JPS6241252B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antistatic polyester composition, and more particularly to an antistatic polyester composition obtained by blending a polyester with a phosphorus-containing polyester polyether containing a polyalkylene glycol and an alkali metal salt of a specific phosphorus compound. It is related to. Aromatic polyester fibers, especially polyester fibers obtained from polyethylene terephthalate, polyethylene terephthalate/isophthalate, polybutylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, poly-p-ethyleneoxybenzoate, or copolymers thereof, are It is used in a variety of applications because of its practical properties such as excellent mechanical properties, heat resistance, and chemical resistance. However, a major drawback of these polyester fibers is that they tend to accumulate static electricity, which can cling to the body when worn, cause it to stick to other clothing, and produce a crackling discharge sound when taken off. They often cause discomfort and are susceptible to dust, which shortens their useful life. Various methods have been proposed to alleviate these drawbacks, but they are complicated to operate, have poor durability, or are accompanied by deterioration of other properties. There are very few that are actually useful. For example, post-processing methods in which antistatic agents are attached to the surface tend to fall off when washed, etc., and even if a temporary effect is observed, there are problems with their durability. Disadvantages such as hardening of the texture are likely to occur. The copolymerization method in which hydrophilic compounds are copolymerized and the kneading method in which antistatic agents are added tend to cause discoloration under the high temperature conditions encountered during polyester production or molding, and a large amount of the compound is required to obtain sufficient antistatic effect. It is necessary to copolymerize or blend polyester, which tends to cause disadvantages such as impairing the good physical properties of polyester. As a result of a detailed study on conventional methods, the present inventors found that when blending an antistatic agent into polyester, if the melt viscosity of the antistatic agent is too low compared to the polyester, it will disperse in a molecular dispersion state, and if it is too high, it will disperse relatively. It should have a large anti-weight shape. If the affinity is too low, spindle formation will occur, and if the affinity is too high, it will be in a dissolved state, making it difficult to obtain a high antistatic effect. If the softening point is too low, the antistatic agent will be eluted during spinning and scum will occur; if it is too high, the fibers will become uneven and breakage will occur, causing operational problems. It has been found that if the hydrophilicity of the antistatic agent is too high, it will be eluted during washing or the like, resulting in poor durability, and if the hydrophilicity is too low, it will be difficult to obtain a high antistatic effect. Furthermore, to explain the conventional method in more detail, as shown in Japanese Patent Publication No. 44-30010, Japanese Patent Publication No. 44-31828, and Japanese Patent Publication No. 44-32309, polyalkylene glycol and organic sulfonic acid which are non-reactive with polyester are used. When combined with alkali metal salts such as phosphoric acid, phosphorous acid, etc., a mutual effect appears and it is possible to reduce the amount of polyalkylene glycol added to some extent. Alkali metal salts such as sulfonic acid and phosphoric acid have poor thermal stability and may significantly color the yarn, reduce the degree of polymerization of polyester during compounding, and significantly deteriorate the physical properties of the yarn.
