JPH0841300A - Soil-releasing polyester composition and fibers thereof having improved wash durability - Google Patents

Abstract

(57) [Summary] [Structure] A specific proportion of one end-blocked polyoxyalkylene polyether having a molecular weight of 6,000 or less is copolymerized and a trivalent carboxylic acid component and / or a trivalent glycol component or a pentavalent Antiesters, especially (a) single hindered phenolic compounds (a component), (b) thiopropionate compounds (b component) and ( c) A soil-releasing polyester composition having an isocyanuric group and containing a hindered phenolic compound (component (c)) other than the compound (a) and having improved wash durability, and a polyester composition thereof. Fiber. [Effect] A polyester fiber having excellent washing durability and soil release property can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soil-releasing polyester composition, and more particularly to a polyester composition having room-temperature soil-releasing property and excellent washing durability and a fiber derived therefrom.

[0002]

2. Description of the Related Art Polyester fiber has excellent dimensional stability,
It is used in a wide range of garments because of its excellent properties such as being strong and less likely to wrinkle. Especially in hospitals,
In recent years, a variety of uniforms have been used in the food industry, offices, etc., and there is a remarkable expansion of polyester fiber into the field of textile uniforms. However, since the polyester fiber having such excellent characteristics is also hydrophobic, the water absorbency and hygroscopicity are remarkably inferior, and oily stains are more likely to adhere to the hydrophilic fiber such as cotton and are difficult to remove. There is a problem that it easily recontaminates during washing. This is a problem that has always been raised since the development of polyester fibers in the field of textile uniforms, and many methods have been proposed to solve this problem.

Among them, the present inventors have prepared a composition obtained by blending a polyoxyethylene-based polyether, which is obtained by copolymerizing ethylene oxide with a specific olefin oxide and insolubilized in water, in a polyester. It was found that the property was improved and proposed (Japanese Patent Laid-Open No. 2-269).
762 and Japanese Patent Application Laid-Open No. 3-182546). However, in this method, since the polyether is merely physically dispersed in the polyester, there is a problem that the washing durability is poor.

On the other hand, as a method of imparting hydrophilicity to polyester, a method of copolymerizing a polyoxyethylene-based polyether with polyester is known, and this method also provides excellent antifouling property as compared with regular products. Can be granted. For example, polyoxyethylene glycol phenyl glycidyl ether (JP-A-1-236236)
Japanese Patent Application Laid-Open No. 1-23), polyoxyethylene glycol methyl 1,2-dihydroxypropyl ether
No. 4420) or polyethylene glycol monomethyl ether (see JP-B-3-23646), it is disclosed that a polyester having excellent water absorption and sweat absorption can be obtained. In the case of polyether copolymerization, physical elution of polyether into wash water is unlikely to occur, so good wash durability is expected, but in reality, unexpectedly, it is not always possible to prevent repeated wash. The reality is that the dirt performance is not maintained for a long time.

Polyoxyalkylene unit-containing polyesters are known to be prone to thermal oxidative deterioration of polyoxyalkylene moieties due to oxygen in the air,
There has been a concern about deterioration due to each step of polycondensation reaction of the copolyester, spinning, heat treatment or the like, or steam caused in industrial washing, drying, ironing and the like. Therefore, these polyoxyalkylene unit-containing copolyesters are required to have improved so-called oxidative decomposition resistance,
Many proposals have been made so far, and specific antioxidants are said to be effective. For example, according to JP-B-44-32311, a polyoxyalkylene glycol copolymerized polyester which is excellent in oxidative decomposition resistance and is easily dyeable by compounding a polyester copolymerized with polyoxyalkylene glycol with a hindered phenol compound. Compositions have been proposed.

Further, according to JP-A-2-38421, a modification obtained by mixing polyethylene glycol with a hindered phenol compound and adding a mixture obtained by heat treatment at a specific temperature and time. The high quality polyester is disclosed to have excellent color tone and oxidative decomposition resistance. Further, according to JP-A-5-214221, excellent oxidative decomposition resistance is obtained for a long period of time by using a single hindered phenol compound and both hindered phenol compounds in combination with a polyoxyalkylene unit-containing copolymerized polyester. It is said that a copolyester composition containing a polyoxyalkylene unit that can be maintained is obtained.

As described above, it has been proved that the addition of a hindered phenolic compound is effective for improving the resistance to oxidative decomposition of the polyoxyalkylene unit-containing polyester, but it is practically used for preventing heat deterioration. To obtain a sufficient effect, it is necessary to add a large amount of hindered phenolic compound. However, in that case, there is a possibility of causing poor spinning and deterioration of physical properties of the obtained fiber.

Further, according to the research conducted by the present inventors, it was found that even if the polyoxyalkylene unit-containing polyester acquires sufficient heat deterioration resistance, the antifouling property and the washing durability are not always maintained. That is, at present, when room-temperature washing at home has become popular, the antifouling performance is reduced by washing, even though it is assumed that thermal deterioration of polyalkylene units derived from steam, drying, iron, etc. in industrial washing is unlikely. It was the reality.

