JPH0491136A - Hygroscopic polyester molding - Google Patents

Abstract

PURPOSE:To obtain hygroscopic polyester moldings excellent in physical properties, moldability, hygroscopicity and antistatic properties, comprising a polyester and a coordinated complex of a metal halide and a polyalkylene oxide. CONSTITUTION:(B) 1-30wt.% coordinated complex of B1 and B2 which is obtained by dissolving B1: a metal halide (preferably magnesium chloride, lithium chloride or sodium iodide) having >=20%, preferably >=40%, especially preferably >=80% saturated rate of moisture absorption at 20 deg.C at 65% relative humidity and B2: a polyalkylene oxide (preferably polyethylene oxide) in solvents, respectively, blending and removing the solvents is blended with (A) a thermoplastic polyester (preferably polyethylene terephthalate) during or after polymerization reaction of the component A or before or during melt molding and molded to give hygroscopic polyester moldings.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a hygroscopic polyester molded article having excellent physical properties and processability.

(Prior Art) Polyester molded products are widely and commonly used in various forms including fibers and films due to their excellent properties.

However, such polyester molded articles are generally hydrophobic and therefore lack hygroscopic and antistatic properties.
There are fields that cannot be used. Particularly in the textile and film fields, this hydrophobic property is fatal.
The field of use is extremely limited.

Therefore, many proposals have been made to impart hygroscopicity and antistatic properties to polyester molded articles, but few have been put to practical use yet.

For example, in order to impart hygroscopicity,
As disclosed in Japanese Patent Publication No. 86 and Japanese Patent Application Laid-open No. 59-47480, a hydrophilic organic compound represented by polyalkylene oxide or polyalkylene glycol is added to polyester forming the fiber, and a hydrophilic organic compound typified by polyalkylene oxide or polyalkylene glycol is added to react and (
or) There are many proposals to mix them.

However, the hygroscopicity of the polyester fiber obtained by this method is not sufficient, and the physical properties such as strength of the obtained fiber are poor in practical use, and the excellent physical properties of the original polyester fiber are not sufficient. I had to sacrifice.

Furthermore, in order to impart hygroscopicity, a method of directly blending a highly hygroscopic metal inorganic compound such as calcium chloride or magnesium chloride into polyamide is also considered. However, the melting point of the inorganic metal compound used is generally several hundred degrees C higher than the melting point of polyester, and it does not melt during molding, resulting in poor uniformity of molded products and poor melt moldability, making it almost impractical. It was something.

[Problem to be solved by the invention]

An object of the present invention is to solve the above-mentioned problems of conventionally known polyester molded products and to provide a polyester molded product having excellent hygroscopicity.

[Means to solve the problem]

As a result of intensive study to achieve the above-mentioned purpose, Ki Oakisha et al. found that, as mentioned above, metal halides generally have 600
Since it has a high melting point of ~800°C, various difficulties arise when directly blending it into polyester. On the other hand, we discovered that these coordination complexes of metal halides and polyalkylene oxides have low melting points of 300°C or less, and we focused on the fact that direct blending with various polyesters can be advantageously carried out. This led to the invention.

That is, the present invention includes: Uj! containing a polyester (A) and a coordination complex (B) of a metal halide and a polyalkylene oxide having a saturated moisture absorption rate of 20% or more at 20°C and a relative humidity of 65%. It is a wet polyester molded product.

The present invention will be explained in detail below.

The hygroscopic polyester molded article of the present invention has a melting point below the processing temperature during polyester molding, which is approximately 300°C or below, so that the hygroscopic polyester molded article of the present invention has a melting point that is lower than the processing temperature during polyester molding. Can be melted. To this end, we provide a polyester molded product that is process-stable and has practical hygroscopicity without impairing the excellent physical properties inherent to polyester.

The metal halide constituting the metal complex (B) in the present invention has a saturated moisture absorption rate of 20% at 20°C and 65%RH.
It is necessary that it is above. Preferably 40% or more,
Particularly preferably, it is 80% or more.

To give specific examples, metal halides with a saturated moisture absorption rate of 80% or more include magnesium chloride, magnesium bromide, magnesium iodide, lithium chloride, lithium bromide, lithium iodide, zinc chloride, zinc bromide, Examples include zinc iodide, nickel bromide, and nickel iodide. Further, examples of the metal halide having a saturated moisture absorption rate of 40% or more include sodium iodide. Among these, magnesium chloride, lithium chloride, and sodium iodide are more preferred.
In addition, if the saturated moisture absorption rate is 20% or more and forms a coordination complex with polyalkylene oxide,
Any metal inorganic compound can also be employed.

On the other hand, if the saturated moisture absorption rate is less than 20%, in order to obtain a polyester molded product having practically sufficient moisture absorption rate and antistatic properties, the coordination complex (B) with polyalkylene oxide must be used.
must be added in an amount of 30% by weight or more to the polyester molded product, which significantly reduces the physical properties such as strength of the resulting polyester molded product, making it generally unsuitable for practical use.

