JPS59117541A - Manufacture of molded article of antistatic polymer - Google Patents

Abstract

PURPOSE:To impart remarkable antistaticity and excellent durability to a molded article of a polymer containing sulfonic acid group, without lowering the moldability and physical properties, by treating the molded article with a polyalkylene oxide compound containing reactive group. CONSTITUTION:A molded article made of a polymer containing sulfonic acid group and/or its metallic salt in the molecular chain (preferably a polyester or polyamide having an alkali metal-5-sulfoisophthalate component as a copolymerized component) is treated is treated with a polyalkylene oxide compound having a quaternary ammonium structure. The amount of the sulfonic acid group in the polymer is >=10 equivalent/ton and preferably <=500 equivalent/ton. The molded article is preferably fiber or film.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polymer molded article with excellent antistatic properties, in which the molded body is treated with a polyalkylene oxide compound having a quaternary ammonium structure.

fiber. Many proposals have been made to make polymer molded products such as films antistatic, and some have even reached the stage of commercialization. Many of these use polyalkylene oxide-based compounds as antistatic agents, and the common method is to blend them with polymers or treat the surface of polymer moldings, but the former has problems with moldability and moldability. This can easily lead to a decline in the physical properties of objects.

The latter has problems such as a lack of durability in antistatic performance.

As a result of various studies on methods for antistaticizing polymer molded articles, the present inventors found that by treating a molded article made of a polymer having a sulfonic acid group as described above with a polyalkylene oxide compound having a reactive group. , I learned that the above-mentioned drawbacks were resolved and that remarkable antistatic properties and excellent durability were realized.

This has led to the present invention.

That is, the present invention provides an antistatic polymer characterized in that a molded article made of a polymer having a sulfonic acid group or/and a metal salt thereof in its molecular chain is treated with a polyalkylene oxide compound having a quaternary ammonium structure. The gist of this paper is a method for manufacturing a composite molded product.

In the present invention, the polymer having a sulfonic acid group or/and its metal salt in its molecular chain includes a copolymer obtained by adding a polymerizable monomer having a sulfonic acid group during its synthesis, and a copolymer obtained after the completion of the polymerization reaction. There are polymers obtained by sulfonation treatment in any step. Preferred specific examples include: (1) polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, etc. whose copolymerization component is a 5-alkali metal (sodium or potassium) sulfoisophthalate component, and polymers containing these as main components; ■Copolymers obtained by adding allyl sulfonic acid, styrene sulfonic acid, etc., and their metal salts during polymerization of acrylonitrile; ■Copolymers obtained by sulfonating polypropylene with chlorosulfonic acid, and these are known. manufactured by the method. Particularly preferred are polyesters or polyamides mentioned above in view of their versatility. And the amount of sulfonic acid groups in the dipolymer is
From the point of view of the expression of antistatic effect by the subsequent treatment reaction, the amount should be 10 equivalents/ton or more, preferably 20 equivalents/ton or more, but in consideration of moldability and physical properties of the molded product, it should be 500 equivalents/ton or less. It is preferable that there be.

The molded product applied in the present invention is preferably in a fibrous or film-like shape from the viewpoint of operability during processing, but it is of course possible to use other shapes.

Next, in the present invention, a polyalkylene oxide compound having a quaternary ammonium structure refers to a compound whose main component is a polyalkylene oxide component such as polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer, etc. Refers to a compound having a quaternary ammonium structure at the end of the molecular chain, and is represented by the following general formula (R1-R4: hydrogen atom or monovalent organic group, at least one of which is a polyalkylene oxide chain A.X:
Halogen (CI, Br, I), fatty acid group, sulfonic acid group, sulfate group, alkyl sulfate group.

Indicates a phosphate or borate group. n: An integer depending on the valence of X. ) The structure represented by the following is the basic skeleton (it goes without saying that one molecule may have a plurality of quaternary ammonium structures). Typical examples include: ■ A compound obtained by adding an alkylene oxide to a -class amine or a secondary amine and then converting it into a quaternary ammonium; ■ A compound obtained by adding acrylonitrile to a polyalkylene oxide having hydroxyl groups at both ends and cyanoethylating it. , which is further reduced and then converted into quaternary ammonium compounds, which can be produced using known formulations. These compounds have a molecular weight of 200 to 10
000. It is preferably 300 to 8,000, and is appropriately selected depending on the type of the sulfonic acid group-containing polymer, the treatment method, etc.

