JPH11158361A - Polyester hollow container and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyethylene naphthalenedicarboxylate hollow container having excellent color tone and transparency. SOLUTION: This hollow container comprises polyethylene naphthalenedicarboxylate containing antimony element and/or germanium element and a dye, and has excellent color tone and a haze of <=3% in the body portion. Preferably the dye is contained in an amount of 0.1-100 ppm and comprises a blue dye and/or a violet dye or an anthracene-based dye.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hollow polyester container and a method for producing the same, and more particularly, to a hollow polyethylene naphthalenedicarboxylate container excellent in hue and transparency and a method for producing the same.

[0002]

2. Description of the Related Art Polyethylene naphthalenedicarboxylate has recently been used in bottles (containers) and sheet materials because of its superior physical properties such as heat resistance, gas barrier property, chemical resistance and the like as compared with polyethylene terephthalate. Many proposals have been made by blending with polyethylene terephthalate or using alone.

[0003] For beverage bottles, excellent quality such as hue and transparency is strongly required from the viewpoint of commercial value.

[0004] Polyethylene naphthalene dicarboxylate can be obtained as a hollow container through a polymerization reaction using a catalyst similar to polyethylene terephthalate, followed by injection molding to form a preform and then blow molding. .

However, polyethylene naphthalene dicarboxylate, which is a raw material polymer for a polyethylene naphthalene dicarboxylate hollow container, has a higher melt viscosity than a polyethylene terephthalate polymer, and when it is formed into a molded product, it is plasticized to a higher temperature. It is difficult to industrially obtain high-purity naphthalenedicarboxylic acid as an acid component used as a raw material, and when the lower alkyl ester is used, it is used in a transesterification reaction step. The fact is that the catalyst tends to yellow due to a catalyst or the like.

As a countermeasure against the yellowing, there is a method of adding a tinting agent such as a cobalt compound to suppress the yellowing of the polymer. In this case, the addition of the cobalt compound can certainly suppress the yellowing of the polymer, but the hue of the polymer becomes gray. The amount increases, the transparency of the polymer itself decreases, and the precipitated metal itself acts as a nucleating agent in the polymer, and when the polymer is molded for bottles and sheet applications,
Problems such as whitening due to accelerated crystallization occur in the polymer.

As described above, the polyethylene naphthalene dicarboxylate polymer has a large coloring depending on its melt viscosity, polycondensation conditions and molding conditions, and a hollow container formed from such a polymer is not necessarily in a state where a good hue can be obtained.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems.
An object of the present invention is to provide a polyethylene naphthalenedicarboxylate hollow container excellent in transparency and a method for producing the same.

[0009]

That is, the present invention relates to a hollow container comprising polyethylene naphthalene dicarboxylate containing an antimony element and / or a germanium element and a dye, having an excellent hue, and having a body haze of 3% or less. The manufacturing method.

The polyethylene naphthalenedicarboxylate in the present invention has a content of 70% based on the total dicarboxylic acid component.
It is a polyester comprising not less than mol% of naphthalenedicarboxylic acid as a dicarboxylic acid component and not less than 70 mol% of ethylene glycol relative to all glycol components as a glycol component.

[0011] Examples of the dicarboxylic acid component include 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, which are preferably at least 80 mol% based on the total dicarboxylic acid component. As the dicarboxylic acid component, 2,6-naphthalenedicarboxylic acid is particularly preferred.

The components copolymerizable in the range of 30 mol% or less with respect to the total acid components include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; Aromatic dicarboxylic acids such as acid, isophthalic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylsulfonedicarboxylic acid, and diphenyletherdicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, decalindicarboxylic acid, and teleralindicarboxylic acid; Oxyacids such as glycolic acid and p-oxybenzoic acid are exemplified.

In the present invention, the glycol component constituting polyethylene naphthalenedicarboxylate is 70
Mole% or more is ethylene glycol, but glycol components other than ethylene glycol may be copolymerized in a range of 30 mol% or less based on all glycol components. Examples of copolymerizable glycol components include trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, cyclohexane dimethanol, and bisphenol A.

If the acid component and / or the glycol component is copolymerized in an amount exceeding 30 mol%, the strength of the polyethylene naphthalenedicarboxylate hollow container is reduced.

As the transesterification catalyst used for producing polyethylene naphthalene dicarboxylate, manganese compounds, calcium compounds, magnesium compounds, titanium compounds, zinc compounds, sodium compounds generally used widely as transesterification catalysts for polyethylene terephthalate , Potassium compounds, cerium compounds, lithium compounds and the like can be used. These can be used in combination.