[0009]

Therefore, the inventors of the present invention have conducted research to improve the soil-releasing laundry durability in room temperature washing, and in addition to the polyalkylene oxide compound, a specific amount of trivalent carboxylic acid component or trivalent carboxylic acid component or trivalent carboxylic acid component. It was found that the washing durability is improved by copolymerizing the glycol component of 1) or the pentavalent phosphorus compound. Furthermore, the so-called washing durability is governed by two different mechanisms: heat deterioration during the process and deactivation of the polyether not dependent on heat during washing. From this, an antioxidant that satisfies both mechanisms at the same time. We have found that a high degree of washing durability can be imparted by designing the system and arrived at the present invention.

Thus, it is an object of the present invention to provide a polyester composition having excellent room temperature soil release properties and excellent wash durability, and a fiber made therefrom.

[0011]

According to the present invention, the object of the present invention is to: (i) copolymerize 0.2 to 10% by weight of a polyoxyalkylene-based polyether having one end blocked with a molecular weight of 6,000 or less. And a polyester having ethylene terephthalate as a main constituent, which is obtained by copolymerizing a trivalent carboxylic acid component and / or a trivalent glycol component in an amount of 0.05 to 0.5 mol%, or (ii) one end having a molecular weight of 6,000 or less 0.2 to 10% by weight of blocked polyoxyalkylene polyether
Copolymerized and a pentavalent phosphorus compound was added to the polyether.
/ 5 to 5 times mole copolymerized ethylene terephthalate-based polyester as a main constituent component, containing a antioxidant, a soil-releasing polyester composition having improved wash durability, and the same This is accomplished with fibers formed from the polyester composition.

Further, according to the present invention, (a) a hindered phenolic compound (a component) as the antioxidant,
(B) Thiopropionate-based compound (b component) and (c) Isocyanuric group-containing and hindered phenol-based compound (c component) other than the above-mentioned compound (a) are used in combination for further excellent washing durability. It has been found that a soil releasable polyester composition and fibers having properties are obtained.

The present invention will be described in more detail below. The copolyester of the present invention has a molecular weight of 6,000.
The following one end-capped polyoxyalkylene-based polyether is copolymerized at a certain ratio, and further, (i) a trivalent carboxylic acid component and / or a trivalent glycol component is copolymerized, or (ii) a pentavalent phosphorus. It is a polyester obtained by copolymerizing a compound. The polyether copolymerized with the polyester can be represented by, for example, the following general formula (I).

[0014]

Embedded image

In the above formula (I), M is a hydrogen atom, 1
Represents a valent metal or quaternary phosphonium. The monovalent metal includes Na, Li, K, Ca, Mg and A.
1 and the like, but especially Na, K, Li and Ca
Is preferred. When M is a quaternary phosphonium salt, the salt is represented by the formula —PR ³ R ⁴ R ⁵ R ⁶ . This R ³ , R ⁴ ,
R ⁵ and R ⁶ are the same or different and each has 1 carbon atom.
25 alkyl groups or aryl groups.

R ¹ is independently the same or different hydrocarbon group having 1 to 25 carbon atoms in the molecule, and at least one is a hydrocarbon group having 6 or more carbon atoms. As the hydrocarbon group, an alkyl group is preferable, and an alkyl group having 6 to 14 carbon atoms is particularly preferable. R ² is a hydrocarbon group having 1 to 21 carbon atoms. The hydrocarbon group may be an alkyl group or an aryl group, and may be a combination of two or more kinds, but an alkyl group is preferable. Specifically, a methyl group, an ethyl group,
Examples thereof include a propyl group, a hexyl group, a dodecyl group and a henicosan group. p is an integer from 0 to 5, q is 0
Is an integer of ˜5, and p and q satisfy (p + q) ≦ 5. p is preferably 0, 1 or 2, and q is preferably 0, 1 or 2. Further, the substitution position of the sulfonic acid group and the R ¹ group on the phenoxy group may be any position.

In the above formula (I), m and n respectively represent the number of the unit --CH ₂ CH ₂ O-- and the unit --CH ₂ CHR ² O-- in the polyether, and m is 15 to 1
20 is an integer, n is an integer of 0 to 50, and (m + n) is preferably an integer of 15 to 120. When a polyether having m of less than 15 is copolymerized with polyester, it is sufficient. A large amount of polyether is required to obtain the soil release property, and in such a case, the polymerization degree of the polyester itself cannot be sufficiently increased because the ends of the polyester are blocked, and the mechanical properties of the resulting fiber Cannot be secured. On the other hand, when m is larger than 120,
The reaction between the polyether and the polyester does not proceed sufficiently, and the result is the same as when the polyether is mixed and dispersed in the polyester, so that a high washing durability cannot be maintained.
The molecular weight of the polyether is not particularly limited as long as it is in the range of copolymerizing with the polyester, but it is 6,000.
It is sufficient if it is below, preferably 5,000 or less, and particularly preferably 4,500 or less. Each unit of the polyether may have an arbitrary arrangement, and may be a block copolymer, a random copolymer, or a combination thereof.

