JPS6020963A - Antistatic polymer composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having durable antistatic properties imparted thereto without detriment to inherent physical properties, by blending a given amount of a specified vinyl polymer with a thermoplastic polymer. CONSTITUTION:A vinyl polymer composed of at least 0.1mol% of a monomer unit (a) consisting of an unsaturated vinyl compd. having a polyoxyalkylene chain having an average MW of 200-5,000 (e.g. a polyoxyalkylene glycol acrylate), at least 1mol% of a monomer unit (b) consisting of an unsaturated vinylsulfonic acid (salt) (e.g. styrenesulfonic acid) and 0-98.9mol% of other unsaturated vinyl compd. (c) (e.g. vinyl acetate), is used. Said vinyl polymer is blended with a thermoplastic polymer such as a polyester in such an amount that the amount of the monomer unit (a) accounts for 0.1-10wt% of the entire compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition that does not impair the excellent physical properties of the original thermoplastic polymer and has excellent antistatic properties.

In general, hydrophobic polymeric substances are easily charged with electricity due to friction, peeling, etc., and this charging causes various problems in molded products, and also has drawbacks such as causing shock due to discharge during use, and causing dust to adhere. ing. In order to eliminate these drawbacks, methods have been proposed in which an antistatic agent is pressure-adhered to the surface of the molded product or mixed into the molded product.

Among the above proposals, the method of blending an antistatic agent into a polymeric substance is known as a relatively durable method. For example, a method of blending a polyoxyalkylene glycol into a thermoplastic polymer such as polyethylene terephthalate has been disclosed. However, in order to obtain polyester molded products such as fibers and films with sufficient antistatic performance by employing the above method, it is necessary to blend polyoxyalkylene glycol in an amount exceeding 10 parts by weight. However, there are disadvantages such as the formability of fibers or films is significantly reduced, and the physical properties of the obtained fibers and films, especially the stability of dyed products against light, are extremely poor. As a method, polyoxyalkylene glycol is blended by using polyethylene glycol insoluble in polyester and having an average molecular weight of 10,000 to 30,000, and further using a low-molecular compound containing a sulfonic acid metal salt such as sodium dodecylbenzenesulfonate. Methods for reducing the amount have been proposed in Japanese Patent Publication No. 44-31828, Japanese Patent Publication No. 46-42629, etc. However, even with such methods, it is still possible to achieve both excellent antistatic properties and the physical properties inherent to polyester. Therefore, in order to obtain excellent antistatic properties, physical properties must be sacrificed, and conversely, if priority is given to physical properties, the antistatic properties will not be satisfactory, especially the durability of the antistatic properties. The drawback is that you only get what you lack.

In view of the above-mentioned circumstances, the present inventors conducted extensive research and study in order to obtain a composition that does not impair the excellent physical properties of the original thermoplastic polymer and has excellent antistatic performance. We have finally completed the present invention. That is, the present invention
The thermoplastic polymer (A) has an average molecular weight of 200 to 5000.
A monomer unit consisting of an unsaturated vinyl compound containing a polyoxyalkylene chain (a) of 0.1 mol or more, a monomer unit consisting of a vinyl unsaturated sulfonic acid or a salt thereof (
b) A monomer unit consisting of 1 mole or more and another unsaturated vinyl compound (c) A vinyl polymer (B) having a constitutional unit of 0 to 98.9 mole This is an antistatic polymer composition characterized in that it is blended in an amount of 0.1 to 10% by weight based on the total composition.

The thermoplastic polymer used in the present invention is typically polyester. Polyester means a linear polymer polymerized from a dibasic acid and a dihydric alcohol or from an oxycarboxylic acid, or a copolymer thereof. Examples include polyesters obtained from glycols. Polyamides are also suitable. Here, polyamide refers to a polymer of monoaminocarboxylic acid, a polymer obtained by polymerizing diamine and dicarboxylic acid, or a copolymer thereof. Others, polyethylene,
It can also be applied to olefinic polymers such as polypropivine, vinylic polymers such as polyvinyl chloride, poly, methyl methacrylate, etc.

