JPS6011945B2 - Antistatic polyester composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antistatic polyester composition that has excellent antistatic properties and physical properties and can be easily made into fibers.

Polyesters, particularly polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, and polyesters based on these have various excellent properties and are therefore widely used in fibers and the like. However, since such polyester is easily charged with static electricity, it has the drawback of easily causing various troubles during spinning, processing, use, and the like.

Various methods have been proposed to solve this drawback. For example, a method of blending polyoxyethylene glycol with polyester is known. However, in order to exhibit sufficient antistatic properties with this method, it is necessary to
As much as 2.2% by weight of polyoxyethylene glycol is required, and the resulting antistatic polyester has significantly reduced physical properties, particularly oxidation resistance, and is unusable. In order to eliminate this drawback, polyoxyethylene glycol has an average molecular weight of 10,000 to 3, which is substantially insoluble in polyester.
A method is also known in which a polyoxyethylene glycol of 0,000 is used and an aromatic sulfonic acid metal salt such as sodium dodecylbenzenesulfonate is further blended.

According to this method, the amount of polyoxyethylene glycol used can be reduced and an antistatic polyester with relatively little deterioration in physical properties can be obtained. However, the antistatic polyester obtained by this method contains a large amount of insoluble foreign matter, and during spinning, the pressure in the paper yarn pack increases significantly, and wrapping and yarn breakage occur frequently during paper yarn production and stretching. The yarn-spinning properties are poor, and moreover, foreign matter may be mixed into the resulting product, reducing its commercial value. Moreover, it cannot be said that the antistatic effect, especially its durability, is sufficient. on the other hand,
A method for producing a dominating film made of a polyester in which a soluble low molecular weight polyoxyethylene glycol and an alkyl sulfonic acid metal salt are blended into the polyester has been proposed.

However, when this method was applied to the production of fibers, the antistatic properties of the resulting drawn yarn were greatly reduced during drawing and heat setting, especially during heat setting, and furthermore, during subsequent scouring, dyeing, and washing. Antistatic properties are significantly reduced. The inventor of the present invention has conducted extensive research in an effort to eliminate such drawbacks, provide an antistatic polyester that has excellent antistatic properties, has little deterioration in physical properties, and has good thread-spinning properties. Conventionally used average molecular weight of 5000
Two types of polyoxyalkylene glycol, a polyoxyalkylene glycol having an average molecular weight of 0 or less and a particularly high molecular weight polyoxyethylene glycol having an average molecular weight of 10 or more, are used in specific proportions, and these and a specific alkyl sulfonic acid metal salt are each used in specific amounts to form a polyester. It has been found that an antistatic polyester without the above-mentioned drawbacks can be obtained by blending it with

The present invention was completed as a result of further research based on this knowledge. That is, the present invention is based on the following general formula [where n represents an integer of 2 to 6].

] Polyoxyalkylene glycol 0.1 to 1 part by weight of polyester 10 mainly containing repeating units represented by
and the following general formula RS03M (wherein, R represents an alkyl group having 8 or more carbon atoms, and M represents an alkali metal.

]0.5-10 alkylsulfonic acid metal salt represented by
parts by weight, and 0.5 to 5% by weight of the polyoxyalkylene glycol has an average molecular weight of 10,000.
The antistatic polyester composition is characterized in that it contains 0 or more polyoxyalkylene glycols, and the remainder is polyoxyalkylene glycols having an average molecular weight of 50,000 or less.

The polyester that is the base of the composition of the present invention has terephthalic acid as the main acid component and alkylene glycol components having 2 to 6 carbon atoms, such as ethylene glycol, trimethylene glycol, tetramethylene glycol, bentamethylene glycol, and hexamethylene. The target is polyester whose main glycol component is at least one type of glycol selected from glycols.

Such polyesters may be produced by any method; for example, in the case of polyethylene terephthalate, terephthalic acid and ethylene glycol may be directly esterified, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene may be produced. Glycol esters of terephthalic acid and/or their oligomers are produced by transesterification with glycol or by reacting terephthalic acid with ethylene oxide, and then the products are heated under reduced pressure to form the desired compound. It is easily produced by carrying out a polycondensation reaction until the degree of polymerization is reached. In addition, in this polyester, a part of the terephthalic acid component may be replaced with another dichotomous carvone brewing component.

