JPH0665479A - Polyester resin composition and molding therefrom - Google Patents

Abstract

PURPOSE:To provide a polyester resin composed of a polyester resin and a specified modifier, exhibiting an excellent moldability, free from a trouble in high-temperature molding, excellent in strength and dyeability and capable of producing a molding such as a fiber, a film or a bottle. CONSTITUTION:The objective composition contains (A) a polyester resin and (B) a compound of formula I or II (X1 to X3 are each a direct bond, S, etc.; R1 to R4 are each an alkyl or an alkoxy; (p), (q), (r) and (s) are 0 or >=1, provided that p+q+r>=1 in formula I and p+q+r+s>=1 in formula II) preferably in an amount of 0.5 to 5 pts.wt. based on 100 pts.wt. component (A). In addition, polyethylene terephthalate, etc., is preferable as the component (A). The component (B) is obtained, e.g. by reacting a compound of formula III with an alpha-olefin in the presence of a Lewis acid catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition containing a specific modifier for a polyester resin and excellent in moldability, and a fiber obtained from the polyester resin composition, which is excellent in strength characteristics and dyeability, And molded products such as films and bottles having excellent strength characteristics.

[0002]

2. Description of the Related Art Conventional polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and wholly aromatic polyester have been used for molded articles such as fibers, films and bottle containers.
Increasing the strength of these molded products is highly demanded from the viewpoint of resource saving and energy saving. For example, although high-strength polyester filaments are widely used as tire cords, higher strength of polyester tire cords not only reduces the amount of cords used in the tires, but also improves the fuel efficiency of automobiles.

Polyethylene naphthalate and wholly aromatic polyester are promising as film materials such as magnetic tapes because they have the property that they are hard to be deformed by heat due to their excellent heat resistance, and because of their excellent strength properties. By further increasing the strength, it is possible to make a thin film, and it is possible to make a compact and lightweight magnetic recording tape. Polyethylene terephthalate (PET), which is a representative polyester resin, is usually used for container molding by a method called biaxial stretch blow molding, and is widely used as a container material having excellent transparency and mechanical strength and relatively good gas barrier properties. There is.

On the other hand, in recent years, environmental problems have been highlighted, use of environmentally friendly materials, resource saving, energy saving,
Recycling, etc. are being clamored for. From the viewpoint of resource saving, it is desired to reduce the amount of resin and develop a thin container. However, if the amount of PET resin is extremely reduced, the strength is insufficient and it is necessary to increase the strength. One of the methods for increasing the strength is to increase the molecular weight, but increasing the molecular weight alone is not enough to increase the effect, and the melt viscosity becomes high, making it difficult to mold, and stretching due to the entanglement of the molecules. Since the effect was insufficient, it was not possible to achieve sufficient strengthening.

For the above reasons, there has been a demand for a modifier that lowers the melt viscosity of the polyester and facilitates stretching. Such a modifier is used not only for high-strength polyester filaments in fiber applications, but also for strengthening cationic dyeable polyester filaments for clothing, which have not been sufficiently strong in the past, for facilitating spinning of short fibers, and for high speed. It is also useful for improving the production of the spinning process. In order to solve these problems, it was considered to add a lubricant, but when, for example, ethylenebisstearic acid amide, stearic acid, stearyl alcohol, etc. are added to the resin, the melt viscosity decreases, but at the same time the polymerization degree of the resin also decreases. I know it will.

Polyester fibers are widely used for clothing because of their excellent feeling, strength and durability. In recent years, in the thin high-class formal wear field,
In addition to the soft, silky texture, there is a demand for a deep color tone that gives a calm feeling, and to obtain a soft texture by the silk-like technology such as fine denier (super multi conversion) of single fiber and alkali reduction. Became possible.

However, polyester, especially PET
Since it has a dense structure, it is difficult to dye, and it must be dyed under high temperature and high pressure conditions, or must be dyed using a dyeing aid such as a carrier. These methods have drawbacks in terms of economy and operation, and also have a problem of waste liquid treatment when using a carrier, and a problem that if a small amount of dyeing aid remains in the yarn, the fastness is lowered. Was.