The polyether represented by the above formula (I) is easily produced by ring-opening polymerization of ethylene oxide and / or alkylene oxide at high temperature and high pressure using a phenoxide having an appropriately substituted sulfonic acid group. be able to. It is known that this polymerization process proceeds stepwise, and by adjusting the type, composition, and amount of alkylene oxide to be produced at any stage, a polyether having a molecular weight and a monomer sequence according to the purpose can be produced. Is possible. The molecular weight of the produced polyether can be easily determined by quantifying the terminal hydroxyl group.

In one type of the copolyester of the present invention, a specific amount of a trivalent carboxylic acid component and / or a trivalent glycol component is copolymerized with the above polyether. Examples of the trivalent carboxylic acid component include tricarboxylic acids such as trimellitic acid, trimellitic anhydride, and trimesic acid, and ester-forming compounds thereof. Examples of the trivalent glycol component include glycerin and trimethylolpropane. Triol is mentioned. Even if a carboxylic acid or alcohol having a valency of 4 or more is copolymerized, it will no longer contribute to the improvement of the room temperature soil release property, and the melt molding will become difficult, so that it cannot be used. These three
The valency of carboxylic acid component and glycol component may be used alone or in combination, but the total amount of copolymerization should be in the range of 0.05 to 0.5 mol%.
If it is less than 0.05 mol%, the effect of copolymerization will not be clearly exhibited, and if it exceeds 0.5 mol%, it will no longer contribute to the improvement of room-temperature washing durability, and the mechanical strength of the obtained yarn may decrease. Not preferable.

On the other hand, in another type of the copolyester of the present invention, a specific amount of a pentavalent phosphorus compound is further copolymerized with the above polyether. Examples of the pentavalent phosphorus compound include compounds represented by the following formula (II).

[0021]

Embedded image

In the formula (II), R ⁷ , R ⁸ and R ⁹ are the same or different and each is a hydrogen atom or an alkyl group, an allyl group,
It is a monovalent organic group such as a phenyl group or a hydroxyalkyl group. The pentavalent phosphorus compounds may be used alone or in combination of two or more. The amount of the pentavalent phosphorus compound used is appropriately in the range of 1/5 to 5 times the mole of the polyether, and particularly preferably in the range of 1/3 to 3 times the mole. If the addition amount of the phosphorus compound is too small, the effect of copolymerization will not be apparent, and if it is too large, it will not contribute to the improvement of the room-temperature washing durability and the mechanical strength of the obtained yarn may decrease, which is not preferable. .

When R ⁷ , R ⁸ and R ⁹ are monovalent organic groups, examples of the organic groups include aliphatic groups having 1 to 30 carbon atoms, preferably aliphatic groups having 1 to 18 carbon atoms, and alicyclic groups. Alternatively, an aromatic hydrocarbon group can be used. Specific examples of the pentavalent phosphorus compound include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, monomethyldiethyl phosphate, monomethyldiphenyl phosphate and the like, and ethylene glycol and propylene glycol. , A reaction product with a glycol component such as tetramethylene glycol and hexamethylene glycol.

The pentavalent phosphorus compound is a specific trivalent carboxylic acid component such as trimellitic acid, trimellitic anhydride, trimesic acid and / or a specific trivalent glycol such as glycerin and trimethylolpropane. You may use together with an ingredient.

The polyester in which the above-mentioned copolymerization component is copolymerized in the present invention is a polyester having terephthalic acid as a main acid component and ethylene glycol as a main glycol component. In such polyester, a part of its acid component, terephthalic acid, may be replaced with another difunctional carboxylic acid. Examples of such other carboxylic acid include diphthalic acid, 5-sodium sulfoisophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-oxyethoxybenzoic acid and p-oxybenzoic acid. Examples thereof include functional aromatic carboxylic acids, sebacic acid, adipic acid, and difunctional aliphatic carboxylic acids such as oxalic acid. Further, a part of the ethylene glycol component may be replaced with another glycol component, and examples of the glycol component include trimethylene glycol, tetramethylene glycol, pentamethylene glycol,
Hexamethylene glycol and other diol compounds. For example, cyclohexane-1,4-dimethanol,
Examples thereof include aliphatic, alicyclic and aromatic diol compounds such as neopentyl glycol, bisphenol A and bisphenol S, and polyoxyalkylene glycol having both ends unblocked. As other ester-forming compounds, aromatic hydroxycarboxylic acids such as β-hydroxyethoxybenzoic acid and p-oxybenzoic acid can be mentioned.