The polyethylene naphthalene dicarboxylate is preferably subjected to a transesterification reaction with the above-mentioned transesterification catalyst, deactivated the transesterification catalyst with a phosphorus compound, and subsequently subjected to a polycondensation reaction at a high temperature and high vacuum. Can be obtained by

As the polycondensation catalyst, a germanium compound and / or an antimony compound are used from the viewpoint of improving polymerization activity and hue.

In the present invention, it is necessary to add a dye in order to improve the hue. As the dye, a blue dye or a purple dye is preferable, and among them, an anthraquinone organic dye is particularly preferable.

Examples of the anthraquinone organic dye include 1,4-bis (2,4,6-trimethylanilino)-
9,10-anthraquinone, 1-hydroxy-4-
((3-hydroxymethyl) phenylanilino) -9,
10-anthraquinone, 1,4,5,8-tetraamino-9,10-anthraquinone, 3-hydroxy-1-
(4-methylphenylanilino) -9,10-anthraquinone and 1,4-diamino-9,10-anthraquinone, among which 1,4-bis (2,4,6-trimethylanilino)- 9,10-anthraquinone, 3-hydroxy-1- (4-methylphenylanilino) -9,1
0-anthraquinone is preferred.

The amount of the dye used is 0.1 to 1 with respect to polyethylene naphthalene dicarboxylate.
Preferably it is 00 ppm. If the amount is less than 0.1 ppm, the coloring of the polyethylene naphthalene dicarboxylate hollow container is insufficient, and the effect of improving the hue is small.
If it exceeds 00 ppm, the appearance in the polyethylene naphthalene dicarboxylate hollow container is lowered, for example, the transparency is undesirably lowered.

The haze of the obtained polyethylene naphthalene dicarboxylate hollow container is preferably 3% or less. This is a value when the thickness is 300 μm. 3
%, It is not preferable in appearance. The thickness of the bottle varies depending on the capacity and application, but is
m.

Although the body haze of the hollow container varies depending on the amount of the dye contained in the polyethylene naphthalene dicarboxylate hollow container, in the present invention in which the dye is added for the purpose of improving the hue, the body haze is 3%. The following is preferred.

The preform, which is a preform of the hollow container of the present invention, is preferably made of a polyester having an intrinsic viscosity of 0.5 to 0.8. If the intrinsic viscosity is less than 0.5, the obtained hollow container is inferior in strength, and molding failure such as uneven wall thickness occurs during blow molding, which is not preferable. If the intrinsic viscosity is more than 0.8, the melt viscosity becomes too high, resulting in poor moldability. If the molding temperature is increased to improve the moldability, the deterioration of the hue due to thermal deterioration becomes unfavorable.

As a method for incorporating a dye into the polyethylene naphthalenedicarboxylate hollow container according to the present invention, a polyethylene naphthalenedicarboxylate masterbatch containing a dye is prepared in advance, and a preform for manufacturing the hollow container is injection-molded. In this case, it is preferable to adopt a production method of dry blending with a polyethylene naphthalenedicarboxylate chip.

When such a method is used, polyethylene naphthalenedicarboxylate hollow containers of different grades of coloring can be easily produced.
That is, the degree of coloring of the hollow container can be controlled by changing the dry blend ratio.

For the masterbatch containing the dye of the present invention, a method in which polyethylene naphthalenedicarboxylate and the dye are melt-mixed with a reaction extruder can be used. It can be produced by adding a dye at an early stage of the transesterification step or the polycondensation step.

When the masterbatch is produced by a reaction extruder, the dye is added in powder form or a solvent which does not substantially depolymerize the polyethylene naphthalenedicarboxylate polymer and is liable to volatilize at high temperatures, for example, water,
A method of adding a dye slurry or a dye solution using an organic solvent is used.

When a masterbatch is prepared by adding a dye in a polycondensation step, it is not substantially copolymerized into ethylene glycol, which is the main component of the polyethylene naphthalenedicarboxylate polymer, or into the polymer molecular chain. In the case where a volatile solvent or a glycol component has a copolymer component, a method of adding it in the form of a dye slurry or a dye solution using the glycol is used.

The concentration of the dye in the polyethylene naphthalene dicarboxylate masterbatch is 10 to 1000.
It is preferably ppm.

If the concentration is less than 10 ppm, the blending ratio of the masterbatch becomes high in order to sufficiently color the obtained polyethylene naphthalenedicarboxylate hollow container, which is disadvantageous economically. Undesirable physical properties due to the above appear undesirably in the hollow container. Such unfavorable physical properties include an increase in the concentration of acetaldehyde in the hollow container. That is, when the master batch is manufactured using a reaction extruder, when the acetaldehyde concentration in the master batch is increased to make it a molten state and the hollow container is formed as a result, by-products are contained at a high concentration. Is not preferred.