The method of the present invention is based on treating a molded product such as a fiber or film made of a sulfonic acid group-containing polymer with a polyalkylene oxide compound having a quaternary ammonium 5-nium structure. Such processing can be performed by a known method. For example, in the case of fiber,■
A method of applying a liquid containing the compound to the undrawn fiber yarn after spinning and carrying out drawing and heat treatment simultaneously or separately; ■ A method of applying the liquid to the drawn yarn and heat-treating it; ■ Adhesion during false twisting 9
Reaction treatment method; ■Method of treating cloth after weaving and before dyeing.

(2) A method in which the compound is added to the staining solution and dyeing and reaction treatment are carried out simultaneously, (2) A method in which reaction treatment is carried out after dyeing, etc. may be adopted. The reaction treatment conditions are appropriately adjusted depending on the characteristics of the polymer molded product, the molecular size of the polyalkylene oxide compound, and the like.

Hereinafter, the present invention will be explained in more detail with reference to Examples. The antistatic property in the examples was measured using a rotary static tester of the Kaken type at 9 Kyoto University.
, in an atmosphere of 40% RH, using cotton cloth as a friction body to determine the frictional charging voltage and charge half-life. Note that "parts" means parts by weight.

6- Example I N, N, N-tris(polyoxyethylene)-N-
Lauryl ammonium chloride (molecular weight 1200) 14
1 part was dispersed in 86 parts of a spinning oil solution.

36f of the 5-sodium sulfoisophthalic acid component running down from the melt spinneret under conditions of a coating amount of 10 cm.
While feeding the molar copolymerized polyethylene terephthalate yarn, the yarn was wound up to 1200271/4 inches.

Next, the yarn was drawn under conditions such as a drawing roller temperature of 90° C., a heat plate temperature of 160° C., and a drawing ratio of 3.3 times for 2 hours and 2 seconds to obtain a drawn yarn of 75 d/36 f.

This drawn yarn has a warp of 110 pieces/2.54 crn and a weft of 100 pieces.
The fabric was woven into taffeta with a weave density of 72.54 m, and after dry heat treatment at 150°C for 10 minutes, it was woven in a bath containing blue disperse dye.
Staining was carried out at 20°C for 30 minutes.

The frictional charging voltage and half-life of the dyed cloth are each 700V.

9 seconds, and this performance hardly decreased even after washing 30 times.

Examples 2 to 4 Polyethylene terephthalate fiber (75d/36
f) taffeta with blue disperse dye 2% owf and first
13 in a dye bath containing 5% owf of the compounds listed in the table.
It was treated at 0°C for 30 minutes.

The results of measuring the antistatic properties of the obtained dyed fabric were confirmed to have the effects of the present invention, as shown in Table 1, Example No.

Table 1 Comparative Example 1 The same operation as in Example 1 was performed on a polyethylene terephthalate yarn containing no 5-sodium sulfoisophthalate component, but the frictional charging voltage and half-life of the dyed fabric were 3000 V and 100 V, respectively. It was more than a second.

9- Comparative Example 2 In Example 3, when polyethylene oxide with a molecular weight of 1000 (hydroxyl groups at both ends) was used as the polyalkylene oxide compound, the dyed fabric had a frictional charging voltage of 3
000v and a half-life of 100 seconds or more.

Patent applicant: Takeo Sanae 2 others 310-year-old male child

Claims (2)

[Claims] (1) Antistatic polymer molding characterized by treating a molded product made of a polymer having a sulfonic acid group or/and its metal salt in its molecular chain with a polyalkylene oxide compound having a quaternary ammonium structure. How things are manufactured. (2) The method for producing an antistatic polymer molded article according to claim 1, wherein the polymer is a polyester or polyamide containing an alkali metal-5-sulfoisophthalic acid component as a copolymerization component.