JPH02238055A - Moisture absorbing molded resin product - Google Patents

Abstract

PURPOSE:To obtain a moisture absorbing molded resin product excellent in physical properties and moldability by blending a coordination complex of a highly moisture absorbing metal halide with a polyalkylene oxide with a synthetic resin. CONSTITUTION:A moisture absorbing molded resin product, obtained by blending (A) a coordination complex prepared by dissolving (A1) a metal halide (preferably magnesium chloride, lithium chloride or sodium iodide) having >=20%, preferably >=40%, especially >=80% saturation moisture absorptivity at 20 deg.C and 65% relative humidity and (A2) a polyalkylene oxide (preferably polyethylene oxide) in respective solvents, mixing the resultant solutions and removing the solvents with (B) a synthetic resin (preferably polyolefin, polyester, etc.) before, during, after polymerization reaction for producing the component (B) or melt molding, etc., and containing 1-30wt.% component (B).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hygroscopic resin molded article having excellent physical properties and moldability. [Prior Art] Synthetic resin molded products are widely and commonly used in various forms, including fibers and films, due to their excellent properties. However, such resin molded products are generally hydrophobic;
Therefore, it lacks hygroscopicity and antistatic properties and cannot be used in some fields. Particularly in the field of Ta fibers and films, this hydrophobic property is fatal and the field of use is extremely limited.

Therefore, many proposals have been made to impart hygroscopic and antistatic properties to resin molded products, but few have been put to practical use yet. For example, in order to impart hygroscopicity to polyester fibers, Japanese Patent Laid-Open No. 47-2948
No. 6 and Japanese Patent Application Laid-Open No. 59-47480, a hydrophilic organic compound typified by polyalkylene glycol is added to the polyester forming the fiber, and then reacted and/or mixed. Many things have been proposed. However, the hygroscopicity of the polyester fibers obtained by this method is not sufficient, and the physical properties such as strength of the obtained fibers are not practical, and the superior properties of the original polyester fibers are insufficient. Physical properties had to be sacrificed. Furthermore, in order to impart hygroscopic properties, a method of directly blending a highly hygroscopic metal inorganic compound into the resin is also considered. However, the melting point of the inorganic metal compound used is
Generally, the melting point is several hundred degrees C higher than the melting point of the resin, and it does not melt during molding, resulting in poor transparency and uniformity of molded products, poor melt moldability, and almost no practical use. [Problems to be Solved by the Invention] It is an object of the present invention to solve the above-mentioned problems of conventionally known resin molded products and to provide a resin molded product having excellent hygroscopicity. [Means for Solving the Problems] As a result of intensive studies to achieve the above-mentioned object, the present inventors found that, as mentioned above, metal halides generally contain 60
Since it has a high melting point of 0 to 800°C, there are various difficulties when directly blending it into resins. On the contrary,
They discovered that these coordination complexes of metal halides and polyalkylene glycols have a low melting point of 300°C or less, and realized that they can be advantageously blended directly with various resins, and completed the present invention. This is what led to this. That is, the present invention is a hygroscopic resin molded article containing a synthetic fat-soluble resin and a coordination complex of a metal halide and a polyalkylene oxide having a saturated moisture absorption rate of 20% or more at 20° C. and 65% RH.