When the masterbatch contains a dye in excess of 1000 ppm, the blending amount of the masterbatch becomes small when performing pale coloring, and the degree of coloring of the resulting polyethylene naphthalene dicarboxylate hollow container tends to vary. Therefore, it is not preferable.

In the case where a masterbatch is produced by a reaction extruder or in the case of production by melt polycondensation of polyethylene naphthalene dicarboxylate, when the preform is molded, the other polyethylene blended with the masterbatch is used. Preferably, the quality of the naphthalenedicarboxylate is the same. If these qualities are not the same, the difference in molecular weight causes a difference in bottle strength and the like, which is not preferable.

The dry blending of the polyethylene naphthalenedicarboxylate masterbatch and the polyethylene naphthalenedicarboxylate according to the present invention is performed in such a manner that the content of the masterbatch is 0.1% based on the total amount of the polyethylene naphthalenedicarboxylate. It is preferable to blend them so as to be 5 to 10 wt%. When the content of the polyethylene naphthalene dicarboxylate masterbatch is less than 0.5 wt%, not only the coloring degree is small and the hue improvement effect is small, but also the masterbatch blended at the time of injection molding is used in a polyethylene naphthalenedicarboxylate chip. It is not preferable because there is a possibility that a difference in the degree of coloring may occur due to variation due to localization. Master batch content is 10
If it exceeds wt%, it is economically and unfavorably quality.
That is, the acetaldehyde content of a by-product generated when a master batch is produced by melt mixing with a reaction extruder increases. In addition, the content of the polyethylene naphthalene dicarboxylate masterbatch is 10 wt.
%, It tends to be affected by a difference in quality such as intrinsic viscosity from the polyethylene naphthalenedicarboxylate to be blended, which is not preferable.

The polyethylene naphthalenedicarboxylate according to the present invention may contain various additives such as an antioxidant, an ultraviolet absorber and an antistatic agent, if necessary.

[0035]

The present invention will be described in more detail with reference to the following examples. Various properties were measured as follows.

Intrinsic viscosity: Calculated from the solution viscosity measured at 35 ° C. using a phenol / tetrachloroethane = 6/4 (weight ratio) mixed solvent.

Color measurement: Z- # 8 manufactured by Nippon Denshoku Industries Co., Ltd.
It measured using 0. When measuring the color of the preform bottle, after crushing the molded product with a crusher,
The crystallization treatment was performed at 1 ° C. for 1 hour.

Haze: A body (thickness: 300 μ) of a polyester hollow container was cut out and measured with a turbidity meter manufactured by Nippon Denshoku Industries Co., Ltd.

Method for producing master batches in parentheses: 2, 6
-100 parts by weight of naphthalenedicarboxylic acid dimethyl ester and 51 parts by weight of ethylene glycol are subjected to a transesterification reaction according to a conventional method, and then subjected to a polycondensation reaction by a conventional method under high temperature and high vacuum using antimony trioxide as a polycondensation catalyst. A strand type chip was obtained. The obtained polymer was continuously subjected to solid-state polymerization at 240 ° C. or lower and high temperature and high vacuum of 1.0 mmHg or lower by a conventional method to obtain a polymer having an intrinsic viscosity of 0.70.

The above polymer was subjected to a reaction extruder using a blue dye, ESTOFIL BLUE S-RBL.
(Manufactured by Clariant) was melt-kneaded at a concentration of 100 ppm to obtain a polyethylene naphthalenedicarboxylate masterbatch () having an intrinsic viscosity of 0.65 and Col-b = -29.3.

Production method of master batch (): ESTOFIL BLUE S-RBL (Cl
(manufactured by Ariant Co., Ltd.) to 200 ppm, in the same manner as in the master batch ().
4. A polyethylene naphthalenedicarboxylate masterbatch (Col-b = -50.1) was obtained.

Method for producing master batch (): 2, 6
-When transesterifying 100 parts by weight of naphthalenedicarboxylic acid dimethyl ester and 51 parts by weight of ethylene glycol by a conventional method, a blue dye ESTOFIL BLU is used.
ES-RBL (manufactured by Clariant) was added to the acid component at a concentration of 50 ppm, and then a polycondensation reaction was performed at high temperature and high vacuum in the presence of an antimony trioxide catalyst.
A polyethylene naphthalenedicarboxylate masterbatch () having an intrinsic viscosity of 0.62 and Col-b = -18.2 was obtained.