The copolyester of the present invention can be produced by any method. For example, polyethylene terephthalate can be described by direct esterification reaction of terephthalic acid and ethylene glycol, transesterification reaction of lower alkyl ester of terephthalic acid such as dimethyl terephthalate with ethylene glycol, or terephthalic acid and ethylene oxide. The reaction of the first step to form a glycol ester of terephthalic acid and / or a low polymer thereof, and then subjecting the product to a polycondensation reaction by heating under reduced pressure to a desired degree of polymerization. It is easily produced by a two-step reaction.

To copolymerize the one-end-capped polyether of the above formula (I) at the end of the polyester chain, the reaction may be carried out at any stage before the completion of the above-mentioned polyester synthesis, for example, before the initiation of the reaction in the first stage. After completion of the reaction, the reaction may be added at an arbitrary stage such as during the second stage reaction, and the production reaction may be completed after the addition.

In this case, if the copolymerization amount of the polyether is too small, the soil release property of the finally obtained polyester fiber and its washing durability become insufficient, and conversely if it is too large, it will occur during the polycondensation reaction. Since the degree of polymerization of the polyester reaches a peak at a low level, the yarn physical properties such as the strength of the finally obtained polyester fiber deteriorate. Further, when the polyether is contained in a large amount, the light resistance of the obtained fiber is deteriorated, so it is desirable that the copolymerization ratio be as small as possible. In the present invention, the copolymerization ratio of polyether is 0.
It should be in the range of 5 to 10% by weight, particularly preferably in the range of 2 to 6% by weight. As described above, in the present invention, the copolymerization amount of the polyether can be suppressed to a small amount, so that the obtained fiber can retain sufficient light resistance.

The other components to be copolymerized with the polyether can be added in the amounts described above at any of the above stages in the production of the polyester.

If necessary, stabilizers, matting agents, other antioxidants, optical brighteners, catalysts, anti-coloring agents, heat-resistant agents,
You may use a coloring agent, an inorganic particle, etc. together. In particular, when the polyether is left at a high temperature such as under melt spinning conditions, it is easily oxidized to easily cause a problem such as a decrease in the degree of polymerization and coloring, so that the combined use of an optical brightener is often preferable. Furthermore, the polyester having the soil release property in the present invention can be easily used together with other additional functions,
For example, if an ionic antistatic agent is used in combination, a fiber having excellent antistatic property can be obtained, and the field of use thereof will be further expanded.

The degree of polymerization of the thus obtained polyester of the present invention is preferably 0.58 or more, and particularly preferably 0.6 or more as an intrinsic viscosity in order to exhibit sufficient fiber characteristics.

The polyester composition of the present invention contains an antioxidant as an essential component of the copolymerized polyester,
In particular, (a) a hindered phenolic compound (a component), (b) a thiopropionate compound (b component) and (c) an isocyanuric group, and a hinder different from the compound (a). It contains a dephenol compound (component c). What is a hindered phenolic compound?
A phenolic compound having a sterically hindering substituent on one or both of two carbon atoms adjacent to a carbon atom having a phenolic hydroxyl group. One having a sterically hindering substituent on one side and a non-sterically hindering substituent such as a hydrogen atom, a primary alkyl group such as a methyl group and an ethyl group on the adjacent carbon atom on the other side It is called a phenolic compound, and a compound having a sterically hindering substituent on both is called a hindered phenolic compound.

A preferred specific example of the one-hindered phenolic compound (component a) is 3,9-bis [2-
[3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene Glycol bis- (3-tert-
Examples thereof include butyl-4-hydroxy-5-methylphenyl) propionate and 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane. Preferable specific examples of the thiopropionate compound (component b) include pentaerythritol-tetrakis (β-dodecyl-thiopropionate). Furthermore, as a preferable example of the hindered phenol-based compound (component c) having an isocyanuric group, tris (4-alkyl-3-hydroxy-2,6-dimethylbenzyl) -s-triazine-2,
4,6- (1H, 3H, 5H) -trione and Tris (2,4
-Dialkyl-3-hydroxy-6-methylbenzyl)
Examples thereof include -s-triazine-2,4,6- (1H, 3H, 5H) -trione, and the alkyl group thereof is preferably a secondary or tertiary alkyl group having 3 to 12 carbon atoms.

The content of the one-hindered phenolic compound (a component) and the thiopropionate compound (b component) in the polyester composition of the present invention is 0,0 based on the weight of the polyoxyalkylene polyether. It is desirable to be in the range of 2 to 10% by weight, preferably 0.5 to 8% by weight. When the content is less than 0.2% by weight, the washing durability of the copolyester is insufficient, and when it exceeds 10% by weight, the washing durability of the fiber made of the obtained polyester composition is not significantly improved. It is not observed, and on the contrary, the polymerization rate may be lowered, the obtained polymer may be colored, and the spinning may be poor. In addition, a single hindered phenolic compound (a
When the weight ratio of the component) to the thiopropionate compound (component b) is in the range of 75/25 to 25/75, the washing durability is preferably exhibited. The addition amount of the hindered phenol-based compound (component c) having an isocyanuric group is preferably in the range of 0.1% by weight to 10% by weight based on the weight of the polyoxyalkylene-based polyether. When it exceeds 10% by weight, no remarkable improvement in washing durability and heat deterioration resistance of the fiber made of the obtained polyester composition can be observed, and on the contrary, there is a risk of poor spinning, which is not preferable. Each component of the composition of the present invention may be a combination of two or more kinds.