Furthermore, the dispersibility of the alkali metal salt used in the polyester is extremely poor, resulting in yarn breakage during spinning, so that it has little practical value. ○B As shown in Japanese Patent Publication No. 46-7213 and Japanese Patent Publication No. 47-19099, when polyester polyether is blended, depending on its composition and manufacturing method, the softening point and melt viscosity can be made quite close to that of polyester. However, it tends to cause problems in affinity and dispersibility with ordinary polyester, and it is difficult to obtain sufficient antistatic effect using ordinary spinning equipment. A special spinning device must be used, and even if such a method is used, the antistatic performance at low humidity is insufficient. ○C Furthermore, JP-A No. 53-94532 discloses an antistatic polyester using a phosphonic acid component copolymerized as part or all of the polymer constituting a composition containing a polyester and a block polyether ester. Compositions have been proposed, but in this case the antistatic effect at low humidity is insufficient. In view of the above, the present inventors have arrived at the present invention as a result of intensive research in order to eliminate the drawbacks of the prior art. The purpose of the present invention is to blend a smaller amount of antistatic agent than the conventional technology, so that when molded into fibers, there is no deterioration of mechanical properties or coloring, and the product has excellent texture and durability. The object of the present invention is to provide a polyester composition that has an excellent antistatic effect at a certain low humidity. For this purpose, during the production of polyester polyether, it is necessary to select a specific phosphor containing an ester-forming functional group that is reactive with polyester polyether, has extremely good thermal stability, and does not cause any problems during the production of polyester polyether. It is essential to blend a phosphorus-containing polyester polyether obtained by copolymerizing an alkali metal salt of a compound with a polyester. That is, the present invention uses a phosphorus-containing polyester polyether containing 0.5 to 50% by weight of an alkali metal salt of a phosphorus compound having an ester-forming functional group represented by the following general formula [] and having a relative viscosity of 1.1 or more. An antistatic polyester composition in which phosphorus-containing polyester polyether is blended in an amount of 0.1 to 5.0% by weight as a polyalkylene glycol component and 50 to 5000 ppm as phosphorus atoms, based on the total composition. (However, R ₁ is −CH ₃ , −CH ₂ CH ₃ ,

[Formula] A group selected from −CH ₂ CH ₂ OH or Na, R ₂ is −CH ₂ −, −CH ₂ CH ₂ −,

【formula】

A group selected from [Formula], R ₃ is a group selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ OH or Na, m is an integer of 0 or 1, and n is an integer of 1 or 2. show. ) Polyester segments of the phosphorus-containing polyester polyether to be blended in the present invention include polyethylene terephthalate, poly-1,4-cyclohexane dimethylene terephthalate, poly-p-ethyleneoxybenzoate, and copolymers thereof. Polyalkylene glycols include polyethylene glycol, methoxypolyethylene glycol, nonylphenol ethylene oxide adduct,
Examples include block copolymers of ethylene oxide and propylene oxide, block copolymers of ethylene oxide and tetrahydrofuran, etc., preferably having an ethylene oxide chain content of 50% or more,
The average molecular weight is 500 to 25,000. If the average molecular weight deviates from the above range, it is unfavorable in terms of softening point and reactivity. Furthermore, if the ethylene oxide chain content is less than 50%, hydrophilicity decreases, making it difficult to provide sufficient antistatic performance. In the production of phosphorus-containing polyester polyether, polyalkylene glycol may be added at any time before the completion of melt polymerization, but it is preferably added at the initial polymerization stage or earlier. The amount of polyalkylene glycol contained in the phosphorus-containing polyester polyether is 10.0 to 90.0% by weight. If it deviates from these ranges, it is unfavorable in terms of hydrophilicity and softening point, and it becomes difficult to obtain sufficient antistatic performance in the resulting fiber. As alkali metal salts of specific phosphorus compounds copolymerized into phosphorus-containing polyester polyethers,
For example, the following alkali metal salts of phosphinic acid and phosphonic acid derivatives having an ester-forming functional group may be mentioned, but the present invention is not limited thereto. Namely, 2-carboxyethylmethylphosphinic acid, 2-carboxyethyl phenylphosphinic acid, 4-carboxyphenylphosphonic acid, carboxymethylphosphonic acid, 2-carboxyethylphosphonic acid, 2-carboxypropylphosphonic acid, 3-carboxy Propylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3
-dicarboxypropylmethylphosphinic acid,