Examples of such carboxylic acids include difunctional aromatic carboxylic acids such as isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxychetane dicarboxylic acid, 8-oxyethoxybenzoic acid, p-oxybenzoic acid, and sebacic acid. , difunctional aliphatic carboxylic acids such as adipic acid and ayalic acid, and difunctional alicyclic carboxylic acids such as 1,4-cyclohexanedicarboxylic acid. Further, a part of the above glycol component may be replaced with another glycol component, such as an aliphatic glycol component such as cyclohexane-1,4-dimethanol, neobentyl glycol, bisphenol A, or bisphenol S. , alicyclic, and aromatic diol compounds. The polyoxyalkylene glycols to be blended into the composition of the present invention include those with an average molecular weight of 10 or more (hereinafter abbreviated as high molecular weight PAG), and those with an average molecular weight of 50,000 or less (hereinafter abbreviated as low molecular weight PAG). ) are used.

As the high molecular weight PAG, polyoxyethylene glycol or a product obtained by polymerizing oxypropylene units with oxyethylene glycol as the main component (usually 50% or more) is preferably used. In addition, the terminal may be a hydroxyl group or may be blocked with an organic group having no ester-forming functional group, and may further be blocked with an organic group having an ester-forming property through an ester bond, an ether bond, a carbonate bond, etc. May be combined with As the low molecular weight PAG, polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol are mainly used, but copolymers of these are also preferably used. The terminal may be a hydroxyl group or other organic group may be bonded to the same group as the high molecular weight PAG. The blending amount of such high molecular weight PAG and low molecular weight PAG is such that the total amount thereof is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on the weight part of polyester 10 serving as the base. 0.5 to 50 weight of this total amount, preferably 1
~20% by weight is high molecular weight PAG and the remainder is low molecular weight PAG.

When the total amount is less than 0.1 part by weight, sufficient antistatic properties cannot be obtained even if a very equivalent amount of the alkyl sulfonic acid metal salt described below is used in combination, and when the total amount is more than 1 part by weight, the resulting composition The physical properties of the product, especially the oxidation stability, are greatly reduced, and even in view of antistatic properties, it is not necessary to use 10 parts by weight or more by using an appropriate amount of the metal alkyl sulfonate described below. Further, even if the total amount satisfies the above range, if the ratio of high molecular weight PAG to low molecular weight PAG does not satisfy the above range, the object of the present invention cannot be achieved. For example, if the proportion of high molecular weight PAG does not reach 0.5% by weight, a sufficiently durable antistatic composition cannot be obtained even if the total amount is appropriate. This high molecular weight PAG
The antistatic durability improves as the proportion increases, but when it exceeds 5% by weight, no further improvement is observed, and the oxidation resistance stability of the resulting composition deteriorates. . In particular, high molecular weight PAG and low molecular weight PA
When used by pre-mixing with G in the above ratio, there is an advantage that the disadvantages of high molecular weight PAG, namely poor handling due to extremely high melt viscosity and inability to fall in solvents, are completely eliminated. . However, even if the two are mixed in advance, when the proportion of high molecular weight PAC exceeds 50% by weight, the above-mentioned drawbacks of high molecular weight PAG suddenly become apparent. Also,
When using a PAG with an average molecular weight greater than 50,000 instead of the above low molecular weight PAG, the above high molecular weight PAG should be
The same drawbacks as when using a larger amount than a low weight% occur, and when FAG with an average molecular weight of less than 100,000 is used in place of the above-mentioned high-molecular-weight PAG, the above-mentioned high-molecular-weight PAG is 0%.
．． Similar drawbacks occur when the amount does not reach 5% by weight. That is, when high molecular weight PAG and low molecular weight PAG are mixed in the above ratio, the melting characteristics of the mixture behaves similar to that of low molecular weight PAG, and the solubility characteristics of the mixture in polyester are different from that of high molecular weight PAG, which is a 4-weight component. Shows similar behavior to molecular weight PAG.