As a method for improving the dyeability of polyester fibers, it is known to add a diaminonaphthalene derivative as disclosed in JP-A-50-135156. However, the polyester fiber produced by this method has a problem that it is yellowed by heat setting and the hue changes after dyeing. Further, as a method of improving the dyeability, as disclosed in JP-A-53-143730, a method of incorporating a porous silicate into a polyester fiber is effective as a means for making the dyeing relatively easy. However, although this method facilitates color development, the drawback of lacking color depth due to the high refractive index of the polyester fiber has not been solved.

Further, a method is known in which synthetic fibers containing particles such as silica and alumina are subjected to a solvent treatment to form complex irregularities on the surface so as to increase the color depth of the dyed product. For this reason, it is necessary to mix a large amount of special silica-based fine particles with the polyester polymer, an increase in cost is inevitable, and dispersion in fibers is not easy. In addition, since single yarn breakage and fluff are likely to occur in the spinning and drawing process, it is difficult to make fine denier of single fibers having a denier of 1.5 or less.

In addition to the above, as a method for improving the dyeability of polyester fibers, an easily dyeable polyester fiber obtained by copolymerizing an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an aliphatic diol is disclosed in, for example, JP-A-51- It is disclosed in JP-A-13032 and JP-A-57-30169. When such a compound is used, the dyeability is improved, but the heat resistance,
There are problems such as light fastness, deterioration of raw yarn strength, yellowing coloring, and poor spinnability.

On the other hand, a method of lowering the orientation of the fibers has been proposed, which is not based on the modification of the raw yarn. However, simply lowering the orientation of the entire inside of the fiber has a high boiling water shrinkage ratio and is difficult to handle in the subsequent step,
In addition, there is a problem that the texture of the dyeing degree becomes hard. As described above, no practical method has been found as a method for improving the dyeability of polyester fibers.

[0012]

The problem to be solved by the present invention is to reduce the melt viscosity to facilitate the molding without substantially lowering the polymerization degree of the polyester resin, and to prevent smoke generation during molding at high temperature. A modifier for polyester resin, and a polyester resin composition containing the resin modifier, which enables the production of molded products such as fibers, films, bottles, etc., which have no problems, and have good stretchability and excellent strength properties. Further, it is to obtain a high-strength molded product obtained from the polyester resin composition. Another problem to be solved by the present invention is that it enables deeper dyeing of polyester fibers than ever before, and retains the strength and heat resistance of polyester and does not cause problems such as poor spinnability and yellowing. To do so.

[0013]

As a result of intensive studies to solve the above problems, the present inventors have found that a specific compound has an excellent performance as a modifier for polyester resin, and a polyester resin composition containing this modifier. The inventors have found that the products exhibit excellent effects on the above problems, and have completed the present invention. That is, the present invention provides a polyester resin modifier comprising a compound represented by the following general formula (1) or (2).

[0014]

[Chemical 5]

[Wherein, X ₁ , X ₂ and X ₃ are each a direct bond, or —O—, —S— or

[0016]

[Chemical 6]

R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups or alkoxy groups. p, q, r, s are each 0 or an integer greater than or equal to 1, and in formula (1), p + q + r is an integer greater than or equal to 1, (2)
In the formula, p + q + r + s is an integer of 1 or more. Further, the present invention is a polyester resin, the general formula (1) or
(2) a polyester resin composition characterized by containing a compound represented by, and a polyester resin molded product obtained by molding the polyester resin composition, especially spinning, film molding in a process involving a stretching step The present invention provides molded articles such as fibers, films and bottles obtained by molding such as bottle molding.