Included are 2,3-dicarboxypropylphosphonic acids and their alcohol, phenol or glycol esters. Alkali metals that form salts with the above phosphorus compounds include sodium, lithium, and potassium. Structural formulas of representative examples of these compounds are shown below. If the sodium salt of the phosphorus compound is added before the completion of polymerization of the polyester polyether, copolymerization will occur, but it is preferable to add it at the initial polymerization stage from the viewpoint of reaction and homogenization of the phosphorus compound and the polyester polyether. Furthermore, it is desirable that the atomic equivalent ratio (M/P) of sodium atoms to phosphorus atoms in the sodium salt of the phosphorus compound copolymerized with the phosphorus-containing polyester polyether does not exceed 2.0. Above this value, the reactivity and compatibility of the sodium salt of the phosphorus compound with the polyester polyether decreases. The content of sodium salt of phosphorus compound in phosphorus-containing polyester polyether is
0.5 to 50% by weight; if the content is too low, the antistatic effect of the obtained fibers at low humidity will be insufficient; if it is too high, the dispersion state in the polyester fiber will deteriorate, resulting in poor operability during spinning. A decrease in It is desirable that all the phosphorus compounds be copolymerized with the polyester polyether, but if the phosphorus compound is in excess, it may be dispersed in the polyester polyether. Further, the relative viscosity of the phosphorus-containing polyester polyether is 1.1 or more, preferably 1.35 to 3.0. When the relative viscosity is 1.1 or less, the dispersibility and workability when blended into polyester are poor, and the durability of the antistatic effect is also unfavorable. On the other hand, in order to obtain a high viscosity phosphorus-containing polyester polyether with a relative viscosity of 3.0 or more, a long time is required for polymerization, which causes discoloration. Moreover, it is undesirable because it has poor solubility and is difficult to mix with polyester. Polyesters modified by the present invention include polyethylene terephthalate, polyethylene terephthalate isophthalate, poly-1,4
Examples include -cyclohexane dimethylene terephthalate, poly-p-ethylene oxide benzoate, and copolymers thereof, such as copolymers with sodium sulfoisophthalic acid and polyethylene glycol. The amount of the antistatic agent of the present invention to be blended into the polyester is such that the polyalkylene glycol component content is 0.1 to 5.0% by weight and the content as phosphorus atoms is 50 to 5000 ppm based on the total composition. It is desirable to do so. Below this range, a sufficient antistatic effect cannot be obtained, and above this range, the physical properties of the thread etc. will deteriorate. The polyester and the antistatic agent of the present invention may contain commonly used catalysts, thermal stabilizers, light stabilizers, antioxidants, matting agents, and the like. The method of mixing polyester and the antistatic agent of the present invention is to mix the chips of both in a commonly used blender, or to mix and mold them using a screw extruder, and then melt-mix using an ordinary spinning device. Alternatively, the two may be melted separately and fibers may be formed using a spinning device equipped with a melt mixer. The fibers obtained by molding the composition of the present invention have excellent texture without deterioration of mechanical properties or coloring, and do not substantially accumulate static electricity even at low humidity, so when made into clothes etc. It does not cause clinging or discharge noise, there is no risk of disaster due to discharge, it attracts little dust, so it is hard to get dirty, and its effectiveness is hardly reduced by normal dry cleaning or home washing. The present invention will be specifically described below with reference to Examples. In the examples, all parts and percentages are by weight. Intrinsic and relative viscosity (0.4
(measured in g/dl) is a value measured at 30°C in a phenol/tetrachloroethane (=6/4) mixture.
The cleansing electrostatic voltage was measured with a Faraday gauge after rubbing 12 times/12 seconds with nylon taffeta at 40%RH, 20°C, and a value of 7V or less indicates that the antistatic effect is present. The frictional charging voltage was measured using a frictional charging voltage measuring device (rotary static tester) at a load of 500g and a rotation speed of 400 times/min.
It was measured by rubbing with a cotton cloth for 1 minute at 40%RH and 20°C, and a value of 600V or less indicates that the antistatic effect is present. The half-life is 30% using a high electrostatic field charging measuring device (honest meter).
It was measured at RH20°C, and if it is 100 seconds or less, it indicates that the antistatic effect is present. Example 1 182 parts of dimethyl terephthalate, 127 parts of ethylene glycol, 0.1 part of zinc acetate, antimony trioxide
0.1 part was placed in a small autoclave equipped with a distiller, and transesterification was carried out at a temperature of 150 to 230°C for 2 hours. Next, 0.1 part of Ionox 330 (phenolic stabilizer trade name), 420 parts of polyethylene glycol (average molecular weight 8000), and 27.2 parts of the compound represented by the above structural formula (E) were added,
The initial polymerization reaction was carried out for 40 minutes at a temperature of 230 to 275°C under reduced pressure, and then the polycondensation reaction was carried out for 45 minutes at 275°C and under reduced pressure of 0.2 mmHg or less.