When the polyester composition of the present invention is formed into a fiber, it is not necessary to employ a special method, and a usual melt spinning method for polyester fiber can be employed under any conditions. For example, a method of melt spinning at a speed of 500 to 2500 m / min, stretching and heat treatment, 1500 to 5000.
A method of performing melt spinning at a speed of m / min and simultaneously performing drawing and false twisting, or a method of performing melt spinning at a high speed of 5000 m / min or more and omitting the drawing step depending on the application To be done. Here, the fiber to be spun may be a solid fiber having no hollow portion or a hollow fiber having a hollow portion. Further, the outer shape of the fiber to be spun in cross section and the shape of the hollow portion may be circular or irregular.

Since the spun fiber exhibits sufficient fiber performance, it preferably has an elongation of 40% or less and a strength of 4 g / g.
It is stretched so that it is equal to or more than de, and heat-treated if necessary.

The reason why the fiber of the present invention thus obtained is excellent in soil release property and its washing durability and heat deterioration resistance is not yet clear, but the soil release property is the hydrophilicity or glass transition temperature of the polyether. ,
The result of complex entanglement of the end group effect, the microphase separation state of the polyether segment in the polyester fiber, the interfacial affinity between the polyester matrix and the polyether segment, the decomposition elution property of the polyether segment with respect to washing water, etc. It is thought to be played as.
Furthermore, addition of an appropriate amount of a trivalent carboxylic acid component, a trivalent glycol component or a pentavalent phosphorus compound significantly disturbs the orientation of the amorphous part, and as a result, microphase separation is more effectively exhibited. In addition, it is considered that the concentration of the antioxidant having poor compatibility with polyester in the amorphous part is promoted, and the heat deterioration and washing deterioration of the polyether are dramatically reduced.

As is clear from the examples, the heat deterioration resistance and the washing durability are sensitively changed depending on the kind and amount of the composition, with the former being mainly hindered phenol having an isocyanuric group and the latter being mainly It can be seen that the one-hindered phenol compound contributes. From this, it is considered that the hindered phenol having an isocyanuric group mainly acts as a scavenger of radicals generated by thermal deterioration, and the one-hindered phenolic compound acts as a scavenger of radicals generated at the time of washing and has a function of stopping the autoxidation of polyester. Furthermore, it is considered that the thiopropionate compound easily interacts with the produced intermediate radical to rapidly deactivate the radical. Thus, it is considered that effective trapping and deactivation of radicals generated by two different mechanisms results in synergistic improvement in washing durability.

[0039]

EXAMPLES The present invention will be further described with reference to the following examples. Parts and% in the examples represent parts by weight and% by weight, respectively. The intrinsic viscosity [η] of the polymer was obtained from the value measured with an orthochlorophenol solution at 35 ° C. In the examples, the following methods were adopted for washing treatment, stain treatment, and determining the stain rate.

(1) Washing treatment Water having a liquid temperature of 10 ° C. was placed in a domestic washing machine, and 2 g of synthetic detergent for clothes was added and dissolved in 1 liter of water to prepare a washing liquid. The sample and the load cloth were put into this washing liquid so that the bath ratio became 1:30, and the operation was started. 50
After the treatment for a minute, the operation was stopped, the sample and the load cloth were dehydrated with a dehydrator, and then overflow water washing was carried out for 15 minutes for dehydration. The above washing was set to LL5 and this was repeated as many times as necessary.

(2) Contamination treatment 10 cm × sandwiched in a holder with an artificial dirt liquid of the following composition
A 13 cm woven fabric was dipped to give stains. Composition of artificial dirt liquid・ Motor oil 99.335% by weight (Dia Queen Motor Oil M-2) Mitsubishi Motors Corporation ・ C heavy oil 0.634% by weight ・ Carbon black 0.031% by weight After that, put the sample between filter papers. To remove excess contaminated liquid,
It was allowed to stand in a dryer at 80 ° C. for 8 hours. The stain-treated sample was washed for 20 minutes in 15 ° C. water containing 2 g / l of Marcel soap under a weak condition of a home washing machine. Then, the soil release property was evaluated by the following method.

(3) Evaluation of Soil Release Property Using a Minolta color-difference meter CR-200 (Minolta Camera Co., Ltd.), the CIE colorimeter of the sample was evaluated by a conventional method.
E ^* was obtained and the soil release property was calculated by the following formula.