Next, in the present invention, the vinyl polymer (B) to be blended with the thermoplastic polymer (A) has an average molecular weight of 200 to 50.
A monomer unit consisting of an unsaturated vinyl compound containing 00 polyoxyalkylene chains (a) 0.1 mole or more and a monomer unit consisting of a vinyl unsaturated sulfonic acid or a salt thereof (b) 1 mole or more It is a polymer that contains as an essential structural unit and, if necessary, other unsaturated vinyl compounds as structural units. Here, as the unsaturated vinyl compound (a) containing a polyoxyalkylene chain, esters such as acrylic ester or methacrylic ester of polyoxyalkylene glycol, itaconic ester, acrylamide, N-substituted methacrylamide, polyoxy Examples include alkylene glycol mono(meth)allyl ether. The average molecular weight of the polyoxyalkylene chain of the monomer unit is 200 or more, preferably 4
00 or more and 5000 or less. If the average molecular weight is less than 200, the antistatic effect will be small, and when formed into fibers, it will be unsuitable because it will cause long-term spinning operability, especially an increase in nozzle back pressure during spinning. On the other hand, if the average molecular weight exceeds 5,000, the polymerization rate decreases during polymerization of the vinyl polymer (C), and the vinyl polymer cannot be obtained efficiently, which is not preferable. The polyoxyalkylene chain may be, for example, polyoxyethylene glycol, polyoxypropylene glycol, polytetrahydrofuran, or a copolymer thereof, preferably containing an oxyethylene unit, or fragments of these polyoxyalkylene chains. The terminal is -01 (even if it is a group, there is no problem even if it is bonded to other organic groups other than polymerizable unsaturated groups through ether bonds, ester bonds, etc.) From vinyl unsaturated sulfonic acid or its salt Examples of the monomer (b) include unsaturated hydrocarbons and salts thereof such as styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, (meth)allylsulfonic acid; (meth)acrylic acid sulfoethyl ester; Sulfoalkyl esters of acrylic acid or methacrylic acid, such as (meth)acrylic acid sulfobutyl ester and (meth)acrylic acid sulfoprobyl ester, or salts thereof; 2-acrylamide-
Examples include 2-methylpropanesulfonic acid or its salts, and in the present invention, styrenesulfonic acid,
Those having an aromatic ring such as vinylbenzyl sulfonic acid or a salt thereof are preferred. Moreover, as the vinyl unsaturated sulfonate, alkali metal salts and alkaline earth metal salts are preferable.

The vinyl polymer (C) is a monomer consisting of the above-mentioned vinyl unsaturated sulfonic acid or its salt (b) and an unsaturated vinyl compound containing a polyoxyalkylene chain (a), as well as other monomers. Polymerizable unsaturated vinyl monomer ()・
) may be contained as a copolymerization component Other polymerizable non-flLl vinyl monomers include conjugated diene monomers such as butadiene and isoprene, 1 styrene, α-methylstyrene, chlorostyrene, etc. Aromatic vinyl monomers; esters of vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; acrylamide, methacrylamide or their N-alkyl substituted products: vinyl chloride, vinyl bromide, vinylidene chloride, bromide Examples include vinyl halides such as vinylidene; vinyl esters such as vinyl acetate and vinyl propionate; these monomers may be used alone or in mixtures. The vinyl polymer (B) contains a monomer unit (b) consisting of a vinyl unsaturated sulfonic acid or a salt thereof in its constituent units at 1 molti or more, preferably 5 molti or more and less than 90 molti. It is desirable to be present. If the monomer unit is less than 1 mole, sufficient antistatic performance cannot be obtained.

Further, if the amount exceeds 90 molt, the spinning properties will deteriorate when forming into fibers, etc., which is not preferable.

