JPH09100397A - Polyester composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyester composition superior in forming characteristics such as spinnability and stretchability and in heat resistance by blending a polyester mainly composed of ethylene terephthalate with a specified organic sulfonate, a metal compound and an antioxidant. SOLUTION: This polyester composition is obtained by blending (A) a polyester with ethylene terephthalate as a main repeating unit with (B) an organic sulfonate as represented by formula I [R<1> is a 3-30C alkyl, a 6-40C aryl or an alkylaryl; M<1> is an alkali (alkaline earth) metal; (i) is 1 or 2] (e.g. sodium octylsulfonate), (C) a metal compound as represented by formula II or formula III [M<2> and M<3> are each an alkali (alkaline earth) metal; R<2> is a 1-10C alkyl, a 6-20C aryl or the like: (i) and (k) is 1 or 2] (e.g. sodium acetate) and (D) an antioxidant having a phenolic structure in which one or two sterically hindered hydrocarbon substituents exist in the ortho position of the phenolic hydroxyl group e.g. 2,4-bis[(octylthio)methyl]-o-cresolo}.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition, and more particularly, it has excellent thermal stability and good moldability such as spinning and drawing. Particularly, foreign matter deposited around the spinneret hole during spinning is extremely high. Low polyester composition.

[0002]

2. Description of the Related Art Polyesters, especially polyethylene terephthalate, are widely used for various purposes, especially for fibers and films, because they have many excellent properties. Regarding such polyester, hygroscopicity (Japanese Patent Publication No.
No. 44065), antistatic property, cation dyeability, and surface property modification by alkali treatment have been proposed.

However, in the above improvement, the modified polyester obtained by using the organic sulfonate compound has a drawback that it is inferior in moldability, particularly in spinnability over a long period of time. That is, in the modified polyester obtained by using the sulfonate compound, foreign matter is deposited around the spinning hole with the lapse of time after the start of spinning, and the bending phenomenon of the polymer flow (hereinafter, referred to as “bending”) occurs. In addition to the occurrence of wrapping, many wraps occur during spinning / drawing, and finally spinning itself becomes impossible. Therefore, when bending occurs, it is necessary to replace the spinneret, and production is significantly hindered.

In order to solve such problems, in order to improve the releasability of the polymer flow from the conventional spinneret, in order to improve the releasability of the polymer spinneret, investigation of a release agent such as silicone, study of the material of the spinneret, and the shape of the spinning hole is carried out. Various measures are being studied, such as. However, the effect was not sufficient.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to reduce the deposition of foreign matters around the spinneret hole, to provide excellent moldability such as spinning and drawability, and to obtain thermal stability that enables molding without problems in practical production. An object is to provide an excellent polyester composition.

[0006]

The above objects and advantages of the present invention are obtained by adding (A) the following formula (1) (R ¹ SO ₃ ) _i M ¹ ... (to polyester containing ethylene terephthalate as a main repeating unit. 1) [In the formula (1), R ¹ is a monovalent group selected from an alkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms and an alkylaryl group having 6 to 40 carbon atoms, M ¹ is an alkali metal or an alkaline earth metal, and i is 1 or 2.]
(Also referred to as “(A component)”) and (B) respectively represented by the following formulas (2) and (3) M ² (OH) _j ... (2) (R ² —COO) _k M ³ ... ( 3) [In the formulas (2) and (3), M ² and M ³ are an alkali metal or an alkaline earth metal, and R ² has 1 to 1 carbon atoms.
A monovalent group selected from an alkyl group having 10 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an alkylaryl group having 6 to 20 carbon atoms, and j and k are 1 or 2]. And at least one metal compound selected from carboxylic acid metal salts (hereinafter, “(B component)”)
(Also referred to as), and (C) one or two sterically hindered hydrocarbon substituents in the ortho position with respect to the phenolic hydroxyl group.
An antioxidant having a phenolic skeleton present individually (hereinafter,
"(C component)") is blended.