Example 1 100 parts by weight of 2,6-naphthalenedicarboxy dimethyl ester and 51 parts by weight of ethylene glycol were subjected to a transesterification reaction by a conventional method, and polycondensation was carried out using antimony trioxide as a polycondensation catalyst in a conventional manner. The polymer was subjected to solid-state polymerization at a high temperature of 240 ° C. or less and a high temperature of 1 mmHg or less under high vacuum to obtain a polyethylene naphthalenedicarboxylate polymer having an intrinsic viscosity of 0.65 and Col-b = 0.8.

The polymer and the master batch () were each dried at 160 ° C. for 5 hours, and then dry-blended at a weight ratio of 30: 1 to obtain an injection molding machine 100 manufactured by Meiki Seisakusho.
It was molded at 305 ° C. using DM to obtain 55 g of a preform. This preform is blow-stretched to obtain an internal volume of 1.
It was a 5-liter hollow container having a body thickness of 300μ.

After crushing the preform, the crystallization treatment at 170 ° C. for 1 hour gave a Col-b value of -7 and an intrinsic viscosity of the preform of 0.56. The haze of the hollow container was 1.2.

Example 2 A preform and a hollow container were obtained in the same manner as in Example 1 except that the blend ratio of polyethylene naphthalenedicarboxylate and polyethylene naphthalenedicarboxylate masterbatch was changed as shown in Table 1. . The quality of the obtained molded body was as shown in Table 1.

[Comparative Example 1] A transesterification reaction, a polycondensation reaction and a solid-phase polymerization were carried out using antimony trioxide as a polycondensation catalyst according to a conventional method.
A polyethylene naphthalenedicarboxylate polymer having lb = 0.8 was obtained. This polymer was dried, injection-molded and blow-stretched to obtain a hollow polyester container. The haze of the obtained polyester hollow container was 1.1, the intrinsic viscosity of the preform was 0.57, and the Col-b value was 3.

Examples 3 to 5 Polyester hollow containers were obtained by setting the polyethylene naphthalenedicarboxylate masterbatch used and the blending ratio as shown in Table 1. The quality of the obtained molded body was as shown in Table 1.

Comparative Example 2 A polyethylene naphthalene dicarboxylate polymer was obtained in the same manner as in Comparative Example 1 except that cobalt acetate tetrahydrate was added in a polycondensation step of 35 mmol% with respect to the acid component in order to improve the hue. . The quality when the obtained polymer was molded into a hollow container was as shown in Table 1.

Comparative Examples 3 to 6 Polyester hollow containers were obtained under the various conditions shown in Table 1. The quality of the obtained molded body was as shown in Table 1.

[0051]

[Table 1]

[0052]

The polyethylene naphthalenedicarboxylate hollow container of the present invention is excellent in hue and transparency, and becomes a bottle product having high commercial value.

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Claims (9)

[Claims] 1. Polyethylene naphthalene dicarboxylate containing an antimony element and / or a germanium element and a dye, excellent in hue, and having a body haze of 3
% Or less. 2. The hollow container according to claim 1, wherein the dye is a blue dye and / or a purple dye. 3. The hollow container according to claim 1, wherein the dye is an anthraquinone dye. 4. The polyester hollow container according to claim 1, wherein the content of the dye is in the range of 0.1 to 100 ppm. 5. A polyethylene naphthalenedicarboxylate containing an antimony element and / or a germanium element and a dye, having excellent hue and having a body haze of 3%.
% Or less, the method comprising dry blending a polyethylene naphthalenedicarboxylate masterbatch containing a dye and polyethylene naphthalenedicarboxylate and then molding the hollow container. 6. The polyethylene naphthalenedicarboxylate masterbatch has a dye content of 10 to 1000 pp.
The method for producing a hollow container according to claim 5, wherein m is m. 7. The method for producing a hollow container according to claim 5, wherein the polyethylene naphthalenedicarboxylate masterbatch containing the dye is a masterbatch obtained by melt-mixing the dye and the polyethylene naphthalenedicarboxylate by a reaction extruder. . Manufacturing method. 8. A masterbatch obtained by adding a dye to polyethylene naphthalenedicarboxylate in a melt polycondensation step when a polyethylenenaphthalenedicarboxylate masterbatch containing a dye is produced in the production of polyethylene naphthalenedicarboxylate. The method for producing a hollow container according to claim 5, wherein 9. The amount of the polyethylene naphthalenedicarboxylate masterbatch containing the dye is 0.5 to 0.5% based on the total amount of the polyethylene naphthalenedicarboxylate.
The method for producing a hollow container according to claim 5, wherein the content is 10 wt%.