JPH0440386B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a synthetic polymer composition having antistatic properties, and particularly to a polymer composition having antistatic properties with high durability and washing resistance. Synthetic polymers are widely used in large quantities in various fields, such as fibers, films, rods, pipes, sheets, and various molded products, depending on the purpose. Synthetic polymers are currently being used as essential materials, and the scope of their use is expanding, but due to the physical and chemical properties of synthetic polymers themselves, there are various obstacles to their use. The following problems have emerged. In particular, hydrophobic polymers such as polyamide, polyester, and polyolefin have various problems such as low hygroscopicity, easy charging, and poor dyeability. Conventionally, various additives have been proposed to impart antistatic properties to synthetic polymers, but some do not have sufficient performance or durability (for example, washing resistance), and some do not have sufficient performance or durability (for example, washing resistance). There were many things that impaired the characteristics. The present invention provides a polymer composition that solves these problems, and is composed of a synthetic polymer, a zwitterionic compound having a sulfonate niaone or a metal salt thereof, and a poly-N-acylalkyleneimine compound. The gist is a polymer composition. Specifically, the zwitterionic compound in the present invention is represented by the following general formula. [R ¹ is a C1-26 hydrocarbon group, R ² is hydrogen or a lower alkyl group, R ³ is an alkylene group, phenylene group, or aralkylene group, X ¹ is hydrogen, a hydroxyl group, or -O-R ³ -SO ₃ 1 /nM (M is a metal ion, n is an integer corresponding to the valence of M), X ² and X ³ are hydrogen or -R ³
-SO ₃ 1/nM, a, b, and c are 0 or positive integers, and a + b + c = 1 to 200. ] In the above zwitterionic compound, R ¹ may have a substitution such as a halogen or a nitro group,
R ² is preferably hydrogen or a methyl group, and a+
It is desirable that b+c≧10. A specific example of R ³ is −
CH ₂ −, −CH ₂ CH ₂ −, CH ₂ CH ₂ CH ₂ −, −CH
_Examples include ( _CH3 )-, _-C6H4- , _-CH2 - _{C6H4- ,} and the like. These zwitterionic compounds are synthesized by the following method. The first method is to react 1,2-epoxyalkane with mono- or diethanolamine, optionally add alkylene oxide, ^and then
This is a method in which a sulfonate compound represented by -SO ₃ 1/nM (X is a halogen), such as sodium monochloromethane sulfonate, is reacted in the presence of a strong base such as NaOH. The second method is R ¹ CH ₂ CH ₂ CH ₂ NH ₂ , R ¹ CH
This is a method in which an alkylene oxide is added to an amine such as (OH)CH ₂ NH ₂ and then a sulfonate compound is reacted in the same manner as in the first method. In these methods, by adjusting the reaction amount ratio when reacting the sulfonate compound,
A compound in which some or all of X ¹ , X ² , and X ³ are sulfonate groups can be obtained. Further, usually a compound in which M is an alkali metal is synthesized, and when a compound of another metal is required, this may be reacted with a corresponding inorganic salt of the other metal. In addition, the poly-N-acylalkyleneimine compound in the present invention means a poly-N-acylalkyleneimine homopolymer and a copolymer containing an N-acylalkyleneimine unit, and specifically, 2-oxazoline, 2-oxazine ,2
-substituted-2-oxazoline or 2-substituted-2
- Those obtained by polymerization of oxazine, those obtained by acylating polyethyleneimine obtained by polymerization of ethyleneimine by a normal acylation method, and random containing N-acyl alkylene imine units and ethylene imine units or trimethylene imine units. Mention may be made of copolymers, graft or block copolymers containing N-acylalkyleneimine units. Specific examples of copolymers include those obtained by a combination of reactions between oxazoline compounds or oxazine compounds and electrophilic reactive monomers such as acrylic acid or derivatives thereof, β-propiolactone, cyclic acid anhydrides, etc.
