JPH0977963A - Polyester composition - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a polyester composition excellent in handleability, in which spinneret back pressure during melt spinning does not increase, yarn breakage does not occur, and filtration pressure during melt molding does not increase. SOLUTION: The polyester is composed of an aromatic dicarboxylic acid component and a diol component, and an organic sulfonic acid metal salt.
A polyester composition blended in an amount of 5 to 5% by weight, wherein the amount of inorganic impurities contained in the composition by the blending of an organic sulfonic acid metal salt is 1500 ppm or less.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester composition for fibers or films.

[0002]

BACKGROUND OF THE INVENTION Polyester is widely used as a fiber, a film, and other molded articles because of its many excellent properties. However, when polyester is used as a fiber, it has drawbacks such as non-water absorbability and slimy feel, and when it is used as a fiber and a film, it has drawbacks such as electrification property. Therefore, a polyester blended with an organic sulfonic acid metal salt has been proposed.

On the other hand, although the required performances for polyesters are different in each application, what is commonly required in the industrial production of fibers and films is the process passing stability. That is, with fibers, the back pressure of the spinneret during melt spinning does not increase and yarn breakage is small, and with films, the filterability and handleability during melt molding are excellent.

However, in conventional polyesters containing a metal salt of an organic sulfonic acid, as the amount of the metal salt of an organic sulfonic acid increases, the process passage stability, which is an important performance requirement for industrial production of fibers or films, deteriorates. To do. In particular, in the case of fibers, the back pressure of the spinneret during melt spinning rises, and in the case of films, the filtration pressure during melt molding rises, and this phenomenon results in problems such as yarn breakage. Was there.

[0005]

DISCLOSURE OF THE INVENTION The present invention has found that the cause of the rise in spinneret back pressure and the increase in filtration pressure in polyester blended with an organic sulfonic acid metal salt is due to the inorganic impurities contained in the organic sulfonic acid metal salt. Based on that.
The object of the present invention is not to increase the back pressure of the spinneret during melt spinning,
It is an object of the present invention to provide a polyester composition which has less yarn breakage and does not increase in filtration pressure during melt molding and has excellent handleability.

[0006]

The present invention relates to a polyester comprising an aromatic dicarboxylic acid component and a diol component, and
(Wherein, R represents an alkyl group having 3 to 20 carbon atoms, an aryl group or an alkylaryl group of 7 to 40 carbon atoms, M represents an alkali metal or alkaline earth metal) general formula R-SO ₃ M shown by Consisting of organic sulfonic acid metal salt,
0.5 to 5 of organic sulfonic acid metal salt to polyester
A polyester composition blended in a weight percentage, wherein the amount of inorganic impurities contained in the composition due to blending of the organic sulfonic acid metal salt is 1500 ppm or less.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester in the composition of the present invention is a polyester composed of an aromatic dicarboxylic acid component and a diol component, wherein the main acid component is an aromatic dicarboxylic acid such as terephthalic acid or its ester-forming derivative, It may be a polyester having ethylene glycol, 1,4-butanediol, etc. as a main diol component, in which a part of the acid component and / or the diol component is replaced with another acid component and / or diol component.

Examples of other acid components include dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid, or ester-forming derivatives thereof. , 5-sodium sulfoisophthalic acid, 2-sodium sulfoisophthalic acid, metal sulfonate group-containing dicarboxylic acid such as sodium 1,8-dicarboxynaphthalene-3-sulfonate or its ester-forming derivative, p-oxybenzoic acid, p Oxycarboxylic acids such as -β-oxyethoxybenzoic acid or ester-forming derivatives thereof, 5-tetrabutylphosphonium sulfoisophthalic acid, 5-tetraphenylphosphonium sulfoisophthalic acid, 5-phenyltributylphosphonium Ruhoisofutaru acid, 5-butyl triphenyl phosphonium sulfo phosphonium sulfonate-containing dicarboxylic acid or ester-forming derivatives such as isophthalic acid and the like.

Other diol components include, for example, lower alkylene glycol having 3 to 10 carbon atoms, 1,4-
Cyclohexanedimethanol, neopentyl glycol, 1,4-bis (β-oxyethoxy) benzene, bisglycol ether of bisphenol A, polyethylene glycol of various molecular weights, polyalkylene glycols such as polypropylene glycol, ethylene oxide-
Examples thereof include propylene oxide copolymer.

Further, within the range where the polyester is substantially linear, polycarboxylic acids such as trimellitic acid and pyromellitic acid, trimethylolpropane or its ethylene oxide addition derivative, pentaerythritol, glycerin or its ethylene oxide addition derivative. Or the like, or a polymerization inhibitor such as monohydric polyalkylene oxide or phenylacetic acid.

The polyester may be synthesized by any known method. For example, when polyethylene terephthalate is explained, terephthalic acid and ethylene glycol are directly esterified or dimethyl terephthalate and ethylene glycol are used. Is used to synthesize a glycol ester of terephthalic acid or a low polymer thereof by transesterification with, and then polymerizing the synthesized product. Further, in the synthesis of polyester, known catalysts, antioxidants, anti-coloring agents, ether bond by-product inhibitors, flame retardants and other additives may be appropriately used.

