the phenol compound were changed as shown in Table 2, and the amount of the phosphorus compound used was also changed as shown in Table 2. The results were as shown in Table 2. [Example 11 and Comparative Example 13] The same operation as in Example 2 was carried out. However, instead of water-insoluble polyoxyethylene polyether, 2 parts of water-soluble polyoxyethylene glycol with an average molecular weight of 20,000 is used, and in place of sodium dodecylbenzenesulfonate, the number of carbon atoms is in the range of 8 to 20. , and 0.4 part of sodium alkylsulfonate having an average number of carbon atoms of 14 was used. The results were as shown in Table 2. [Table 3] [Table 4] The abbreviations in Table 2 are as follows. A: 3,9-bis[2-{3-(3-t-butyl-4-
Hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane (manufactured by Sumitomo Chemical:
Sumilizer GA-80) B: Tetrakis[methylene-3-(dodecylthio)propionate]methane (manufactured by Asahi Denka: Adekastab AO-4
12S) C: 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite (Asahi Denka: Adekastab HP-10) D: 1,3,5-tris(4-t-butyl- 3-Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (manufactured by American Cyanamid: Cyanox 1790) E: Distearyl- 3,3'-thiodipropionate (Sumitomo Chemical: Sumilizer TPS) F: Tetrakis(2,4-di-t-butylphenyl)-
4,4'-biphenylenephosphonite (manufactured by Ciba Geigy: Irgafos P-EPQ) G: Tris(2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Geigy: Irgafos 168) H
: Distearyl pentaerythritol diphosphite (
Manufactured by Asahi Denka: Adekastab PEP-8) I: Pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-
4-Hydroxyphenyl)propionate] (manufactured by Ciba Geigy: Irganox 1010)

Claims (2)

[Claims] Claim 1: (a) 100 parts by weight of an aromatic polyester, (b) 0.2 to 30 parts by weight of a polyoxyethylene polyether having an average molecular weight of 5,000 or more, and (c) the polyoxyethylene polyether. 1.0-30 against
(d) a thiopropionate compound in an amount ranging from 0.2 to 5 times the weight of the phenol compound; and (e) the polyoxyethylene polyether. 3,9-bis[2-{3-(3-t-butyl-4 -Hydroxy-5
-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane and/or 1,3,5-tris(4-t-butyl- 3-Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6
-(1H,3H,5H)-trione, and the thiopropionate compound is tetrakis[methylene-3-(dodecylthio)propionate]methane and/or distearyl-3,3'-thiodipropionate. , and the phosphorus compound is 2,2-methylenebis(4,6
-Di-t-butylphenyl)octyl phosphite and/or tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylenephosphonite, which is a hydrophilic compound with excellent color fastness. polyester composition. [Claim 2] The polyoxyethylene polyether is represented by the following general formula (I) and has an average molecular weight of 5000.
The hydrophilic polyester composition according to claim 1, which is a water-insoluble, non-random copolymerizable polyoxyethylene polyether having a molecular weight of 16,000 to 16,000. [Chemical formula 1]