[0043]

[Equation 1]

In the above formula, ΔE ^* : Soil release property L ₁ , a ₁ , b ₁ : E ^* (L *, a *, b *) L ₂ , a ₂ , b ₂ of the sample before contamination: Washing E ^* (L *, a *, b *) of the later sample

(4) Heat deterioration resistance 10 mg of the drawn yarn sample was weighed and analyzed by a differential thermal analyzer (DS).
C; manufactured by Rigaku) under air atmosphere at 20 ° C./min for 19
The temperature was raised to 0 ° C and then to 210 ° C at 10 ° C / min.
After that, the temperature is maintained at the same temperature, and the time until the exothermic peak derived from the burning of polyether is observed (exothermic induction time) is 3
It was measured up to 00 minutes, and it was determined as heat deterioration resistance.

Example 1 100 parts of dimethyl terephthalate, ethylene glycol 6
0 part, 0.06 part of calcium acetate monohydrate (0.066 mol% relative to dimethyl terephthalate) and 0.009 part of cobalt acetate tetrahydrate as a color matching agent (0.007 mol relative to dimethyl terephthalate). %) In a transesterification reactor, the temperature of this reaction product is raised from 140 ° C. to 220 ° C. in a nitrogen gas atmosphere over 4 hours, and transesterification is carried out while distilling off the methanol produced in the reaction can out of the system. It was made to react. After the completion of the transesterification reaction, 0.058 part of trimethyl phosphate (0.080 mol% based on dimethyl terephthalate) as a stabilizer and 0.024 part of dimethylpolysiloxane as a defoaming agent were added to the reaction mixture. Then, after 10 minutes, 0.04 part of antimony trioxide (0.027 mol% relative to dimethyl terephthalate) was added to the reaction mixture,
At the same time, distilling off excess ethylene glycol,
The temperature was raised to 0 ° C., and then the reaction-finished product was transferred to a polymerization reaction can. Next, the reaction mixture was added with the following formula:

[0047]

[Chemical 3]

4 parts of a polyether having an average molecular weight of 2480 represented by (m is an average of 48) and 0.3 part of trimellitic anhydride (0.3 parts based on dimethyl terephthalate).
3 mol%), and the pressure in the reaction vessel was increased to 7
The pressure was reduced from 60 mmHg to 1 mmHg, and at the same time, the temperature of the reaction mixture was raised from 240 ° C to 285 ° C. 1m
Polymerization was further carried out under reduced pressure of mHg, and at this stage, 3,9-bis [2- [3- (3-ter] was added to the reaction mixture as an antioxidant.
t-Butyl-4-hydroxy-5-methylphenyl) propioxy] -1,1-dimethylethyl] -2,4,8,1
0.2 parts of 0-tetraoxaspiro [5,5] undecane (Sumilyzer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.)) (5 parts with respect to polyether), pentaerythritol-tetrakis (β-dodecyl-) Thiopropionate) (Adeka Stab AO-412S (manufactured by Asahi Denka Co., Ltd.)) and 0.2 parts (5 parts based on polyether) and tris (4-alkyl-).
3-hydroxy-2,6-dimethylbenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione)
(0.1 part of Sianox 1790 (manufactured by American Cyanamid Co., Ltd.) (2.5 parts with respect to polyether) was added, and the mixture was polymerized until the melt viscosity of the system reached a predetermined value. The polymer was made into chips by a conventional method.

After drying the obtained chips by a conventional method,
Melt at 285 ° C using an extrusion spinning machine having a spinneret with 24 circular spinning holes having a hole diameter of 0.3 mm, and discharge amount 3
The undrawn yarn thus obtained was spun at 7.5 g / min and a take-up speed of 1500 m / min, and the undrawn yarn thus obtained was subjected to a stretching treatment machine having a heating roller at 80 ° C. and a plate heater at 160 ° C. Draw heat treatment at a draw ratio of 30%
A drawn yarn of denier / 24 filament was obtained. A knitted fabric was produced using the obtained drawn yarn, and was scoured by a conventional method and heat set (180 ° C x 1 minute) to obtain a knitted fabric. This was subjected to the above-mentioned stain treatment, and the stain removability was evaluated. The results are shown in Table 1 below.

Examples 2 to 3 The same operation as in Example 1 was performed. However, the content and the result of changing the antioxidant composition are shown in Table 1 below.

Comparative Examples 1 to 5 The same operation as in Example 1 was performed. However, the content and the result of changing the antioxidant composition are shown in Table 1 below. However, in Comparative Example 5, the yarn breakage was remarkable during spinning, and the antifouling evaluation was impossible.

Comparative Example 6 The same operation as in Example 1 was performed. However, 0.2 parts of pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 (manufactured by Ciba Geigy)) was used as the antioxidant composition. (5 parts with respect to polyether) and the contents shown in Table 1 were replaced. The results are shown in Table 1.

Examples 4 to 5 The same operation as in Example 1 was performed. However, as a polyether, the following formula

[0054]

[Chemical 4]

A polyether having an average molecular weight of 2500 represented by (m is 55 on average) was used and the composition of the antioxidant was as shown in Table 1. The results are shown in Table 1.