In the hygroscopic resin molded article of the present invention, the coordination complex hygroscopic (antistatic) agent has a melting point below the processing temperature during resin molding, approximately 300 yen
Because it has a melting point below ℃, it can be melted at the molding temperature of the resin, so it has good transparency, is stable in terms of process, and has practical hygroscopicity without impairing the excellent physical properties of the resin. We provide molded products. The metal halide referred to in the present invention is 20°C, 65%R
It is necessary that the saturated moisture absorption rate in H is 20% or more. Preferably 40% or more, particularly preferably 80%
That's it. Specific examples include magnesium chloride, magnesium bromide, magnesium iodide, lithium chloride, lithium bromide, lithium iodide, zinc chloride, zinc bromide, zinc iodide, and magnesium chloride with a saturated moisture absorption rate of 80% or more. These include nickel oxide and nickel iodide. Further, examples of metal halides 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, the saturated moisture absorption rate is 2
Any metal inorganic compound can be used as long as it has a content of 0% or more and forms a coordination body with the polyalkylene oxide. On the other hand, if this saturated moisture absorption rate is less than 20%, in order to obtain a resin molded article with practically sufficient moisture absorption rate and antistatic properties, it is necessary to apply a coordination complex with polyalkylene oxide to the resin molded article. , must be added in an amount of 30% by weight or more, and if this is done, the physical properties such as strength of the resulting resin molded product will be significantly reduced, making it generally unsuitable for practical use. The polyalkylene oxide referred to in the present invention means that the repeating unit is -CIIRI-CHRI-0
- (However, R+..Rx is 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 can be used. are preferred, and among these, polyethylene oxide is preferred.

Furthermore, 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.

Solvents that can be used in the synthesis vary depending on the type of metal halide and polyalkylene oxide and their combination, but ethanol and acetonitrile are preferred for the magnesium chloride-polyethylene oxide coordination complex, respectively. Furthermore, the resin referred to in the present invention may be any thermoplastic resin, including polyolefins such as polyethylene and polypropylene, polystyrene, polyacrylonitrile, and polyesters such as polyethylene terephthalate and polybutylene terephthalate. and/or polyamides such as nylon 6 and nylon 66 are particularly preferred. It should be noted that there is no problem with resins containing these as main components and copolymerized and/or mixed with other components, or even mixtures thereof. The coordination complex may be added to the resin molded product before, during, or after the polymerization reaction for producing each resin, or after resin production, before or during melt molding. In addition, the content of the coordination complex of the present invention in the resin molded product is not particularly limited, but from the viewpoint of moldability and retention of physical properties,
Generally, 1 to 30% by weight is preferred. If it is less than 1% by weight, hygroscopicity is not sufficient. However, if the purpose is to impart antistatic properties to resin molded products, sufficient performance can be obtained with a blending amount of 0.1% or more. On the other hand, if it exceeds 30% by weight, it is undesirable because the physical properties deteriorate significantly and transparency and moldability become poor. If necessary, various additives such as dyes, pigments, fillers, lubricants, reinforcing agents, flame retardants, stabilizers, and ultraviolet absorbers may be added to this resin molded article. This resin molded product includes various fibers, their knitted fabrics, non-collared fabrics,
It includes any form such as film, sheet (board), tube, etc. The resin molded article of the present invention can be easily produced from a resin raw material and a coordination complex by any molding or shaping method, such as spinning, stretch molding, extrusion molding, injection molding, or compression molding. [Examples] Hereinafter, the present invention will be specifically explained using Examples, but these are not intended to limit the scope of the present invention. % in examples
is an abbreviation for % by weight, and part is an abbreviation for parts by weight. ■Melting point: Measured with PerkinElmer DSC-4. ■Moisture absorption rate (
(hereinafter abbreviated as MR); 20°C, 65% RH constant temperature and humidity chamber (manufactured by Tabai, PR-2
This is the value obtained by leaving it for 48 hours in G> and was calculated using the following formula. Weight of bone-dried molded product ■Frictional charging voltage of long fibers; For fibers, use JIS L-1094B method, and for film specific volume resistivity, use JIS K
Measured using the -6911 method. Example 1 6 parts of polyethylene oxide with a molecular weight of 3 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 both, the solvent was removed, and further 10 parts of anhydrous magnesium chloride was dissolved under reduced pressure (1 mmHg).
Dry at 0°C for 48 hours, melting point 183°C, molar ratio 1:
A magnesium chloride-polyethylene oxide coordination complex of 4 (1 mole was defined as 44 of CHzCHtO-, which is a constituent unit of polyethylene oxide) was obtained.