In the compound represented by the formula (1) or (2) according to the present invention, X ₁ , X ₂ and X ₃ can be arbitrarily selected within the above range, but the weather resistance of the resin molded article is not sufficient. In order not to touch it, it is better that X ₁ , X ₂ and X ₃ do not form a continuous direct bond. R ₁ , R ₂ , R ₃ and R ₄ can be arbitrarily selected within the above range. The carbon number of R ₁ , R ₂ , R ₃ and R ₄ is preferably 6 or more in the case of an alkyl group and 5 or more in the case of an alkoxy group. When the number of carbon atoms is smaller than this range, it tends to be volatilized, the melt viscosity is not sufficiently lowered, and the effect of improving the stretchability becomes small. The total carbon number of R ₁ , R ₂ , R ₃ and R ₄ , that is,

[0019]

[Equation 1]

It is preferable that the value is 9 or more and 40 or less. Particularly preferably, it is 12 or more and 26 or less. If the total carbon number of R ₁ , R ₂ , R ₃ and R ₄ is too large, the compatibility with the resin deteriorates,
May cause defects in molded parts. Specific examples of R ₁ , R ₂ , R ₃ and R ₄ include a methyl group, an ethyl group, an n-propyl group,
n-butyl group, n-hexyl group, n-octyl group, n-
Decyl group, n-dodecyl group, n-tetradecyl group, n-
Hexadecyl group, n-octadecyl group, n-eicosyl group, n-docosyl group and other linear alkyl groups, iso-propyl group, sec-propyl group, iso-butyl group, sec-butyl group, tert-butyl group, iso-pentyl group, neo-pentyl group, tert-pentyl group, 2-ethylhexyl group,
1-hexylnonyl group, 1-butylpentyl group, methyl branched heptadecyl group, 1,1,3,3-tetramethylbutyl group, 1,3,5-trimethylhexyl group, 1,3,5,7-tetramethyl A branched alkyl group such as an octyl group, and n-
Propyloxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group,
Examples thereof include an alkoxy group such as an n-decyloxy group, an n-dodecyloxy group and a 2-ethylhexyloxy group, but an alkoxy group having 5 or more carbon atoms is particularly preferable.

In the above equations (1) and (2), p, q, r, s
Are 0 or an integer of 1 or more, and in the formula (1),
p ＋ q ＋ r is an integer of 1 or more, and p ＋ q ＋ r ＋ s in Eq. (2)
Is an integer of 1 or more, but it is preferable to select p, q, r and s so that the total number of carbon atoms of R ₁ , R ₂ , R ₃ and R ₄ is in the above range.

The compound represented by the general formula (1) or (2) according to the present invention can be easily obtained by a known reaction. For example, general formula (3) or (4)

[0023]

[Chemical 7]

The compound represented by the formula (wherein X ₁ , X ₂ and X ₃ have the above-mentioned meanings) and the α-olefin or alkyl chloride are reacted under a Lewis acid catalyst to give the above alkyl-substituted compound. Obtainable. In addition, the general formula (5) or
(6)

[0025]

[Chemical 8]

By reacting a compound having a phenolic OH group such as a compound represented by the formula (wherein X ₁ , X ₂ and X ₃ have the above-mentioned meanings) with an alkyl halide in the presence of an alkali. Alkoxy substituents can be obtained.

Specific examples of the polyester resin according to the present invention include polyesters synthesized from alkylene glycols such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polybutylene isophthalate, and aromatic dicarboxylic acids, and terephthalic acid. Polyester obtained from 1,4-cyclohexanedimethanol, polyester obtained by condensing polyoxyethylene (addition mole number 2) bisphenol A with maleic acid, phthalic acid, adipic acid, aromatic dicarboxylic acid and aromatic dihydroxy compound, and / Or a wholly aromatic polyester obtained by condensing an aromatic hydroxycarboxylic acid, more specifically, a condensate of terephthalic acid and bisphenol A, isophthalic acid and hydroxy p-hydroxybenzoic acid Can be mentioned. Among these, a polyester resin containing ethylene terephthalate, ethylene naphthalate or butylene terephthalate as a main repeating unit is particularly preferable.

If necessary, these polyester resins may contain a copolymerization monomer such as sulfonated sodium isophthalate, polyethylene glycol, polypropylene glycol, polyoxyethylene (2 moles added) bisphenol as a modifying monomer. It may contain carbon black, organic or inorganic pigments, titanium oxide as a matting agent, silica, and a modifier such as a phosphorus-based or halogen-based flame retardant.