The polyalkylene oxide constituting the metal complex (B) referred to in the present invention has repeating units of -CHR, -CHR,
-0 (However, R4 and R1 are H or a hydrocarbon.) Any material may be used as long as it can form a coordination complex with the metal halide mentioned above, but polyethylene oxide and polypropylene oxide are preferred. Preferred, particularly polyethylene oxide.

Moreover, the method for synthesizing the coordination complex referred to in the present invention is obtained by dissolving and mixing a metal halide and a polyalkylene oxide in their respective solvents, and then removing the solvent.

The solution Fl that can be used for synthesis varies depending on the type of metal halide and polyalkylene oxide and their combination, but ethanol and acetonitrile are preferable for the coordination complex of magnesium chloride polyethylene oxide, respectively.

The polyester (A) referred to in the present invention may be any thermoplastic polyester, but polyethylene terephthalate and polybutylene terephthalate are preferred, with polyethylene terephthalate being particularly preferred.

Note that, for example, it may be one in which polyethylene terephthalate is the main component and an isophthalic acid component is copolymerized, or one in which polybutylene terephthalate is copolymerized and/or mixed. That is, a polyester containing these as main components and copolymerized and/or mixed with other components, or even a mixture of these may be used without any problem.

The timing of blending this coordination complex (B) into the polyester molded product is during the early, middle, and early stages of the polymerization reaction for producing polyester.
The coordination complex (B) of the present invention in a polyester molded product may be used at a later stage, after polyester production, before or during melt molding.
Although the content is not particularly limited, it is generally preferably 1 to 30% by weight from the viewpoint of moldability and retention of physical properties.

If it is less than 1% by weight, the hygroscopicity is not sufficient. On the other hand, if it exceeds 30% by weight, it is not preferable because the physical properties will be significantly reduced and the processability will be poor.

In this polyester molded product, various additives such as dyes, pigments, fillers, lubricants, reinforcing agents, flame retardants,
Stabilizers, ultraviolet absorbers, etc. may be added.

This polyester molded product includes various fibers, their knitted fabrics,
It includes any form such as non-woven fabric, film, sheet (board), tube, etc.

The polyester molded article of the present invention comprises a polyester raw material (A
) and coordination complex (B) etc. by any molding or shaping means,
For example, it can be easily manufactured by spinning, stretch molding, extrusion molding, injection molding, compression molding, etc.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but these are not intended to limit the scope of the present invention.

In addition, in the examples, % means % by weight, and parts means parts by weight.

■Melting point; Measured using PerkinElmer DSC-4.

■ Moisture absorption rate (hereinafter abbreviated as MR); 20℃, 65%
This value was obtained by leaving the temperature in an RH constant temperature and humidity chamber (manufactured by Tabai, PR-2G) for 48 hours, and was calculated using the following formula.

(2) Frictional charging voltage of long fibers; Regarding the fibers, the frictional charging voltage was measured using the JIS L-1094B method. Moreover, the volume resistivity of the film was measured by JIS K-6911 method.

Example 1 6 parts of polyethylene oxide having a molecular weight of 1 million is dissolved in 200 parts of anhydrous acetonitrile. In addition, 4 parts of anhydrous magnesium chloride was dissolved in 40 parts of absolute ethanol, and after mixing the two, the solvent was removed, and the mixture was washed under reduced pressure (0.1 mHg).
, dried at 100°C for 48 hours to obtain magnesium chloride-polyethylene oxide with a melting point of 183°C and a molar ratio of 1:4 (however, in polyethylene oxide, 44 of its constituent units, CHZCHzO-, constituted 1 mole). A coordination complex was obtained. The synthesis of the magnesium chloride-polyethylene oxide coordination complex was conducted by L, L, and Yan.
It was carried out according to the literature of G et al. [J, Electroch
em, Soc, vol. 133, pp. 1380-1384 (
1986)] 10 parts of this coordination complex was blended with 90 parts of ordinary polyethylene terephthalate (η-/C = 0, 73; in a 1 wt% solution of orthochlorophenol at 35°C) during melt molding, and MR= 6.1%, long fiber (150 denier, 24 filaments) with frictional charging voltage of 1,600v, MR=6.5%, bulk exchange resistivity 8.5X
A 10'°Ω·l film (thickness 100μ) was obtained.

Example 2 8 parts of polyethylene oxide having a molecular weight of 1 million was dissolved in 480 parts of anhydrous methanol. Further, 2 parts of lithium chloride was similarly dissolved in 20 parts of methanol, and after mixing both, the solvent was removed to obtain a coordination complex of lithium chloride-polyethylene oxide.

15 parts of this coordination complex was blended with 90 parts of polyethylene terephthalate used in Example 1 during melt molding, and MR=8
．． Long fibers (150 denier, 24 filaments) with a friction charging voltage of 890 V and a friction charging voltage of 890 V were obtained.

Example 3 5.4 parts of polyethylene oxide having a molecular weight of 1 million was dissolved in 450 parts of anhydrous methanol. Further, 4.6 parts of sodium iodide was similarly dissolved in 50 parts of anhydrous methanol, and after mixing the two, the solvent was removed to obtain a sodium iodide-polyethylene oxide coordination complex.