The present invention will be described in detail below, by which other objects, advantages and effects of the present invention will be apparent.

The polyester in the present invention is a polyester having an ethylene terephthalate unit as a main repeating unit. The term "mainly" as used herein means that a repeating unit other than the ethylene terephthalate component is copolymerized by 20 mol% or less, preferably 15 mol% or less, and particularly preferably 10 mol% or less with respect to all repeating units constituting the polyester. It means that it may be contained. Examples of the difunctional carboxylic acid component other than terephthalic acid that can be copolymerized include, for example, isophthalic acid, naphthalene dicarboxylic acid,
Aromatic and aliphatic bifunctional carboxylic acids such as diphenyldicarboxylic acid, diphenyloxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, P-oxybenzoic acid, adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid are used. Can be mentioned.

As the diol component other than ethylene glycol which can be copolymerized, for example, trimethylene glycol, tetramethylene glycol, cyclohexane-
Examples thereof include aliphatic, alicyclic and aromatic diol compounds such as 1,4-dimethanol, neopentyl glycol, bisphenol A and bisphenol S, and polyoxyalkylene glycol.

Further, the following formula (4) HO- (R ³ -O) _n H (4) [In the formula (4), R ³ is a linear or branched alkylene having 2 or 3 carbon atoms. Group, and n is an integer of 2 to 4], for the purpose of further suppressing the accumulation of foreign matter in the spinneret, for example, 1 to 5% by weight may be copolymerized in the polyester. Examples of the diol component represented by the formula (4) include diethylene glycol, triethylene glycol, tetraethylene glycol and dipropylene glycol.

Further, within the range where the achievement of the object of the present invention is not substantially impaired, trifunctional or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid; glycerin, trimethylolpropane and pentaerythritol. A trifunctional or higher functional polyol may be used as a copolymerization component.

As the polyester in the present invention, a polyester synthesized by any method is used. For example, polyethylene terephthalate will be described. Usually, terephthalic acid and ethylene glycol are directly esterified, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol, or terephthalic acid and ethylene glycol are used. The reaction of the first step to form a glycol ester of terephthalic acid and / or its low polymer by a method of reacting with oxide, and the reaction product of the first step is heated under reduced pressure in the presence of a polymerization catalyst to obtain a desired degree of polymerization. It is produced by a second stage reaction of polycondensation reaction until

In the above formula (1) showing the component (A) used in the polyester composition of the present invention, R ¹ is a carbon number of 3 to 3.
It is an alkyl group of 0 or an aryl group or an alkylaryl group having 6 to 40 carbon atoms, and when R ¹ is an alkyl group or an alkylaryl group, it may be linear or branched. M ¹ is an alkali metal such as Na, K and Li or an alkaline earth metal such as Mg and Ca, and Na and K are preferable. Such organic sulfonates may be used either individually or as a mixture of two or more, and preferred specific examples include sodium stearyl sulfonate, sodium octyl sulfonate, sodium dodecyl sulfonate, and alkyl having an average carbon number of 14 Mention may be made of sodium sulfonate mixtures.

The amount of the organic sulfonate added to the polyester is 0.1 to 15 mol%, particularly 0.1 to 5 mol% based on the bifunctional carboxylic acid component constituting the polyester.

The component (A) can be blended with the polyester at any stage before the completion of the polyester synthesis, preferably in the second stage.

Component (B) used in the resin composition of the present invention
In the above formulas (2) and (3)^TwoIs carbon
C1-C10 alkyl group, C6-C20 aryl group
Or an alkylaryl group having 6 to 20 carbon atoms, which is directly
It may be chain-like or branched. M ¹And M^TwoIs Na, K,
Alkali metals such as Li or alkalis such as Mg and Ca
It is an earth metal.

Specific examples of the metal hydroxide represented by the formula (2) include sodium hydroxide and potassium hydroxide. As the carboxylic acid metal salt represented by the formula (3), potassium acetate, sodium acetate, lithium acetate, calcium acetate, sodium benzoate, potassium benzoate, magnesium benzoate, sodium propionate,
Examples thereof include potassium propionate, lithium propionate, sodium toluate, potassium toluate, lithium toluate and the like. As the component (B), sodium acetate and potassium acetate are preferable. The component (B) can be used either individually or in combination of two or more.