The compound represented by the formula (1) or (2) of the present invention is preferably used for 100 parts (weight basis, the same applies hereinafter) of the raw material polyester resin in order to exert its intended performance. It is preferable to add 0.1 to 10 parts, more preferably 0.5 to 5 parts. If the addition amount is less than 0.1 part, the effect becomes small, and if it exceeds 10 parts, the physical properties of the resin are adversely affected. The method of adding the compound represented by the formula (1) or (2) according to the present invention to the raw polyester resin may be added at an appropriate step during or after resin production, or resin pellets during molding. Alternatively, they may be mixed and added to the molten resin. Further, a high-concentration master chip may be prepared, and the polyester resin not containing the compound represented by the formula (1) or (2) and the master chip may be melt-mixed at the time of molding. The compound represented by the formula (1) or (2) according to the present invention is uniformly added to and mixed with the polyester resin, and even if exposed to a high temperature during melt spinning, it hardly fumes or decomposes, Excellent heat resistance.

From the polyester resin composition to which the compound represented by the formula (1) or (2) according to the present invention is added, high-strength polyester fibers, films, and molded articles such as bottles can be obtained. The reason for this is not clear, but in addition to the fact that it is possible to mold resins with high viscosity and high degree of polymerization, which have not been able to be molded by lowering the melt viscosity of the resin, the stretching process after melt extrusion is smoothed, and a more highly oriented molded product can be obtained. It is presumed that this is due to what can be obtained.

A part of the compound represented by the general formula (1) according to the present invention is used as a modifier for polyester resin.
-93753. However, JP-A-58
-93753 relates to a polyethylene terephthalate resin composition containing a crystal nucleating agent as an essential component and having a relatively low molecular weight. This resin composition is used at a relatively low temperature of around 100 ° C in injection molding applications that do not require stretching. The purpose is to realize mold molding in. On the other hand, in the case of the present invention, when a crystal nucleating agent is used in combination, the crystallization of the resin is promoted during extrusion, cooling and solidification in the molding of fibers and films, and during the injection of preform in the molding of bottles, and the subsequent stretching. It is not possible to obtain a high-strength molded article for the purpose of the present invention that does not impair the process.

If desired, various additives such as colorants, oxidation stabilizers, ultraviolet absorbers, antistatic agents, flame retardants, etc. may be added to the polyester resin composition of the present invention. . However, the use of a crystal nucleating agent is not preferable as described above.

Next, a method for producing fibers, films and bottles using the polyester resin composition of the present invention will be described. [1] Fiber In the polyester fiber of the present invention, the raw material polyester resin as described above and the compound represented by the formula (1) or (2) which is the modifier of the present invention are uniformly mixed and spun in a molten state, It is obtained by stretching after cooling and heat treatment. The spun yarn may be cooled and once wound up as an undrawn yarn, then preheated and drawn, and subsequently heat treated under tension, or the spun yarn may be taken up by a take-up roller without being taken up, and then on a heating roller. You may draw and heat-process. Stretching and heat treatment can be performed without changing the same as for ordinary polyester fibers. When the resin is polyethylene terephthalate, the preferred preheating temperature during stretching is 60 to 100 ° C, and the preferred temperature for heat treatment is 150 to 250 ° C. It is desirable that the draw ratio for obtaining high-strength fiber is 4 times or more.

In order to obtain a high strength polyester fiber, it is preferable to use a resin having a high degree of polymerization. For example, when polyethylene terephthalate is used as the resin, it is desirable that the intrinsic viscosity at 25 ° C. in phenol / tetrachloroethane (60/40, weight ratio) is 0.9 or more. When the polyester resin is a cationic dyeable polyester resin in which sulfonated sodium isophthalate is copolymerized, it has a higher melt viscosity and is inferior in stretchability to ordinary polyethylene terephthalate resin, and thus it is difficult to obtain a fiber having high strength. However, it is possible to obtain a cationic dyeable yarn having a higher strength than ever before by spinning and drawing the cationic dyeable polyester resin composition containing the modifier of the present invention by the above method. In this case, the intrinsic viscosity of the cationic dyeable polyester resin is preferably 0.5 or more.