Examples include those obtained by cationic polymerization of an oxazoline compound or an oxazine compound to a polymer having cationic polymerization initiating ability, such as chloromethylated polystyrene, polystyrene having a halogen end group, or polybutadiene. As the synthetic polymer in the present invention, polyamides such as nylon 6 and nylon 66, polyesters such as polyethylene terephthalate and its copolymers, polyolefins such as polyethylene and polypropylene, and polyvinyl chloride are used. The composition of the present invention contains a zwitterionic compound and poly-N during the synthesis of a synthetic polymer or in a synthesized polymer.
-Acyl alkylene imine compound. Usually, after mixing the synthesized polymer with a zwitterionic compound and a poly-N-acylalkyleneimine compound in the form of particles, powder, or solution, drying treatment is performed as necessary, followed by melt spinning, solution spinning, Used for extrusion molding, injection molding, etc. The blending ratio varies depending on the type of each ingredient, but
In general, zwitterionic compounds are 0.05% of synthetic polymers.
~10% by weight, the poly-N-acylalkyleneimine compound accounts for 0.5~10% by weight of the synthetic polymer, and 0.1~10% by weight relative to the zwitterionic compound.
The ratio is preferably 10 times the amount. If the amount of these compounds is too small, the modification effect will be poor, and if the amount is too large, the inherent properties of the synthetic polymer may be impaired. In the present invention, R of the acyl group RCO- of the poly-N-acylalkyleneimine compound is hydrogen,
It can be selected from alkyl groups or aryl groups having 1 to 26 carbon atoms, but it is desirable to select an appropriate one depending on the type of synthetic polymer to be added. For example, when adding to polyamide, R is a lower alkyl group such as a methyl group or ethyl group for better miscibility; when adding to aromatic polyester, R is an aryl group such as phenyl group or a higher alkyl group. is preferred. Furthermore, the molecular weight of the poly-N-acylalkyleneimine compound can range from several thousand to tens of thousands, but it should be selected appropriately depending on the type of synthetic polymer to be added and the type of molded product to be manufactured. is desirable. For example, when melt-spinning polyester, the greater the molecular weight of this compound, the better the durability of antistatic properties, but it is more likely to cause thread breakage during spinning, so it is preferable to choose a compound with a moderate molecular weight. Although it is known to add a conventional zwitterionic compound having a carboxylate anion to a synthetic polymer as an antistatic agent, the heat resistance was not sufficient. The zwitterionic ionizable compound having a sulfonate anion in the present invention has good heat resistance and does not cause coloring even when a synthetic polymer composition containing it is melt-molded, and poly-N-
When used in combination with an acylalkyleneimine compound, it imparts a high degree of antistatic property to the synthetic polymer. Various additives may be further added to the composition of the present invention, and in particular, when a hydrophilic polymer such as polyethylene glycol, polyacrylic acid, etc. is used in combination, the hydrophilicity and antistatic property can be greatly improved. . Other additives include pigments, dyes,
Examples include clay and other fillers, stabilizers, and flame retardants. Next, examples of the present invention will be shown. Example 1 100 parts of nylon 6 chips were mixed with 1 part of each of the zwitterionic compounds shown in Table 1 above and 1 part of poly-N-propionylethyleneimine, and dried in a vacuum dryer for 100 parts. After drying for 48 hours at 0.degree. C., the resulting mixture was melt-spun at 260.degree. C. by a conventional method and then drawn to a factor of 3.0 to obtain a drawn yarn of 250 denier/30 filaments. A fiber made of nylon 6 alone was also produced under the same conditions and used as a comparative example.