1.756 and a softening point of 205.7, a slightly yellow and translucent phosphorus-containing polyester polyether was obtained. Separately, 2,480 parts of dimethyl terephthalate, 1,740 parts of ethylene glycol, 0.88 parts of zinc acetate, and 0.75 parts of antimony trioxide were placed in an autoclave, and a transesterification reaction was carried out according to a conventional method.
Initial polymerization reaction was carried out for 40 minutes at 230 to 275°C under reduced pressure, and polycondensation reaction was further carried out at 275°C under reduced pressure of 0.2 mmHg or less. The obtained polyester had an intrinsic viscosity of 0.615 and a softening point of 260.5°C. Next, the former phosphorus-containing polyester polyether was added to 95 parts of the latter polyester chips.
The chips were mixed at a ratio of 5 parts, dried, and then spun at 290°C using an extruder type spinning machine.
After stretching 4.5 times and heat setting at 150℃, the strength was 5.04.
A filament with g/d and elongation of 27.4% was obtained. The polyethylene glycol content in this filament was 3.3%, and the phosphorus content was 290 ppm. This filament is knitted into a double-sided fabric, refined,
After repeated home washing 20 times, we measured the electrostatic voltage and found that the cleaning electrostatic voltage was -5.2V, and the frictional electrostatic voltage was -5.2V.
It exhibited excellent antistatic properties at 510V and a half-life of 64.2 seconds. For home washing, use a household electric washing machine, wash with 0.05% Monogen Uni (neutral detergent brand name) in a 40℃ warm water bath, bath ratio 1:100 for 10 minutes, then rinse with 40℃ warm water for 10 minutes. It was further rinsed with water at 20°C for 5 minutes, and then dehydrated for 2 minutes. Example 2 182 parts of dimethyl terephthalate, 127 parts of ethylene glycol, 0.1 part of zinc acetate, antimony trioxide
0.2 part was placed in a small autoclave equipped with a distiller, and transesterification was carried out at a temperature of 150 to 230°C for 2 hours. Then Ionox 330 0.1
parts, polyethylene glycol (average molecular weight 8000)
420 parts, and the compound represented by the above structural formula (F)
Add 300 parts of 50% ethylene glycol solution and perform initial polymerization at a temperature of 230 to 275°C under reduced pressure.
Furthermore, a polycondensation reaction was carried out at 275℃ and under reduced pressure of 0.2mmHg or less, resulting in a pale yellow, translucent phosphorus-containing polyester polyether with a relative viscosity of 1.514 and a softening point of 175.0℃.
I got it. Next, the polyester chips obtained in Example 1
95 parts of the above phosphorus-containing polyester polyether chips were mixed in a ratio of 5 parts, dried, and then operated in the same manner as in Example 1 to obtain a filament by spinning, stretching, and heat setting, knitting, and processing. When the electrostatic voltage was measured on the knitted fabric that had been washed 20 times at home, it showed extremely excellent antistatic properties with a cleansing electrostatic voltage of -5.0V, a frictional electrostatic voltage of 505V, and a half-life of 42.6 seconds. The polyethylene glycol content in this filament is 2.8%, and the phosphorus content is
It was 1200ppm. Example 3 182 parts of dimethyl terephthalate, 127 parts of ethylene glycol, 0.1 part of zinc acetate, antimony trioxide
0.15 part was charged into a small autoclave equipped with a distiller, and the transesterification reaction was carried out at a temperature of 150 to 230°C for 2 hours. Then Ionox 330 0.1
parts, polyethylene glycol (average molecular weight 8000)
420 parts, and a compound represented by the above structural formula (C)
Add 91.0 parts, perform initial polymerization reaction at a temperature of 230 to 275°C under reduced pressure, and further at 275°C and 0.2 mmHg.
The polycondensation reaction is carried out under reduced pressure as follows, and the relative viscosity
A slightly yellow, translucent phosphorus-containing polyester polyether having a softening point of 1.606 and a softening point of 182.7 was obtained. Next, the latter polyester chip used in Example 1 and the above phosphorus-containing polyester polyether were combined.
were mixed in the proportions shown in Table 1, dried, and then operated in the same manner as in Example 1 to obtain a filament by spinning, stretching, and heat setting, knitting, processing, and washing at home 20 times. When the charging voltage was measured on ground, all showed excellent antistatic properties as shown in Table 1.