[2] Film In the polyester film of the present invention, the polyester resin and the compound represented by the formula (1) or (2) which is the modifier of the present invention are uniformly mixed and extruded in a molten state through a T-die. After cooling, biaxial stretching is performed simultaneously or sequentially under heating, and then heat treatment is performed. For example, when the resin is polyethylene terephthalate, the preferable preheating temperature during stretching is 60 to 120 ° C, and the preferable temperature for heat treatment is 150 to 250 ° C. The preferred draw ratio for obtaining a high-strength film is 3.5 times or more in both the longitudinal and transverse directions.

[3] Bottle As the method for molding the polyester bottle container of the present invention, the biaxially stretch blow molding used in the case of manufacturing a normal PET container is preferable, and the preform (preform) is once taken out and then separated. Any of a method called a cold parison method in which stretch blow molding is performed in a step, and a method called a hot parison method in which a step of forming a preform and a step of stretch blow molding are continuous can be adopted.
In producing the polyester bottle container of the present invention, the effect is small only by adding the compound represented by the general formula (1) or (2) to the polyester resin, and the effect of the present invention is obtained only after stretch blow molding. Is achieved.

In the present invention, when the preform and the container excluding the non-stretched mouth portion and the longitudinal and transverse dimensional ratios are used to determine the longitudinal and transverse stretching ratios and the product of each is defined as the area stretching ratio, in the present invention. Is preferably four times or more. When it is less than 4 times, the degree of strength increase is small as compared with the case where the compound represented by the general formula (1) or (2) is not added. Although the mechanism by which the strength is increased in the present invention is not clear, it is considered that addition of the compound represented by the general formula (1) or (2) facilitates orientation of the polyester resin during stretching. Further, the above general formula (1) or (2)
The compound represented by also has the property of lowering the melt viscosity of the polyester resin, and has the advantage of improving the processability in the injection step of molding the preform and improving the productivity.

[0038]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples and examples, but the present invention is not limited to these examples. Synthesis example 1

[0039]

[Chemical 9]

0.3 mol of 1,3-bis (4-hydroxyphenoxy) benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 500 g of dimethyl sulfoxide, and 0.6 mol of KOH was added thereto to form a phenolate. 0.6 mol of octyl bromide was added dropwise at 80 ° C, and the mixture was aged for 5 hours. The formed KBr was filtered and desolvated, and then 1 liter of chloroform was added and washed with water. Chloroform was distilled off, and the residue was crystallized from isopropanol to obtain the desired product in a yield of 80%. Synthesis example 2

[0041]

[Chemical 10]

Nitrobenzene 16.8 was added to 400 ml of methylene chloride.
ml, Ph ₃ CAsF ₆ 350 mg and p-bis (2-chloroisopropyl) benzene 0.33 mol, octyloxybenzene
0.66 mol was added and the mixture cooled to -42 ° C. Hydrogen chloride gas was generated when 3.75 g of crushed aluminum chloride was added thereto. After 3 hours, it was decomposed in an ice bath of dilute hydrochloric acid, and the oil phase was washed with water. The solvent was distilled off and the residue was crystallized from isopropanol to obtain the desired product in a yield of 70%.

Synthesis Example 3

[0044]

[Chemical 11]

To 300 ml of 1,2-dichloroethane, 0.5 mol of 3-phenyloxyphenyl-3'-phenylphenyl ether (Tetraphenyl ether S-3103 manufactured by Matsumura Oil Research Institute) and 1.0 mol of propylene tetramer were added, and the mixture was further crushed into aluminum chloride. 0.01 mol was added and reacted at 60 ° C. for 4 hours. The reaction solution was decomposed in an ice bath of dilute hydrochloric acid, the dichloroethane phase was washed with water and then desolvated to obtain the desired product.

Synthesis Example 4

[0047]

[Chemical 12]

To 30 ml of 1,2-dichloroethane, 0.5 mol of 1,4-diphenoxybenzene (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 1.0 mol of diisobutylene were added, and 0.01 mol of crushed aluminum chloride was added, and the mixture was reacted at 60 ° C. for 4 hours. It was The reaction solution was decomposed in an ice bath of dilute hydrochloric acid, and the dichloroethane phase was washed with water to remove the solvent. Further, unreacted raw materials were removed under high vacuum, treated with clay and activated carbon, and filtered to obtain the desired product.