Comparative Example 7 The same operation as in Example 5 was performed. However, the composition of the antioxidant was changed as shown in Table 1. The results are shown in Table 1.

Example 6 The same operation as in Example 1 was carried out except that trimethylolpropane was used as the trivalent compound. The results are shown in Table 1.

Comparative Examples 8 to 9 The same operation as in Example was carried out except that pyromellitic acid and pentaerythritol were used instead of trimellitic anhydride, respectively, but the yarn was cut during melt spinning and the obtained yarn was obtained. It was impossible to evaluate the antifouling property due to the remarkable deterioration of physical properties. The results are shown in Table 1.

[0059]

[Table 1]

(In the table, the amount of each antioxidant added is shown in parts by weight based on 100 parts by weight of one end-blocked polyoxyalkylene-based polyether copolymerization.) Examples 1 to 6 and Comparative Examples 1 to 1 Each of the fibers obtained in Example 9 was subjected to a soil release property evaluation test. The results are shown in Fig. 1.

Example 7 100 parts of dimethyl terephthalate, ethylene glycol 6
0 part, 0.06 part of calcium acetate monohydrate (0.066 mol% relative to dimethyl terephthalate) and 0.009 part of cobalt acetate tetrahydrate as a color matching agent (0.007 mol relative to dimethyl terephthalate). %) In a transesterification reactor, the temperature of this reaction product is raised from 140 ° C. to 220 ° C. in a nitrogen gas atmosphere over 4 hours, and transesterification is carried out while distilling off the methanol produced in the reaction can out of the system. It was made to react. After completion of the transesterification reaction, 0.058 parts of stabilizer trimethyl phosphate (0.080 mol% relative to dimethyl terephthalate), 0.024 parts of dimethylpolysiloxane as a defoaming agent, and a pentavalent phosphorus compound were added to the reaction mixture. Then, 0.29 parts of trimethyl phosphate (0.4 mol% based on dimethyl terephthalate) was added. Next, 0.04 parts of antimony trioxide (0.027 mol% with respect to dimethyl terephthalate) was added to the reaction mixture, and at the same time, the excess ethylene glycol was distilled off while the temperature was raised to 240 ° C., and thereafter, The reaction completion product was transferred to a polymerization reaction can. next,
In this reaction mixture, the following formula

[0062]

[Chemical 5]

4 parts of polyether having an average molecular weight of 2600 represented by (m is 50) is added, the pressure in the reaction vessel is reduced from 760 mmHg to 1 mmHg over 1 hour, and the temperature of the reaction mixture is adjusted to 240 28 degrees Celsius
The temperature was raised to 5 ° C. Polymerization was further performed under a reduced pressure of 1 mmHg, and at this stage, the reaction mixture was treated with 3,9-
Bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] Undecane (Sumilyzer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.)) of 0.16 parts (4% for polyether)
Part), pentaerythritol-tetrakis (β-dodecyl-thiopropionate) (Adeka Stab AO-412S (manufactured by Asahi Denka Co., Ltd.)) and 0.16 part (4 parts with respect to polyether).
Part) and tris (4-alkyl-3-hydroxy-)
2,6-dimethylbenzyl) -s-triazine-2,4,
6- (1H, 3H, 5H) -trione) (Cyanox 1790 (manufactured by American Cyanamid)) was added in an amount of 0.08 parts (2 parts based on polyether), and then the melt viscosity of the system was adjusted to a predetermined value. Polymerization was carried out until the value of was reached.The obtained polymer was made into chips by a conventional method.

After drying the obtained chips by a conventional method,
Melt at 285 ° C using an extrusion spinning machine having a spinneret with 24 circular spinning holes having a hole diameter of 0.3 mm, and discharge amount 3
The undrawn yarn obtained by spinning at 7.5 g / min and a take-up speed of 1500 m / min was subjected to a stretching treatment machine having a heating roller at 80 ° C. and a plate heater at 160 ° C., and the elongation was 30%. Was drawn and heat-treated at such a draw ratio as to obtain 75 denier / 24 filament drawn yarn. A knitted fabric was produced using the obtained drawn yarn, and was scoured by a conventional method and heat set (180 ° C x 1 minute) to obtain a knitted fabric. This was subjected to the above-mentioned stain treatment, and the stain removability was evaluated. The results are shown in Table 2 below.

Examples 8 to 9 The same operation as in Example 7 was performed. However, the composition of the antioxidant was changed. The contents and results are shown in Table 2 below.

Example 10 The same operation as in Example 7 was performed. However, as a pentavalent phosphorus compound, 100 parts of ethylene glycol and 5 parts of trimethyl phosphate are charged under a pressure of ² kg / cm ^{2 in} a closed container.
The reaction solution obtained by reacting at 5 ° C. for 3 hours and then cooled was 6.0.
9 parts (amount corresponding to 0.29 parts as trimethyl phosphate) was added. The results are shown in Table 2.