In the present invention, polyester is blended with an organic sulfonic acid metal salt, but an organic sulfonic acid metal salt, for example, an organic sulfonic acid sodium salt, is generally
After sulfonation of paraffin, alkylbenzene, etc.,
It is produced through a neutralization step. During this production, sodium chloride and sodium sulfate are produced as by-products, and the produced sodium salt of organic sulfonic acid is contained as an inorganic impurity. The organic sulfonic acid sodium salt is purified by an extraction method or a recrystallization method. If it is unpurified or has a low degree of purification, it contains sodium chloride or sodium sulfate of several% by weight. Whether sodium chloride or sodium sulfate is contained more depends on the method for producing the organic sulfonic acid sodium salt.

When such an organic sulfonic acid sodium salt is blended with the polyester, sodium chloride and sodium sulfate derived from the blending of the organic sulfonic acid sodium salt are added to the filter during melt spinning or melt molding of the polyester containing the sodium organic sulfonate. Easy to catch,
It accumulates on the filter over time, resulting in an increase in spine back pressure or an increase in filtration pressure. This phenomenon becomes more remarkable as the blending amount of the organic sulfonic acid sodium salt increases.

Examples of the organic sulfonic acid metal salt in the composition of the present invention include sodium, potassium, lithium, calcium, magnesium, alkyl sulfonic acid having 3 to 30 carbon atoms, toluene sulfonic acid, dodecylbenzene sulfonic acid. Sodium, potassium salt, lithium salt, calcium salt of alkylbenzene sulfonic acid, etc.
Magnesium salt may be mentioned. The organic sulfonic acid metal salt may be a mixture of these same species or different species,
As the organic sulfonic acid metal salt, organic sulfonic acid sodium salt is preferably used.

The amount of the organic sulfonic acid metal salt compounded in the composition of the present invention is 0.5 to 5% by weight based on the polyester.
And If the blending amount is less than 0.5% by weight, the amount of inorganic impurities in the composition resulting from the blending of the organic sulfonic acid metal salt will naturally decrease, but there is no effect of improving the defects of the polyester by blending the organic sulfonic acid metal salt. 5% by weight
When it exceeds, the physical properties of the fiber or film are deteriorated, and it becomes difficult to reduce the amount of inorganic impurities.

In the composition of the present invention, it is necessary that the amount of inorganic impurities contained in the composition is 1500 ppm or less within the range of the compounding amount of the organic sulfonic acid metal salt that exerts the effect of improving the defects of polyester. Is. When the amount of inorganic impurities exceeds 1500 ppm, the back pressure of the spinneret in melt spinning increases or the extrusion overpressure in melt molding increases. When compounding an organic sulfonic acid sodium salt that is preferably used as the organic sulfonic acid metal salt, the total amount of sodium chloride and sodium sulfate contained in the composition is preferably 60 ppm or less, and more preferably in the composition. The amount of sodium chloride contained is 10 ppm or less and the amount of sodium sulfate is 20 ppm or less.

The composition of the present invention is formed by blending an organic sulfonic acid metal salt with polyester, and the organic sulfonic acid metal salt is added at any stage until the melt spinning or melt molding of the polyester is completed. It is formed by blending, for example, is added and blended into the raw material of polyester, is blended into the reaction system during the synthesis of polyester, is kneaded in the extruder, is blended during melt shaping in the spinning machine or molding machine. And the like.

In the composition of the present invention, in addition to the organic sulfonic acid metal salt, high molecular weight polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, high molecular weight polyalkylene oxide, polyalkylene glycol, etc. A polymer substance that does not react with polyester may be added.

The composition of the present invention may further contain a heat stabilizer, an antioxidant and the like in order to further improve the heat stability. As the heat stabilizer and the antioxidant, hindered Phenol compounds, thioether compounds and the like are used.

[0020]

The present invention will be described below in more detail with reference to examples. The characteristic values and evaluations in the examples are based on the following methods and standards. In addition, parts and% in the examples mean parts by weight and% by weight.

Intrinsic viscosity: A sample was dissolved in a phenol / tetrachloroethane (50/50) mixed solvent and measured at 25 ° C. using an Ubbelohde viscometer.

Amount of inorganic impurities: The amount of sodium chloride in sodium alkylsulfonate was determined by the silver nitrate method, and the amount of sodium sulfate was determined by the barium chromate emission method.

Stability during spinning process: Judged by spinneret back pressure increase and yarn breakage during 8 hours of spinning process.

Increase in spinneret back pressure: When 8 hours passed after the start of melt spinning, the following criteria were used for judgment. ○: The back pressure increase of the mouthpiece is less than 5% of the initial pressure. △: The back pressure increase of the mouthpiece is 5% or more and less than 15% of the initial pressure. ×: The back pressure increase of the mouthpiece is 15% or more of the initial pressure. : The initial pressure of 1 before the back pressure rise of the mouthpiece reaches 8 hours.
The spinning rate was stopped at over 00%

Thread breakage: Judgment was made according to the following criteria by thread breakage in the spinning process for 8 hours. ◯: The number of thread breaks is 0. Δ: The number of thread breaks is 1 to 2 ×: The number of thread breaks is 3 or more.