[Table] Comparative Example 1 A polyester polyether having a relative viscosity of 1.743 and a softening point of 213.9 was obtained by repeating the same procedure as in Example 1 except that the sodium salt of the phosphorus compound of the present invention was not used in Example 1. . Next, the electrostatic voltage was measured on the knitted fabric which was spun, drawn, heat-set, knitted and treated in the same manner as in Example 1 and washed 20 times at home.The cleaning electrostatic voltage -
7.6V, frictional charging voltage of 950V, and half-life of 300 seconds or more, indicating insufficient antistatic properties. Comparative Example 2 In Example 1, the sodium salt of dimethylphosphonobenzene (atomic equivalent ratio of sodium atom to phosphorus atom: 1.00) was used instead of the sodium salt of the phosphorus compound of the present invention, and the other conditions were exactly the same as in Example 1. Through this operation, phosphorus-containing polyester polyether-V was obtained. This polymer was lumpy and non-uniform with poor flowability. Next, when the phosphorus-containing polyester polyether obtained above was blended with polyester and spun in the same manner as in Example 1, the nozzle back pressure increased significantly and normal fibers could not be obtained. Comparative Example 3 When 424 parts of sodium dodecylbenzenesulfonate was added instead of adding the sodium salt of the phosphorus compound of the present invention in Example 1, foaming was intense and the same operation as in Example 1 could not be performed. However, it was not possible to produce a polyester polyether containing sodium dodecylbenzenesulfonate. Comparative Example 4 Since it was not possible to produce a polyester polyether containing sodium dodecylbenzenesulfonate in Comparative Example 3, the polycondensation reaction was carried out in the same manner as in Example 1 except that the sodium salt of the phosphorus compound was not added in Example 1. After this, 424 parts of sodium dodecylbenzenesulfonate was added, stirred for 25 minutes, and then discharged. The resulting polymer has a relative viscosity of
1.497, the softening point was 259°C, and it was colored yellow. Next, in the same manner as in Example 1, the mixture was blended with polyester, spun, stretched, and heat-set to obtain a filament. This filament has a strength of 3.81g/d and an elongation of 23.2%.
With a value of 10.2, it was strong, but the color tone was not practical. The obtained filament was knitted, scoured, bleached, and washed at home 20 times, and the charging voltage was measured, and the cleaning charging voltage was -6.9V, and the friction charging voltage was
At 900V and half-life of 200 seconds, the antistatic properties were slightly insufficient. Note that the double-sided knitted fabric of polyethylene terephthalate that does not contain a modifier has a cleansing voltage of -
The voltage was 12.4V, the friction voltage was 2140V, and the half-life was over 300 seconds. Comparative Example 5 A phosphorus-containing polyester polyether was obtained in the same manner as in Example 1 except that phenylphosphonic acid was added instead of adding the sodium salt of the phosphorus compound of the present invention in Example 1. Similarly, it is blended with polyester, spun, stretched,
A filament was obtained by heat setting. The obtained filament was knitted, scoured, bleached, and washed 20 times at home, and the charging voltage was measured.The cleaning charging voltage was -7.2V, and the friction charging voltage was
At 870V and half-life of 200 seconds, antistatic properties were not satisfactory.

Claims (1)

[Scope of Claims] 1. An alkali metal salt of a phosphorus compound having an ester-forming functional group represented by the following general formula []
A phosphorus-containing polyester polyether containing 0.5 to 50% by weight and a relative viscosity of 1.10 or more is added to the polyester, and a phosphorus-containing polyester polyether containing 0.1 to 5.0% by weight as a polyalkylene glycol component and phosphorus 50 as an atom
An antistatic polyester composition containing 5000ppm. (However, R ₁ is −CH ₃ , −CH ₂ CH ₃ ,
[Formula] A group selected from −CH ₂ CH ₂ OH or Na, R ₂ is −CH ₂ −, −CH ₂ CH ₂ −,
[Formula] A group selected from [Formula], R ₃ is a group selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ OH or Na, m is 0 or 1, n is 1 or 2 indicates an integer. ) 2 The antistatic polyester composition according to claim 1, wherein in the general formula [], R ₂ is an ethylene group.