This behavior is due to having two different maxima in the molecular weight distribution, and cannot be manifested simply by expanding the molecular weight distribution. Furthermore, the dispersion and affinity of the mixture into polyester are extremely good, and the resulting composition has excellent moldability, especially thread-spinning properties. The alkylsulfonic acid metal salt used in combination with the above polyoxyalkylene glycol has the general formula RS03.
It is represented by M.

M here represents an alkali metal, usually sodium, potassium, or lithium, with sodium being particularly preferred. The sulfonic acid metal base is preferably located other than at the terminal end, particularly at the 8-position. R represents an alkyl group having 8 or more carbon atoms. Carbon number 7
In the case of the following alkyl groups, the compatibility with polyester is poor, and when such alkyl groups are used, moldability, particularly thread-spinning properties, deteriorate. Moreover, the durability of the antistatic properties of the resulting product also becomes poor. Usually, those in which R is an alkyl group having 8 to 20 carbon atoms are used, and it is convenient to use them as a mixture. In addition, when using such alkyl sulfonic acid metal salt, a small proportion (usually 0% relative to polyester) is required.
．． 001 to 1% by weight), such as sodium chloride, lithium chloride, potassium chloride, sodium bromide, potassium bromide, sodium sulfate, lithium sulfate, etc. It is also good for improving sexuality. The amount of the alkylsulfonic acid metal salt to be blended is in the range of 0.5 to 1 part by weight based on the weight of the polyester 10 used as the base.

When the amount is less than 0.5 parts by weight, no effective antistatic effect can be obtained even if a sufficient amount of the polyoxyalkylene glycol is used.

That is, by using 0.5 parts by weight or more of the alkylsulfonic acid metal salt, a synergistic effect with polyoxyalkylene glycol can be obtained, and a sufficient antistatic effect can be achieved with a small amount of polyoxyalkylene glycol. Furthermore, even if the amount is more than 1 part by weight, no improvement in the Liuden effect is observed, and on the contrary, the physical properties of the resulting composition deteriorate, and when it is made into fibers, the texture deteriorates. Become. Any method can be used to blend the polyoxyalkylene glycol and the alkyl sulfonic acid metal salt, and both can be blended into the polyester at the same time or in any order.

That is, at any stage until the end of polyester molding, for example, before the start of the military condensation reaction of the polyester, during the military condensation reaction, at the end of the polycondensation reaction when it is still in a molten state, in the powder state, in the molding (grade) Both may be added at the same time or in any order, such as in the thread) stage. Further, both may be added after being melt-mixed in advance, or may be added in two or more portions, or both may be separately blended into polyester and then mixed before molding or the like. Furthermore, when it is added before the middle stage of the polycondensation reaction, it may be added after being dissolved or dispersed in a solvent such as glycol. The composition of the present invention may also contain an oxidizing agent such as a sterically hindered phenol compound or a triazole compound, and it is preferable to do so.

In addition, other antistatic agents, colorants, matting agents, other additives, etc. may be added as necessary. The composition of the present invention comprises:
By using relatively small amounts of two types of polyoxyalkylene glycols, it exhibits excellent durable antistatic properties, has little deterioration in its physical properties, and has good moldability, especially thread-spinning properties.
It is possible to provide an excellent antistatic polyester fiber.

When the composition of the present invention is used for fiber applications, any yarn spinning conditions can be employed without any problem.

For example, threading is carried out at a speed of 500 to 2,500/min, and then
A method of heat treatment, a method of threading at a speed of 1,500 to 5,000 threads per minute, followed by stretching and false twisting, a method of paper threading at a high speed of 5,000 threads per minute or more, and depending on the use, omitting the drawing step, etc. Any spinning conditions are adopted. In addition, heat-treating the obtained fibers or woven or knitted fabrics at a temperature of 10 pi or higher helps to stabilize the structure and to prevent the polyoxyalkylene glycol and alkyl sulfonic acid metal salt contained in the composition from reaching near the surface. This is preferable because migration is facilitated. Furthermore, relaxation heat treatment or the like can be used in combination as necessary. Furthermore, the composition of the present invention can also be used for films and sheets, and in this case as well, arbitrary molding conditions can be employed without any problems. For example, any conditions may be employed, such as a method of applying tension in only one direction after film formation to provide anisotropy, a method of stretching in two directions simultaneously or in an arbitrary order, a method of multi-stage stretching of two or more stages, etc. Further, it is preferable to heat-treat the film, sheet, etc. at a temperature of 10 mm or higher for the reasons mentioned above. The present invention will be explained in further detail by giving examples below.