The synthesis of the magnesium chloride-polyethylene oxide coordination complex is described by L. The procedure was carried out according to the literature of L., Yang et al. (J. Electrochem, Soc, vol.13
3, pp. 1380-1384, (1986)] 10 parts of this coordination complex was mixed with ordinary polyethylene terephthalate (ηsp/c=0.73, orthochlorophenol 1
It was blended into 90 parts of 35°C (weight% solution) at the time of melt molding, MR = 6.1%, and a long fiber with a frictional charging voltage of 1500V (
150 denier, 24 filaments) and MR=6.
A film (thickness: 50 μm) with a specific volume resistivity of 7.9×10”Ω·cm and a volume resistivity of 3% was obtained.

Example 2 20 parts of the coordination complex used in Example 1 was added to ordinary nylon 6
(ηr=2.43, 98% H, So. 1% by weight solution,
25°C) and 80 parts at the time of melt molding, MR = 1
Long fibers (70 denier, 20 filaments) with a friction charge voltage of 1,600 V and a friction charge voltage of 5.2% were obtained. Example 3 Example! 15 parts of the coordination complex used in MR-9. was blended with 85 parts of ordinary polypropylene (MFR = 4.5 g/10 min, according to JISK-6758 method) during melt molding.
A film (thickness: 50 μm) with a volume resistivity of 0% and a volume resistivity of 8.6×10”Ω·cm was obtained. However, MFR is an abbreviation for melt flow index (MeltF 1 ow Rate). Example 4 Implementation 10 parts of the coordination complex used in Example 1 were added to ordinary polystyrene (MFR=7.5g/10min, 5Kg, 200'C)
Example 5 10 parts of the coordination complex used in Example 1 was added to 0 parts during melt molding to obtain a plate with an MR of 6.8% and a volume resistivity of 6.4XlO''Ωcm. of polymethyl methacrylate (VFR=5.1g/10min, 10Kg,
200°C) at the time of melt molding, and MR-7.
A plate with a specific volume resistivity of 4.2 x 10" Ωcm was obtained. Example 6 8 parts of polyethylene oxide with a molecular weight of 3 million was dissolved in 480 parts of anhydrous methanol. Also, 2 parts of lithium chloride was dissolved in the same solution. After dissolving in 20 parts of methanol and mixing the two, the solvent was removed to obtain a coordination complex of lithium chloride and 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 950 V and a friction charging voltage of 7% were obtained.

Example 7 5.4 parts of polyethylene oxide with a molecular weight of 3 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 mixed with polymethyl methacrylate (PMM).
In A), a long fiber having an MR of 2.3% and a frictional charging voltage of 950 V was obtained in the same manner as in Example 1.

Comparative Example 1 Although 35 parts of the coordination complex used in Example 1 and 65 parts of polyethylene terephthalate were blended during melt molding, moldability was poor and long fibers and films could not be obtained. Comparative Example 2 4 parts of anhydrous magnesium chloride used in Example 1 was blended with 6.96 parts of polyester and nylon during melt molding, but the moldability was very poor and no long fibers or film were obtained. Comparative Examples 3 to 5 The polyethylene terephthalate, nylon 6, and polypropylene used in Examples 1 to 3 were molded in the same manner as in Examples 1 to 3, and the moisture absorption rate, frictional charging voltage, and specific volume resistivity were measured. The moisture absorption rate, frictional charging voltage, and volume resistivity of Comparative Examples 3 to 5 are shown in Table 1. Comparative Example 6 0.5 part of the coordination complex used in Example 5 was blended with 99.5 parts of polyethylene terephthalate used in Example 1 during melt molding, and a long fiber (150 denier, 24 filament) was obtained.

The results are also shown in Table 1. [Effects of the Invention] In the present invention, metal halides, which have high hygroscopicity but lack meltability and compatibility with resins, are used as hygroscopic (antistatic) agents for resin molded products in combination with polyalkylene oxides. Since it is blended into the resin in the form of a coordination complex, the melting point of this coordination complex is significantly lowered, resulting in a resin molded product with excellent moldability, hygroscopicity, and antistatic properties. .

(1 other person) Procedural amendment May 1, 1990

Claims (1)

[Claims] characterized by containing a synthetic resin and a coordination complex 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%,
Hygroscopic resin molded product.