Synthesis Example 5

[0050]

[Chemical 13]

The target compound was synthesized in exactly the same manner as in Synthesis Example 4, except that 1,4-diphenylbenzene was used in place of 1,4-diphenoxybenzene and 0.6 mol of 1-octadecene was used in place of 1.0 mol of diisobutylene. did.

Example 1 The modifier shown in Table 1 was added to 100 parts by weight of a polyethylene terephthalate resin at a ratio of 5 parts by weight, and the mixture was melt-mixed by an extruder. The obtained strand was water-cooled and cut to prepare a sample. The melt viscosity of this resin composition was measured using a flow tester at 280 ° C, load 10kgf, die diameter 1.0mm, length 10m.
The measurement was performed under the conditions of m and a plunger area of 1.0 cm ² . The sample after the flow tester measurement was dissolved in a phenol / tetrachloroethane (60/40, weight ratio) mixed solution, and the intrinsic viscosity [η] at 25 ° C was measured. In the following, [η] in each example shows the value under this condition. [Η]
However, it can be said that the same thing as the one without the addition of the modifier has essentially no decrease in the degree of resin polymerization. The results are shown in Table 1.

[0053]

[Table 1]

Example 2 The resin was changed to polybutylene terephthalate and polyethylene naphthalate, and the temperature was set to the temperature conditions shown in Table 2,
Otherwise, the melt viscosity and the intrinsic viscosity were measured in the same manner as in Example 1. The results are shown in Table 2.

[0055]

[Table 2]

Example 3 100 parts by weight of polyethylene terephthalate resin (intrinsic viscosity
1.2) was added with 3 parts by weight of the modifier of the present invention shown in Table 3,
The mixture was melt-mixed by an extruder and extruded from a nozzle having a diameter of 0.4 mm and 48 holes at a discharge rate of 85 g / min. Extrusion temperature is
It was 310 ° C. The spun yarn was wound at 720 m / min to obtain an undrawn yarn. The unstretched yarn obtained was stretched at a preheating temperature of 90 ° C. by a roller type stretching machine, and then the second roller (temperature 120
℃), stretching plate (210 ℃), third roller (temperature 20
It was further stretched twice at 0 ° C.), heat-fixed with a third roller and wound up.

The amount of modifier contained in the obtained fiber was quantified by the following method. 50 mg of fiber is dissolved in 2 ml of hexafluoroisopropanol, and chloroform is added to make the total volume 20 ml. This liquid was analyzed by high performance liquid chromatography (column WAKOSIL 5SIL, diameter 4.6 ml, length 250 mm).
Chloroform was used as an eluent and quantified under the following detection conditions. Detection conditions ... Detector UV285 nm, flow rate 1 ml / min Under these conditions, the polyester is not eluted and only the modifier of the present invention can be quantified. The results are summarized in Table 3. The draw ratio was 0.9 times the maximum draw ratio.

[0058]

[Table 3]

As is clear from Table 3, the addition of the modifying agent of the present invention facilitates spinning, and the modifying agent of the present invention remains in the yarn substantially entirely, and the draw ratio increases and finally obtained. The drawn yarn has higher strength than that of no addition.

Example 4 100 parts by weight of polyethylene terephthalate resin (intrinsic viscosity
To 1.2), 1 to 3 parts by weight of the modifier of the present invention shown in Table 4 is added, and the mixture is melt-mixed by an extruder, and the width is 0.3 m at a temperature of 300 ° C.
An unstretched film having a thickness of about 240 μm was obtained by extruding from a T die having a length of 10 cm and a length of 10 cm at a constant discharge amount, winding the film around a cooling drum, cooling and solidifying the film. The unstretched film was simultaneously biaxially stretched at a temperature of 90 ° C. at the same ratio of length and width to 0.9 times the maximum stretching ratio, and further heat-set at a temperature of 210 ° C. The stress-strain curve of the obtained film was measured according to ASTM D-882. The results are summarized in Table 4.

[0061]

[Table 4]

Example 5 Using the modifiers of the present invention shown in Table 5, the resin was changed to polyethylene naphthalate (intrinsic viscosity 0.9) and the extrusion temperature 310
The test was conducted in the same manner as in Example 4 except that the stretching temperature was 130 ° C and the heat setting temperature was 240 ° C. The results are summarized in Table 5.