In the examples, parts indicate parts by weight, and [knife] is the intrinsic viscosity determined from the solution viscosity measured at 35° C. in oxochlorophenol. Thread reelability is determined by the increase in pack pressure at the time of thread removal (initial pressure and
Comparison with pack pressure after 1 day), number of thread breaks (times/1 kite), and wrap rate during stretching (number of roller wraps due to single thread cutting when drawing 100 2.5k 9-wound bobbins) . The antistatic property was tested by scouring and air-drying a final knitted fabric made from the obtained filament using a conventional method, presetting it at 160q0 for 1 minute, and measuring IK using a Statec Neometer. V
．． was applied, and its half-life was measured at a relative humidity of 50%. This value was indicated as Lo. The durability of military control was determined by washing the above-mentioned wire cloth in a household washing machine with a 0.2% aqueous solution of Neoberex P (manufactured by Kao Soap Co., Ltd.) at 40°C for 10 minutes, and then washing it in a moat at 40°C for 5 minutes. After rinsing with overflow water for 18 minutes, it was dehydrated and dried at 60° C. for 3 minutes. The half-life after washing and drying is repeated 5 times is indicated by L5, and the half-life after washing and drying is repeated 10 times in total is Lo, and the half-life after returning 50 times in total is L.
Shown separately. The oxidation resistance stability was expressed as the temperature at which the exothermic peak appeared, that is, the oxidation start temperature, when the above-mentioned drawn yarn sample was heated in air at a heating rate of 20 qo/min using a differential thermal analyzer. For normal uses, this oxidation initiation temperature is required to be 240°C or higher. Examples 1 to 4 and Comparative Examples 1 to 4 10 parts of dimethyl terephthalate, 7 parts of ethylene glycol
Manganese acetate 0.02 as anchor and transesterification catalyst
Five parts of the mixture was heated under hawking and transesterification was carried out for 90 minutes while the generated methanol was distilled off.

Next, 0.015 part of phosphorous acid as a stabilizer and 0.041 part of antimony trioxide as a polycondensation catalyst were added, and 28
The temperature was raised to 5°C, and the system was then reduced to a vacuum of 6 Hg for 30 minutes, then 80°C under a high vacuum of 0.5 skin Hg.
In producing polyethylene terephthalate having a polycondensation reaction of approximately 0.65 minutes, at the time when the polycondensation reaction under a highly reduced pressure of 0.5 hours Hg is completed, 2 parts of sodium dodecylsulfonate is added. and the two types of polyoxyalkylene glycol mixtures listed in Table 1 were added and blended in the amounts listed in the table. The obtained composition was once made into chips, dried in accordance with a conventional method, and then wound using a paper thread nozzle having 48 peacock-0.3 willow-grade thread holes at a discharge rate of 80 min/min and a paper thread temperature of 290°C. Paper yarn was drawn at a speed of 1500 m/min.

After that, it was stretched at a temperature of 85q0 and a magnification of 3.2 times to 150
A fiber of denier/48 filament was obtained. The antistatic properties, spinning properties, and oxidation resistance stability of this fiber are shown in Table 1. In addition, PEG (70), PEG (11000), PEG showing the types of polyoxyalkylene glycol in Table 1
(500) and PEG (70,000) represent polyoxyethylene glycols with an average degree of polymerization of 70-11,000, 500, and 70,000, respectively.

Examples 5 and 6 and Comparative Examples 5 to 10 As the sulfonic acid metal salt, an alkyl group having 8 to 20 carbon atoms (
Same as Example 1 except that a mixture of sodium alkyl sulfonates having an average carbon number of 14) was used in the amount specified in the second specification, and a polyoxyalkylene glycol was used in the amount specified in the second specification. I did it.