From the viewpoint of suppressing the accumulation of foreign matters on the die surface and keeping the hue of the polyester good, the amount of the component (B) added to the polyester is 1 mol of the organic sulfonate as the component (A). , Preferably 0.01 to 3 mol, particularly preferably 0.1 to 2 mol. The component (B) may be blended with the polyester at any stage before the completion of the polyester synthesis, but it is preferably blended in the first stage.

The component (C) used in the polyester composition of the present invention is an antioxidant having a phenol skeleton having one or two sterically hindered hydrocarbon substituents in the ortho position with respect to the phenolic hydroxyl group. It is an agent. The sterically hindered hydrocarbon substituent is not particularly limited, but typically includes an alkyl group having 1 to 4 carbon atoms.
Specific examples of the alkyl group include methyl group, ethyl group, n
-Propyl group, isopropyl group, n-butyl group, t-butyl group and the like can be mentioned. Of these, a t-butyl group is preferred.

As the component (C), there can be used those commercially available. Specifically, the following compound No.
1 to No. 14 can be mentioned.

Compound No. 1 Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate]

[0022]

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Compound No. 2 1,6-hexanediol-bis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]

[0024]

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Compound No. 3 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5
-Triazine

[0026]

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Compound No. 4 pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate]

[0028]

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Compound No. 5,2,2-thio-diethylenebis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate]

[0030]

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Compound No. 6 Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate

[0032]

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Compound No. 7 N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxyhydrocinamide)

[0034]

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Compound No. 8 3,5-di-t-butyl-4-hydroxy-benzylphosphonate diethyl ester

[0036]

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Compound No. 9 1,3,5-trimethyl-2,4,6-tris (3.5-di-t-butyl-4-hydroxybenzyl) benzene

[0038]

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Compound No. 10 bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium

[0040]

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Compound No. 11 Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate

[0042]

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Compound No. 12 2,4-bis [(octylthio) methyl] -O-cresol

[0044]

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Compound No. 13 Isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate

[0046]

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Compound No. 14 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy-
1,1-Dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane]

[0048]

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Among them, compounds No. 3, No. 4 and N
No. 5 and No. 14 are preferable, and Compound No. 14 is particularly preferable.

These components (C) may be used alone or in combination of two or more.

The content of the component (C) is generally 0.01 to 5% by weight in the polyester composition, preferably 0.05 to 2% by weight. If the amount is too small, the effect of suppressing foreign substance accumulation on the die will not be expressed,
On the other hand, excessive blending causes a problem that the hue of the polymer is deteriorated and the yarn after spinning is colored.

The component (C) may be added to the polyester at any stage before the completion of the polyester synthesis, but it is more preferable to add it in the second stage.

The polyester composition of the present invention may optionally contain various additives such as an ether bond inhibitor, a stabilizer, a color-preventing agent, a heat-resistant agent, a flame retardant, a matting agent, a coloring agent and inorganic fine particles. Can be included.

Thus, the polyester composition of the present invention can be stably molded under a wide range of molding conditions. For example, with regard to yarn production, a method of preventing at a speed of 500 to 2500 m / min, drawing and heat treatment, 1500 to 50
Spinning at a speed of 00 m / min, drawing or false twisting at the same time or subsequently, spinning at a high speed of 5000 m / min or more, and depending on the application, spinning conditions may be omitted. Then, the yarn can be made.

Also when forming into a film or sheet, a method of imparting anisotropy by applying tension only in one direction after film formation, a method of stretching in two directions simultaneously or in any order, two or more steps The desired conditions can be adopted without any problem in the method of multi-stage drawing, etc., and the industrial significance of the present invention is extremely large.