[0063]

[Table 5]

Example 6 Using the modifiers of the present invention shown in Table 6, the resin was changed to polybutylene terephthalate (intrinsic viscosity 1.2) and the extrusion temperature 290
The same test as in Example 4 was carried out except that the temperature was 90 ° C., the stretching temperature was 90 ° C., and the heat setting temperature was 190 ° C. The results are summarized in Table 6.

[0065]

[Table 6]

As shown in Examples 4 to 6, the resin composition of the present invention can lower the extrusion pressure and increase the draw ratio, and the strength of the obtained film is increased. Therefore, it is possible to reduce the thickness of the magnetic tape or the like.

Example 7 100 parts by weight of polyethylene terephthalate resin (intrinsic viscosity
In 1.2), the modifier of the present invention was added in the amount shown in Table 7, and the mixture was melt-mixed by an extruder and the portion excluding the mouth had an outer diameter of 20 m.
m, length 85 mm, weight 23 g preform (preform)
Was molded by injection molding. The molding conditions at that time were that the cylinder temperature was set at 290 ° C and the mold temperature was set at 20 ° C.
Subsequently, biaxially stretch blow molding was performed at 110 ° C to obtain a volume of 1
A cylindrical container having a liter, a body diameter of 90 mm, a height excluding the mouth portion of 160 mm, and a mouth diameter of 20 mm was formed. The draw ratio of this container is 1.9 times in the longitudinal direction, 4.5 times in the transverse direction, and the area drawing ratio is 8.6 times. An injection blow molding machine manufactured by Nissei ASB Machine Co., Ltd. was used as a molding machine.
Using the obtained container, the drop strength and the tensile strength were measured by the following methods. The results are shown in Table 7.

<Test method> Drop strength The container was filled with water and capped with a cap, and then naturally dropped onto the concrete surface from a height of 1 m. Ten containers were dropped up to 10 times and evaluated by the number of times two (20%) cracked. -Tensile strength The container was cut open and a test piece was prepared with dumbbell No. 3.
Using Tensilon UCT-100 manufactured by Orientec, the stress was measured while pulling at a constant speed of 10 mm / min, and the yield stress, the breaking stress, and the elastic modulus were determined. The results are summarized in Table 7.

[0069]

[Table 7]

As is clear from Table 7, the resin composition of the present invention can increase the strength of the obtained container (bottle), and enables the production of a high-strength thin bottle.

Example 8 3 parts by weight of the modifier of the present invention shown in Table 8 was added to 100 parts by weight of a pulverized product of polyethylene terephthalate (J-125, manufactured by Mitsui Pet Resin Co., Ltd.) chips, and the temperature was 140 ° C. and 2 mmHg. Under the conditions
It was dried for 10 hours. Next, this mixture was uniformly kneaded into chips by a biaxial melt extruder. The chips were dried under the above conditions and spun at 290 ° C. using an ordinary uniaxial spinning device, and then the undrawn yarn wound was made to have an elongation of the drawn yarn of about 30%. The fiber was obtained by stretching at 80 ° C. and heat setting at 180 ° C. A sock knitted fabric (one-piece tubular knitted fabric) was knitted from this fiber, dyed under the following conditions, washed with water, reduced and washed, and air-dried.

<Dyeing conditions> Dyeing: Foron Navy S-2GL gran, 200% (Sandoz
Co., Ltd.) Staining density: 5% o. w. f. Dyeing aid: Rebenol TD-660 (manufactured by Kao Corporation) Dyeing aid concentration: 1 g / l Dyeing bath pH: 4.5 Dyeing bath ratio: 1/20 Dyeing temperature, time: 130 ° C, 30 minutes <Reduction washing> Hydro Sulfite: 2 g / liter Caustic soda: 1 g / liter Washing temperature, time: 80 ° C, 10 minutes Bath ratio: 1/30 Next, spectral whiteness meter ERP-80WX (manufactured by Tokyo Denshoku Co., Ltd.)
After measuring the L value (%) and the b value with, the dry fastness and wet friction fastness were measured according to (JIS L 0849), and these physical property values are shown in Table 8. Further, a dyeing fastness test for carbon arc lighting was performed by the following method. That is, the dyeing fastness is JIS L
According to 0842, using a Sunshine Super Long Life Weather Meter (Suga Test Instruments Co., Ltd.), the carbon arc method was carried out at 63 ° C. for 40 hours, and the grade was judged by the simultaneously exposed blue scale. The results are shown in Table 8.