[Table] The obtained drawn yarn was braided into a tricot, and heated at 60°C.
30 minutes, Actinol R-100 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.)
After scouring at a bath ratio of 1:100 and drying, Supranor Cyanine G (manufactured by Bayer) 0.3
% (owf), acetic acid 0.2cc/, in a system with a bath ratio of 1:100.
Staining treatment was performed by boiling for 45 minutes. For the above dyed products, relative humidity 40%, 20℃
So, the static honest meter (manufactured by Shishido Shokai)
The half-life and electrical resistance of each sample were determined using an electrical resistance measuring device (according to the current-voltage method according to AATCC-76-75). The results obtained are shown in Table-2. Table -
From the results in Example 2, it was confirmed that the nylon 6 composition of the present invention has excellent antistatic properties.

【table】

[Table] Example 2 To 100 parts of polyethylene terephthalate chips, 1 part each of the compounds No. 4, 9, and 10 in Table 1 and 1 part each of the poly-N-acylalkyleneimine compounds shown in Table 3 were added. Mix and dry in a vacuum dryer at 130℃ for 48 hours, and dry the resulting composition at 275℃.
The fibers were melt-spun at 0.degree. C. and then stretched 3.0 times to obtain a 250 denier/25 filament drawing system. In addition, fibers with 2 parts of compound No. 4 in Table 1 added alone, fibers with 2 parts of compounds Nos. 3 and 4 in Table 3 added alone, and fibers made of polyethylene terephthalate alone were also spun in the same way. , and was produced under stretching conditions and used as a comparative example. The polyethylene terephthalate composition of the present invention has no defective biting of pellets into the spinning machine.
The spinnability was good. What is noteworthy is that the polyethylene terephthalate fiber containing the zwitterionic compound does not show any coloring, and the fiber of the present invention containing the poly-N-acyl alkylene imine compound has excellent antistatic performance and washing resistance. The retention rate was good. For evaluation, the obtained drawn yarn was braided into a tight
60℃, 30 minutes, Actinol R-1001g/, after scouring with bath ratio 1:100, after drying, relative humidity 40%,
This was done by measuring each half-life using a static honest meter at 20°C. Further, the dried sample was further boiled for 1 hour and then dried, and the half-life of the boiled sample was also measured for evaluation of washing resistance. The results obtained are shown in Table 4.

【table】

【table】

[Table] (Test No. 1 is a blank test, Nos. 8 to 10 are comparative examples.) Example 3 No. 4 in Table 1 was added to the various synthetic polymers shown in Table 5.
A monofilament (approximately 5 denier) was produced by extrusion spinning by adding and mixing the compound in the amount shown in Table 5 and 1% poly-N-acetylethyleneimine. Table 5 shows the results of measuring the half-life and electrical resistance of this monofilament. In both cases, no coloration was observed in the filament and excellent antistatic properties were observed.

【table】

Claims (1)

[Scope of Claims] 1. A synthetic polymer selected from polyamide, polyester, polyolefin, and polyvinyl chloride, a zwitterionic compound having a sulfonate anion represented by the following general formula or a metal salt thereof, and poly-
A polymer composition comprising an N-acyl alkylene imine compound. [R ¹ is a C1-26 hydrocarbon group, R ² is hydrogen or a lower alkyl group, R ³ is an alkylene group, X ¹ is hydrogen, a hydroxyl group, or -O-R ³ -SO ₃ 1/nM (M is a metal ion) ,
n is an integer corresponding to the valence of M), X ² and X ³ are hydrogen or -R ³ -SO ₃ 1/nM, a and bc are 0 or a positive integer, and a+b+c = 1 to 200. 2. The polymer composition according to claim 1, wherein the poly-N-acylalkyleneimine compound is obtained by polymerizing an oxazoline compound or an oxazine compound. 3. The polymer composition according to claim 1, wherein the poly-N-acylalkyleneimine compound is obtained by acylating polyethyleneimine. 4. The zwitterionic compound or its metal salt accounts for 0.05-10% by weight of the synthetic polymer, and the poly-N-acylalkyleneimine compound accounts for 0.5-10% by weight of the synthetic polymer.
% by weight of a polymer composition according to claim 1.