[0056]

[Examples] Examples will be further described below. Parts and% in the examples represent parts by weight and% by weight, respectively, unless otherwise specified. The measurement and evaluation methods of each physical property were as follows. (1) Intrinsic viscosity [η] Measured with an orthochlorophenol solvent at 35 ° C. (2) Hue The values are shown by L value and b value by a Hunter type color difference meter. The larger the L value is, the better the whiteness is, and the b value is the + side, the stronger the yellowness is.

(3) Spinnability Spinneret plate 4 shown in FIG. 1 (large diameter of introduction hole 1 is 5 mm, diameter of discharge hole 2 is 1.3 mm, length is 1.0 mm, number of discharge holes 2 is 2)
4) and the spinning liquid guide rod 7 shown in FIG. 2 (the diameter of the columnar portion 12 is 1.0 mm and the length is 5 mm) are combined to form the spinneret shown in FIG. 3 (the guide rod protruding below the discharge surface 9). (3 mm length), spinning temperature 284 ° C., winding speed 120
The height of the foreign matter around the outer periphery of the spinning hole and the number of breaks during the melt spinning at 0 m / min for 3 days are shown. The stretchability of the unstretched yarn obtained as described above is 8
5 ° C, draw ratio 3.5 times, draw speed 1100 m / min
Stretched at 150 denier / 30 filament 25 kg
The wrap rate when wound was shown. The lap rate is
The following equation shows how much the broken single yarn is wound around various rollers (feeding roller, heating roller, stretching roller) used when drawing the undrawn yarn (original yarn).

Lapping rate (%) = (number of winding-occurring yarns /
Supplied yarn count) x 100

Examples 1 to 7 and Comparative Examples 1 to 4 100 parts of dimethyl terephthalate, ethylene glycol 6
A transesterification vessel was charged with 0 part of the polyalkylene glycol shown in Table 1 and the amount shown in Table 1 and 0.032 part of manganese acetate tetrahydrate (0.025 mol% with respect to dimethyl terephthalate) in a nitrogen gas atmosphere. Take 3 hours down 1
The temperature was raised from 40 ° C. to 220 ° C. and the produced methanol was distilled out of the system to carry out a transesterification reaction. Then
After the addition of 0.020 part of trimethyl phosphate as a stabilizer, the temperature-controlled expulsion of excess ethylene glycol was started. After 10 minutes, 0.04 part of antimony trioxide was used as a polycondensation reaction medium (0.02 parts based on dimethyl terephthalate).
27 mol%) was added. Then, the component (B) shown in Table 1 was added in an amount shown in Table 1, and when the internal temperature reached 240 ° C., the purging of ethylene glycol was terminated and the reaction product was transferred to a polymerization vessel.

Then, after the reaction was carried out at normal pressure for 30 minutes while raising the temperature, sodium dodecylsulfonate was added in the amount shown in Table 1. 760 mmHg to 1 mmHg over 1 hour
Depressurize to 290 ℃ at the same time over 1 hour and 30 minutes
Temperature. Here, the component (C) shown in Table 1 was added in the amount shown in Table 1, and after that, when the polymerization was further performed for 2 hours at a polymerization temperature of 290 ° C. under a reduced pressure of 1 mmHg or less, the nitrogen gas was broken to break the polymerization reaction. 29 nitrogen gas pressurization
The polymer was discharged at 0 ° C., cooled with water, and cut into pellets. The obtained pellets were dried by a conventional method, melt-spun, and stretched. The polymer quality and spinning tone thus obtained were as shown in Table 2.

In Table 1, each component is as follows. B-1: Sodium acetate B-2: Potassium acetate C-1: Compound No. 4 C-2: Compound No. 14 D-1: Diethylene glycol D-2: Triethylene glycol

[0062]

[Table 1]

[0063]

[Table 2]

As is clear from these results, the polyester compositions of the present invention (Examples 1 to 10) have a small amount of foreign matter accumulated in the spinneret, a good spinning condition, and excellent fiber quality. .