The results are shown in Table 2. Note that DOPG (20), which indicates the type of polyoxyalkylene glycol in Table 2, has an average polymerization degree of 2 with both ends blocked with P-octylphenol.
0 polyoxyethylene glycol and PEG (2
2000), PEG (200) and PEG (11000)
0) have an average degree of polymerization of 22000, 200 and 1100, respectively.
00 polyoxyethylene glycol.

Ships Examples 7 to 10 and Comparative Examples 11 to 13 Sodium stearyl sulfonate was used as the sulfonic acid metal salt in the third category, and as the polyoxyalkylene glycol, the third category was used as the quantity in the category. However, the same procedure as in Example 1 was conducted except that the timing of these additions was varied as shown in Table 3, and the results are shown in Table 3.

In addition, the time of completion of polymerization shown in the column of addition time in Table 3 is 0.
This indicates the point at which the polycondensation reaction is completed under a reduced pressure of 50000 Hg, the initial stage of polymerization indicates just before the transition to reduced pressure, and the middle stage of polymerization indicates the time at which the polycondensation reaction is completed under reduced pressure of 6000000 Hg. shows.

Also, the types of boroxyalkylene glycols in the table are PEG (90), PEG (110000), PEG (
200) and PEG (11000) each have an average degree of polymerization of 9.
0, 110,000, 200 and 11,000 polyoxyethylene glycols are shown. Ship Comparative Example 14 Peel 15 Example except that 3 parts of aromatic sodium dodecylbenzenesulfonate was used as the sulfonic acid metal salt, and the specified amount of the 4th grade was used as the polyoxyalkylene glycol. The same procedure as in Example 1 was carried out, and the results are shown in Table 4.

In addition, DOP (20), which indicates the type of polyoxyalkylene glycol in Table 4, indicates polyoxyethylene glycol with an average degree of polymerization of 20, which has both ends blocked with P-octylphenol, and PEG (200), PEG ( 2200
0) and PEG (110000) each have an average degree of polymerization of 2
0022000, 110000 polyoxyethylene glycol.

Table 4 Example 11 10 dimethyl terephthalate, 180 parts of 1,4-butanediol, 0 titanium tetrabutoxide as a catalyst
．． A mixture of 0.0 parts and 0.1 parts of Irganox 1076 (manufactured by Ciba-Geigy) as a stabilizer was heated under pressure, and while the generated methanol was distilled off, a transesterification reaction was carried out for 90 minutes.

Next, the reaction product was maintained at 240°C and the system was reduced to a reduced pressure, and finally, the temperature was reduced to 9°C under a reduced pressure of 0.5°C.
The polycondensation reaction was carried out for 0 minutes to obtain polybutylene terephthalate having a molecular weight of 0.60. Here, the inside of the system was returned to normal pressure with nitrogen gas, and 3 parts of polyoxyalkylene glycol and sodium stearyl sulfonate listed in Table 5 were added and mixed. The resulting composition was drawn into a twill yarn in the same manner as in Example 1, except that the grade yarn temperature was 280°C and the drawing temperature was 50°C, to obtain a 150 denier/48 filament fiber.

The antistatic properties, spinning properties, and oxidation resistance stability of this fiber are shown in Table 1. In addition, DOPG (50) indicating the type of polyoxyalkylene glycol in Table 5 indicates polyoxyethylene glycol with an average degree of polymerization of 50 with both ends blocked with P-octylphenol, and PEG (110000),
PEG (140) and PEG (11000) represent polyoxyethylene glycols with average degrees of polymerization of 110,000, 140, and 11,000, respectively.

Table 5

Claims (1)

[Claims] 1. The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, n represents an integer from 2 to 6. ] Polyester 100 mainly consisting of repeating units represented by
0.1 to 1 part by weight of polyoxyalkylene glycol
0 parts by weight and the following general formula RSO_3M [In the formula, R represents an alkyl group having 8 or more carbon atoms, and M represents an alkali metal. ]0.5-10 alkylsulfonic acid metal salt represented by
parts by weight, and 0.5 to 50% by weight of the polyoxyalkylene glycol has an average molecular weight of 10,000.
An antistatic polyester composition comprising 0 or more polyoxyalkylene glycols, the remainder being polyoxyalkylene glycols having an average molecular weight of 50,000 or less.