Furthermore, the vinyl polymer CB) is an unsaturated vinyl compound containing a polyoxyalkylene chain in its constituent units (
It is necessary to contain at least 1 mol, preferably 1 mol, or more of the monomer consisting of (b).0 It is only by containing 0.1 mol or more of the monomer that an excellent improvement in the antistatic effect can be seen, and also for a long period of time. Improvements are also made in the fiber formability and increase in nozzle back pressure during special trap spinning.

Note that any method can be used to obtain the vinyl polymer (B), such as ordinary radical addition polymerization such as emulsion polymerization, suspension polymerization, and solution polymerization, and ionic polymerization. . In addition to these methods, it is of course possible to adopt a method of introducing the monomer units by sulfonating the vinyl polymer.

Vinyl polymer (B) having the above structure in the present invention
is 0.1 to 10% by weight, preferably 0.5 to 10% by weight, based on the entire composition as a monomer unit consisting of an unsaturated vinyl compound containing a polyoxyalkylene chain, which is the structural unit.
The content must be 7% by weight. If the monomer unit is less than 0.1 double unit, effective antistatic properties cannot be obtained, and if the monomer is increased by more than 10% by weight, the light resistance of the resulting composition decreases. So I don't like it.

In the present invention, any method can be used to blend the vinyl polymer (B) into the thermoplastic polymer (A). For example, a method in which a vinyl polymer (B) is applied to a film, fiber, or knitted fabric made of a thermoplastic polymer (A), or a method in which a vinyl polymer (B) is blended with a thermoplastic polymer (A) Methods can be mentioned, but in order to impart sufficient durable antistatic properties, a method of blending a vinyl polymer (B) with a thermoplastic polymer (A) is preferred.0Thermoplastic polymer (A) K vinyl polymer (B
) As a method of blending Th, thermoplastic synthetic polymer (A
) may be mixed during the synthesis, or after the synthesis is complete, the molten (
A method of adding and stirring the vinyl polymer (B) to A),
The pellets of (A) and (B) are stirred and mixed in an extrusion molding machine or a spinning machine, or a so-called master chip with a high mixing ratio of antistatic components is made by such a method, and this is used as required. Examples include a method of mixing with a chip consisting of the amount (A) before molding.

Further, the composition of the present invention may contain other optional additives such as antioxidants, ultraviolet absorbers, flame retardants, pigments, etc., but this does not impede the effects of the present invention in any way.

As described above, the composition of the present invention having such a structure maintains extremely excellent antistatic performance semi-permanently, incomparably with conventional compositions, and also maintains excellent antistatic performance of the target thermoplastic polymer. The composition does not impair its physical properties and in particular has good sunlight stability of the dyed product, and the various problems caused by electrostatic charge that have hitherto been troubled can be solved at once. Furthermore, the composition enables stable operation over a long period of time when formed into fibers, films, sheets, etc. according to conventional methods,
It has extremely high industrial value.

EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is of course not limited to the following Examples.

It should be noted that the percentages and parts shown in the examples are based on the amount of M unless otherwise specified.

The half-life and light resistance of the following examples were measured by the following methods.

(1) Half-life: The filaments obtained by melt spinning are knitted into a stockinette knitted fabric. After the silk fabric is scoured and air-dried in a conventional manner, it is preset at 160°C for 1 minute, and then measured using a static honest meter. (manufactured by Shishido Shokai) and applied a voltage of 10 KV for 30 seconds, and the relative humidity was 50.
q6. Its half-life was measured at 20°C. The durability of the antistatic property was determined by washing the above knitted fabric in a household washing machine with an aqueous solution of 0.5 f/neutral activator at 40°C for 20 minutes.
Wash with hot water for 5 minutes at 0°C, then wash with overflow water for 20 minutes.
After that, it was dehydrated and dried at 60°C for 30 minutes. Evaluation was made by measuring the half-life of the sample after repeating this operation. In addition, the half-life measured by the above method is 100
If it was less than 2 seconds, it was determined that it had antistatic properties.