Examples 11 to 12 The same operations as in Example 10 were performed. However, the composition of the antioxidant was changed. The contents and results are shown in Table 2.

Example 13 The same operation as in Example 7 was performed. However, 0.20 parts of phosphoric acid (0.4 mol% based on dimethyl terephthalate) was added as a pentavalent phosphorus compound. The results are shown in Table 2.

Examples 14 to 15 The same operation as in Example 13 was performed. However, the composition of the antioxidant was changed. The contents and results are shown in Table 2.

Comparative Examples 10 to 14 The same operations as in Example 7 were performed. However, the composition of the antioxidant was changed. The contents and results are shown in Table 2. However, in Comparative Example 14, the fiber was severely broken during spinning, and the stainproof evaluation was impossible.

Comparative Example 15 The same operation as in Example 7 was performed. However, 0.116 parts of pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 (manufactured by Ciba Geigy)) was used as the antioxidant composition. (4 parts with respect to polyether) and the contents shown in Table 2 were replaced. The results are shown in Table 2.

Examples 16 to 17 The same operation as in Example 7 was performed. However, as a polyether, the following formula

[0073]

[Chemical 6]

A polyether having an average molecular weight of 2500 represented by (n is 55 on average) was used, and the antioxidant composition was as shown in Table 2. The results are shown in Table 2.

Comparative Example 16 The same operation as in Example 16 was performed. However, the composition of the antioxidant was changed. The contents and results are shown in Table 2.

[0076]

[Table 2]

(In the table, the amount of each antioxidant added is shown in parts by weight based on 100 parts by weight of one end-blocked polyoxyalkylene-based polyether copolymerization.) Further, Examples 7 to 17 and Comparative Examples 10 to 10 A soil release property evaluation test was performed on each of the fibers obtained in Example 16. The result is shown in FIG.

[0078]

EFFECT OF THE INVENTION The polyester composition of the present invention has excellent antioxidant properties. Particularly, when a pentavalent phosphorus compound is used, flame resistance is also excellent. The polyester fiber of the present invention exhibits its characteristics particularly in the field of clothes, such as uniforms and blouses for women, in which the frequency of home washing has been extremely high in recent years, and the soil is excellent in durability even under severely repeated washing processes. Releasable. Therefore, the polyester fiber of the present invention is extremely useful in the field of textile uniforms. In addition, application to the linen supply field and women's clothing field is also effective.

Furthermore, the polyester fiber of the present invention is optionally used for blending with natural fibers such as cotton and wool, regenerated fibers such as rayon and acetate, and synthetic fibers other than the polyester of the present invention, and mixed weaving. Moreover, since a trivalent carboxylic acid component and / or a trivalent glycol component or a pentavalent phosphorus compound is used as a copolymerization component of polyester, the polymerization time is significantly shortened and the whiteness is also greatly improved.

[Brief description of drawings]

FIG. 1 is a soil release property (ΔE ^* ) of each fiber obtained in Examples 1 to 6 and Comparative Examples 1 to 9 of the present invention.
It is a graph which shows the result of having evaluated.

FIG. 2 is a graph showing examples 7 to 17 of the present invention and comparative examples 10 to 10.
The soil release property of each fiber obtained in No. 16 (△
It is a graph which shows the result of having evaluated E ^* ).

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Claims (6)

[Claims] 1. A polyoxyalkylene-based polyether having a molecular weight of 6,000 or less and having one end blocked of 0.2 to 10 is used.
A polyester containing ethylene terephthalate as a main constituent, which is copolymerized by weight% and is copolymerized with a trivalent carboxylic acid component and / or a trivalent glycol component in an amount of 0.05 to 0.5 mol%, or (ii) a molecular weight of 6, 000 or less of one end-blocked polyoxyalkylene-based polyether is reduced to 0.
An antioxidant is contained in a polyester having ethylene terephthalate as a main constituent, which is copolymerized with 2 to 10% by weight and a pentavalent phosphorus compound is copolymerized with 1/5 to 5 times the molar amount of the polyether. A soil-releasing polyester composition having improved wash durability characterized by: 2. The antioxidant having (a) a hindered phenol compound (a component), (b) a thiopropionate compound (b component) and (c) an isocyanuric group, and (a) The polyester composition according to claim 1, which uses a hindered phenolic compound (component c) other than the compound (1). 3. The content ratio of the component (a) is 0.2 to 10 with respect to the polyoxyalkylene polyether.
The polyester composition according to claim 2, which is in the range of% by weight. 4. The content ratio of the component (b) is 0.2 to 10 with respect to the polyoxyalkylene polyether.
The polyester composition according to claim 2, which is in the range of% by weight. 5. The content ratio of the component (c) is 0.1 to 10 with respect to the polyoxyalkylene polyether.
The polyester composition according to claim 2, which is in the range of% by weight. 6. A fiber formed from the polyester composition of claim 1.