[0065]

Industrial Applicability According to the present invention described in detail above, a polyester composition having excellent thermal stability and good moldability such as spinning and stretching, and particularly having less accumulation of foreign matter on the die surface can be obtained.
The whiteness of the fiber obtained by spinning from the composition is as excellent as the conventional one.

[Brief description of the drawings]

FIG. 1 is a sectional view of a main part of a spinneret.

FIG. 2 is a spinning liquid guide rod used for a spinneret.

3 is a cross-sectional view (a) of a main part of the spinneret having the spinning guide rod of FIG. 2 inserted therein and a cross-sectional view (b) of the main part taken along the line AA ′ of the cross-sectional view (a) of the main part.

[Explanation of symbols]

 1 Spinning Liquid Introduction Hole 2 Spinning Liquid Discharge Hole 3 Spinning Hole 4 Spinneret Plate 5 Blade 6 Guide Rod Tip 7 Guide Rod 8 Lower Introduction Hole 9 Discharge Surface 10 Introduction Hole Large Diameter Inner Wall 11 Passage 12 Guide Rod Columnar 13 Annular Passage

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[Procedure amendment]

[Submission date] January 16, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

The compounds No.7 N, N'-hexamethylene-bis (3,5-di -t- butyl-4-hydroxy hydro Shin'namamido)

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction contents]

Thus, the polyester composition of the present invention can be stably molded under a wide range of molding conditions. For example, regarding yarn production, a method of spinning at a speed of 500 to 2500 m / min, drawing and heat treatment, 1500 to 50
Spinning at a speed of 00 m / min, drawing or false twisting at the same time or subsequently, spinning at a high speed of 5000 m / min or more, and depending on the application, spinning conditions may be omitted. Then, the yarn can be made.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction contents]

Then, after the reaction was carried out at normal pressure for 30 minutes while raising the temperature, sodium dodecylsulfonate was added in the amount shown in Table 1. 760 mmHg to 1 mmHg over 1 hour
Depressurize to 290 ℃ at the same time over 1 hour and 30 minutes
Temperature. Here, the component (C) shown in Table 1 was added in the amount shown in Table 1, and thereafter, when the polymerization was further performed at a polymerization temperature of 290 ° C. under reduced pressure of 1 mmHg or less for 2 hours , the vacuum was broken with nitrogen gas. Then, the polymerization reaction is completed, and 29
The polymer was discharged at 0 ° C., cooled with water, and cut into pellets. The obtained pellets were dried by a conventional method, melt-spun, and stretched. The polymer quality and spinning tone thus obtained were as shown in Table 2.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08K 5/42 C08K 5/42

Claims (2)

[Claims] 1. A polyester containing ethylene terephthalate as a main repeating unit, wherein (A) the following formula (1) (R ¹ SO ₃ ) _i M ¹ ... (1) [wherein R ¹ is carbon; A monovalent group selected from an alkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 40 carbon atoms and an alkylaryl group having 6 to 40 carbon atoms, M ¹ is an alkali metal or an alkaline earth metal, i is 1 or 2], (B) the following formula (2) and the following formula (3) M ² (OH) _j ... (2) (R ² —COO) _k M ³ (3) [In the formulas (2) and (3), M ² and M ³ are an alkali metal or an alkaline earth metal, and R ² has 1 to 1 carbon atoms.
A monovalent group selected from an alkyl group having 10 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an alkylaryl group having 6 to 20 carbon atoms, and j and k are 1 or 2]. And at least one metal compound selected from carboxylic acid metal salts, and (C) a phenolic skeleton having one or two sterically hindered hydrocarbon substituents in the ortho position relative to the phenolic hydroxyl group. A polyester composition comprising an antioxidant. 2. The organic sulfonate is 0.1 to 0.1 with respect to the difunctional carboxylic acid component constituting the polyester.
5 mol% is blended, the metal compound is blended in an amount of 0.01 to 3 mol with respect to 1 mol of the organic sulfonate, and the antioxidant is blended in a composition of 0.01 to 5 wt%. The polyester composition according to claim 1.