Passage stability in the flame-extending step: The stability of passage in the flame-extending step was judged by the following criteria due to the breakage of single fibers in the flame-extending step for 16 hours. ◯: The number of single fiber breaks is 0 Δ: The number of single fiber breaks is 1 to 2 ×: The number of single fiber breaks is 3 or more XX: Flame spread is difficult

Example 1 100 parts of terephthalic acid and 52 parts of ethylene glycol were charged into an esterification tank and 4 kg.
The esterification reaction is carried out at 260 ° C. under a pressure of / cm ² .
Then, 0.01% of trimethyl phosphate, 0.04% of antimony trioxide, and 0.5% of titanium dioxide were added to the obtained reaction product as an ethylene glycol solution or dispersion, respectively, and transferred to a polymerization tank.

The pressure in the polymerization tank was reduced, and 30 minutes after the degree of vacuum in the polymerization tank became 1 Torr or less, and 70 minutes after the start of the polymerization reaction, sodium alkylsulfonate having an average carbon number of 15.5. 2.0 in the molten state for the polymer produced
% Was added. The added sodium alkylsulfonate contained 30 ppm of sodium chloride and 100 ppm of sodium sulfate as inorganic impurities. After the addition, the polycondensation reaction was further performed at 285 ° C. under high vacuum to obtain a polyethylene terephthalate polymer having an intrinsic viscosity of 0.70.

This polymer was made into chips by a conventional method, dried, and melt-spun at a spinning temperature of 285 ° C. using a spinneret having 72 circular spinning holes having a hole diameter of 0.2 mm. At this time, the filter configuration in the spinneret pack was as follows: 6 600 mesh wire mesh filters, 9 325 mesh wire mesh filters, 6 mesh screens 120 mesh
There were a total of 27 sheets, which consisted of 6 sheets of 50-mesh wire mesh filter. After the discharged yarn was cooled and solidified with a cooling air flow, an oil agent was applied, and the yarn was wound at a spinning speed of 1600 m / min.

The unstretched yarn was stretched through a heat roller at 84 ° C. at a stretch ratio of 72% of the maximum stretch breaking ratio and was heat treated by contacting it with a hot plate at 150 ° C.
It was wound at a speed of minutes to obtain a drawn yarn of 100 denier / 72 filaments. Table 1 shows the evaluation results of the spinning process passing stability and the flame spreading process passing stability when obtaining this drawn yarn.
It was shown to.

(Example 2, Comparative Examples 1 to 7) In Example 1, except that the amount of sodium chloride and the amount of sodium sulfate contained as inorganic impurities were different from those shown in Table 1, sodium alkylsulfonate was used. A drawn yarn was obtained in the same manner as in 1. Table 1 shows the evaluation results of the spinning process passing stability and the flame spreading process passing stability when obtaining the drawn yarn. In Comparative Examples 4 to 7, the spinneret back pressure increased remarkably and the spinning was aborted midway. was detected.

[0032]

[Table 1]

[0033]

According to the polyester composition of the present invention,
There is no rise in spinneret back pressure during melt spinning or filtration pressure during melt molding, and there are very few problems such as yarn breakage, excellent process stability, and stable quality fibers, films, and other molded products are obtained. be able to.

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[Procedure amendment]

[Submission date] December 20, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

[0006]

The present invention relates to a polyester comprising an aromatic dicarboxylic acid component and a diol component, and
_(Wherein, R represents an alkyl group having 3 to 30 carbon atoms, an aryl group or an alkylaryl group of 7 to 40 carbon atoms, M represents an alkali metal or alkaline earth metal) general formula R-SO 3 M shown by Consisting of organic sulfonic acid metal salt,
0.5 to 5 of organic sulfonic acid metal salt to polyester
A polyester composition blended in a weight percentage, wherein the amount of inorganic impurities contained in the composition due to blending of the organic sulfonic acid metal salt is 1500 ppm or less.

Claims (3)

[Claims] 1. A polyester comprising an aromatic dicarboxylic acid component and a diol component, and a general formula R—SO ₃ M (wherein R is an alkyl group having 3 to 20 carbon atoms, and 7 to 40 carbon atoms).
Of the aryl group or alkylaryl group, M represents an alkali metal or an alkaline earth metal), and the organic sulfonic acid metal salt is blended in an amount of 0.5 to 5% by weight with respect to the polyester. A polyester composition, wherein the amount of inorganic impurities contained in the composition by the addition of an organic sulfonic acid metal salt is 1500 ppm or less. 2. The organic sulfonic acid metal salt is an organic sulfonic acid sodium salt, the inorganic impurities are sodium chloride and sodium sulfate, and the amount of sodium chloride and the amount of sodium sulfate contained in the composition are 60 ppm or less. Item 2. The polyester composition according to item 1. 3. The polyester composition according to claim 1, wherein the amount of sodium chloride contained in the composition is 10 ppm or less and the amount of sodium sulfate contained in the composition is 20 ppm or less.