Comparative Example 1 A sock knitted fabric was knitted in the same manner as in Example 8 without adding the modifier of the present invention, and the same test was conducted. The results are shown in Table 8.

Comparative Example 2 When dyeing the sock knitted fabric obtained in Comparative Example 1, a carrier, o-phenylphenol emulsified with a nonionic activator (Emulgen 913: manufactured by Kao Corporation) was added to the dyeing solution. The o-phenylphenol was adjusted to 10% owf. After dyeing and reduction washing at 100 ° C. for 60 minutes, air-drying, heat treatment at 180 ° C. for 2 minutes as a general condition of the carrier, removal of the carrier, various measurements were conducted in the same manner as in Example 8, and Table 8 The results are shown.

[0075]

[Table 8]

As is clear from Table 8, all of the additives to which the modifying agent of the present invention was added were deep blue, but the dyes without addition (Comparative Example 1) were slightly lighter. Further, in the conventional carrier dyeing (Comparative Example 2), the dyeing was performed in a dark color as in the case of adding the modifier of the present invention, but after dyeing, heat treatment is required, and the light fastness is Fell.

[0077]

As described above, the polyester resin composition of the present invention containing the compound represented by the general formula (1) or (2) as shown in the examples is used in molded articles such as fibers, films and bottles. It has excellent strength and dyeability. That is, it is suggested from Examples 1 and 2 that the modifier of the present invention can reduce the melt viscosity of the polyester resin composition to produce a high-strength yarn, and from Examples 3 and 8 The polyester fiber of the present invention exhibits excellent stretchability, high strength and excellent dyeability, and the polyester film of Examples 4 to 6 exhibits excellent stretchability and high strength, and Example 7
From the above, it is understood that the polyester bottle of the present invention exhibits excellent stretchability and high strength.

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Claims (10)

[Claims] 1. A polyester resin and the general formula (1) or
A polyester resin composition comprising a compound represented by (2). [Chemical 1] [In the formula, X ₁ , X ₂ and X ₃ are each a direct bond or -O.
-, -S- or R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups or alkoxy groups.
p, q, r, s are each an integer greater than or equal to 0, and (1)
In the formula, p + q + r is an integer of 1 or more, and in formula (2),
p + q + r + s is an integer of 1 or more. ] 2. The polyester resin composition according to claim 1, wherein the polyester resin is a polyester resin containing ethylene terephthalate, ethylene naphthalate or butylene terephthalate as a main repeating unit. 3. A polyester resin molded article obtained by molding the polyester resin composition according to claim 1. 4. A polyester resin molded product obtained by molding the polyester resin composition according to claim 1 or 2 in a process including a stretching step. 5. A polyester fiber obtained by spinning the polyester resin composition according to claim 1. 6. A polyester film obtained by film-forming the polyester resin composition according to claim 1. 7. A polyester bottle obtained by biaxially stretch blow molding the polyester resin composition according to claim 1. 8. The polyester resin composition according to claim 1, wherein the polyester resin has an intrinsic viscosity of 0.9 or more at 25 ° C. in phenol / tetrachloroethane (60/40, weight ratio). 9. A polyester resin modifier comprising a compound represented by the general formula (1) or (2). [Chemical 3] [In the formula, X ₁ , X ₂ and X ₃ are each a direct bond or -O.
-, -S- or R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups or alkoxy groups.
p, q, r, s are each an integer greater than or equal to 0, and (1)
In the formula, p + q + r is an integer of 1 or more, and in formula (2),
p + q + r + s is an integer of 1 or more. ] 10. The polyester resin modifier according to claim 9, wherein R ₁ , R ₂ , R ₃ and R ₄ are alkoxy groups having 5 or more carbon atoms.