(2) Sub-light property: Resolin blue FBL (manufactured by Bayer AG, dispersible dye) 1
The dyed knitted fabric was dyed with a dye solution of %owf at 130° C. for 1 hour in a conventional manner, and then subjected to reduction washing and irradiated for 40 hours using a fade meter.The degree of discoloration was evaluated by grading it on a blue scale.

Example 1 Methoxypolyethylene glycol (30 mol) monoallyl ether (written as PEG(ao)・AE) 85
Part and p-styrene sulfonate (SPSS) 1
5 parts and a redox catalyst (potassium persulfate-acidic sodium sulfite) in an aqueous system to obtain an aqueous solution of the heel vinyl polymer (B). The obtained aqueous polymer solution and ethylene glycol are mixed and heated to remove water and produce a vinyl polymer (
B) and ethylene glycol mixture obtained gold. Using this mixture and terephthalic acid, polyethylene terephthalate r and B were combined according to a conventional method to obtain polyethylene terephthalate (polyethylene terephthalate) /
(B) A composition consisting of -97/3 was obtained (2.55% of PEG (30)-AEid was contained in the composition).
After drying the obtained composition according to a conventional method, using a spinneret having 24 spinning holes with a hole diameter of 0.3 using a test spinning method, the composition was discharged for 7 minutes at a spinning temperature of 280°C and a winding speed of t3oom. /min. After 5 days, the nozzle back pressure increased to 1.3 ky/cA, indicating good spinning properties. Thereafter, the filament was drawn, knitted, and its half-life and light resistance were measured.

The half-life is 6.3 seconds after one wash, and 6.3 seconds after washing f7420 times.
．． 9. seconds, and the light resistance was good at 4 to 5R, indicating excellent durable antistatic properties and light resistance.

Examples 2 to 6, Comparative Examples 1 and 2 Polyester filaments were obtained in the same manner as in Example 1, except that the vinyl polymer (B) used in Example 1 had the composition shown in Table 1. The antistatic property (half-life) and light resistance of the obtained filament were measured, and the results are shown in Table 1.

Table 1 (However, in Comparative Example 2, yarn breakage occurred frequently and samples could not be obtained.) As is clear from Table 1, the unsaturated vinyl compound containing polyoxyalkylene chains in the vinyl polymer was 0.
．． It can be seen that 1 mole or more is suitable for the vinyl unsaturated sulfonic acid or its salt.

Examples 7-10. Comparative Examples 3 and 4 Same as Example 1 except that the content of the vinyl polymer CB) used in Example 1 was changed and the amount of PEG (30)/E in the composition was changed to the amount shown in Table 2. A polyester filament was obtained using this method. The half-life and light resistance of the obtained filaments were measured, and the results are shown in Table 2.

Table 2 It is found that 0.1 to 10 weight 1i% is appropriate for the report.

Example 11 Example 1 except that instead of the vinyl polymer (B) used in Example 1, a vinyl polymer having a composition of KP group (30)AE/5PSS/5t=7015/25 weight ratio was used. A polyester filament was obtained in the same manner. The half-life of the obtained filament after 20 washes was 5.5 seconds, and the secondary lightness was grade 4-5.

Example 10 Nylon 6 chips and the vinyl polymer obtained in Example 1 were thoroughly mixed in a ratio of nylon 6/(B) = 98/2, and kept in an extruder. Melt extrusion spinning. Obtained t: The half-life of the filament was 8.7 seconds, and the light resistance was grade 4 to 5. However, the light resistance was Sol.
A sample dyed with waY Blue B (manufactured by IC1, an acid dye) was evaluated.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Claims] (1) The thermoplastic polymer (A) has an average molecular weight of 11,200
Monomer unit (a) consisting of an unsaturated vinyl compound containing ~5000 polyoxyalkylene chains (a) Vinyl type having a constitutional unit of 0.1 mol% or more and 98.9 mol% of vinyl unsaturated sulfonic acid or its salt The polymer (B) contains the monomer unit (a) in an amount of 0.1 to 10% by weight based on the total composition.
An antistatic polymer composition characterized by being blended so as to have the following properties.