10 parts of this coordination complex was blended with 90 parts of polyethylene terephthalate used in Example 1 during melt molding, and MR=2
．． 6%, long length 1II (150
denier, 24 filaments).

Example 4 5 parts of the coordination complex used in Example 1 were blended into 95 parts of polybutylene terephthalate (η-/c-1, 05; in a 1% by weight solution of orthochlorophenol at 35°C) when melted, A long fiber (150 denier, 24 filaments) with MR=6.5% and frictional charging voltage of 1.450 V was obtained.

Example 5 A coordination complex was obtained in the same manner as in Example 1 except that 6 parts of polyethylene oxide having a molecular weight of 140,000 was used. 5 parts of this coordination complex was melt-blended with 95 parts of polyethylene terephthalate used in Example 1, and MR=6.6%, 11! Long fibers (150 denier, 24 filaments) with a friction voltage of 1.200 V were obtained.

Example 6 A coordination complex was obtained in the same manner as in Example 1 except that 6 parts of polyethylene oxide having a molecular weight of 50,000 was used. Five parts of this coordination complex were melt-blended with 95 parts of polyethylene terephthalate used in Example 1 to obtain long fibers (150 denier, 24 filaments) with MR = 6.5% and Wl triboelectric voltage of 1,300 V.

Example 7 A coordination complex was obtained in the same manner as in Example 1 except that 6 parts of polyethylene oxide having a molecular weight of 20,000 was used. 5 parts of this coordination complex were melt-blended with 95 parts of polyethylene terephthalate used in Example 1, and MR=6.7% and frictional charging voltage 1
, 280v long fibers (150 denier, 24 filaments) were obtained.

Example 1 A coordination complex was obtained in the same manner as in Example 1, except that 6 parts of polyethylene oxide having a molecular weight of 6.000 was used. Five parts of this coordination complex were melt-blended with 95 parts of polyethylene terephthalate used in Example 1 to obtain long fibers (150 denier, 24 filaments) with MR = 6.4% and frictional charging voltage of 1.450V.

Example 9 A coordination complex was obtained in the same manner as in Example 1, except that 6 parts of polyethylene oxide having a molecular weight of J12,000 was used.

5 parts of this coordination complex was melt-blended with 95 parts of polyethylene terephthalate used in Example 1, MR=6.6%, and the length M1i1[! (150 denier, 24 filaments) was obtained.

Example 10 A coordination complex was obtained in the same manner as in Example 1, except that 6 parts of polyethylene oxide having a molecular weight of 1600 was used. Five parts of this coordination complex were melt-blended with 95 parts of polyethylene terephthalate used in Example 1 to obtain long fibers (150 denier, 24 filaments) with MR = 6.2% and frictional charging voltage of 1.800V.

Example 11 5 parts of the coordination complex used in Example 6 were melt-blended with 95 parts of polyethylene terephthalate used in Example], and then,
Solid phase polymerization was carried out at 200°C for 24 hours under nitrogen flow. After this, it was normally spun and drawn to obtain a long fiber (150 denier, 24
Got a filament date.

Comparative Example 1 40 parts of the coordination complex used in Example 1 and 60 parts of polyethylene terephthalate were blended during melt molding, but the moldability was poor (no long fibers or film were obtained).

Comparative Example 2 4 parts of anhydrous magnesium chloride used in Example I was added to Example 4.
It was added to 96 parts of the polybutylene terephthalate used in the above during melt molding, but the melt moldability was very poor and long fibers and films could not be obtained.

Comparative Example 3 The polyethylene terephthalate used in Example 1 was individually molded in the same manner as shown in Example 1, and the moisture absorption rate, frictional charging voltage, and volume surface resistivity were measured.

Comparative Example 4 The polybutylene terephthalate used in Example 4 was individually molded in the same manner as shown in Example 4, and the UXI humidity, frictional charging voltage, and specific volume resistivity were measured.

The moisture absorption rate, frictional charging voltage, and specific volume resistivity of Comparative Examples 3 and 4 are shown in Table 1.

Comparative Example 5 0.5 part of the coordination complex used in Example 1 was blended with 99.5 parts of polyethylene terephthalate used in Example 1 during melt molding, and a long fiber (150 denier, 24 filaments) were obtained.

The results are also shown in Table-1.

(Effects of the invention) In the present invention, moisture absorption (control t) for polyester molded products is provided.
As an agent, a metal halide, which has high hygroscopicity but lacks meltability and compatibility with polyester, is blended into polyester in the form of a coordination complex with polyalkylene oxide. Due to the significantly lowered melting point, polyester molded articles with excellent moldability, hygroscopicity, and antistatic properties can be obtained.

(1 other person)

Claims (1)

[Claims] A polyester (A) and a coordination complex (B) of a metal halide and polyalkylene oxide having a saturated moisture absorption rate of 20% or more at 20°C and 65% relative humidity. , hygroscopic polyester molded product.