JPH0347296B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating synthetic polymer molded articles, and more particularly to a treatment method for imparting durable antibacterial properties to synthetic polymer molded articles.

Conventionally, methods for imparting durable antibacterial properties to polymer molded articles include the use of specific antibacterial compounds, such as 2-
A method in which (4-thiazolyl)benzimidazole, an organotin compound, etc. is mixed into a polymer before molding and then spun, and a method in which a polymer molded product is post-processed with a polymeric antibacterial agent such as bis(tributyltin) itaconate polymer. (Special Publication No. 43-4240) etc. have been proposed. However, since the antibacterial effect only affects the surface of the molded product, in the former method it is necessary to add a larger amount than necessary, which may cause problems such as discoloration, and the antibacterial effect is poor especially after washing. Because the effect is limited to a very narrow area, the effect is insufficient especially when used in combination with other fibers, and various problems may occur during the molding process and during the dyeing process after molding. have. In addition, the latter method has drawbacks such as poor washing durability compared to hydrophobic polymers and impairs the texture of molded products. In addition, when tin compounds are generally used, there are problems with heavy metal pollution and problems specific to organic tin. It is not practical because it has an unpleasant odor.

Recently, treatment with an organopolysiloxane having a quaternary ammonium base has also been proposed, and has shown good durability for natural fibers that are swellable and have active groups, such as cotton. However, the durability of the effect is insufficient for synthetic polymer molded articles that have no swelling properties and are poor in active groups.

The present inventors have conducted extensive research into post-processing methods for imparting durable antibacterial properties to synthetic polymer molded articles, and have arrived at the method of the present invention. That is, the present invention relates to a synthetic polymer molded article, which is characterized in that an anionic group is introduced onto the surface of the synthetic polymer molded article and then treated with a quaternary ammonium group organosilicone compound having the following general formula []. Processing method.

[However, R: lower alkyl group, R ₁ : alkylene group, R ₂ , R ₃ : same or different lower alkyl group,
_R4 : _C12-22 alkyl group, X: anionic group] According to the present invention, by introducing an anionic group, the adhesion and durability of the antibacterial agent are improved, and wetting is improved. Therefore, it has the characteristics that the area over which its antibacterial action can be applied is widened. Therefore, the synthetic fiber obtained by the method of the present invention has the characteristic of exhibiting an excellent antibacterial effect even on textile products in which the synthetic fiber is composited with other unprocessed fibers.

The synthetic polymer molded articles used in the present invention include molded articles made of hydrophobic synthetic polymers such as polyester, polyamide, polypropylene, and polyacrylonitrile, but in particular polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and Molded products made of polyesters such as copolyesters mainly composed of cyclohexane dimethylene terephthalate and alkylene terephthalate, polyester polyether elastomers, and polyester polylactone elastomers, and polyamides such as nylon 6, nylon 6,6, and nylon 12 are preferred.

Molded products include fibers, films, molded products, etc. Fibers include filaments, cotton, slivers,
Examples include woven and knitted fabrics, nonwoven fabrics, synthetic paper, rugs, pile fabrics, and the like. In addition to molded products made of synthetic polymers alone, composite molded products of synthetic polymers and natural polymers, such as fibers, synthetic fibers and natural fibers,
It may also be a product mixed with recycled fibers or the like. In the case of fibers, the cross section may of course be irregular or hollow.

As a method for introducing anionic groups onto the surface of a synthetic polymer molded article, a method of graft polymerizing a vinyl monomer having an anionic group onto the molded article is preferable, and in particular, a method of graft polymerizing a vinyl monomer having a carboxylic acid group is preferable. Particularly preferred is a method in which a vinyl monomer having a carboxylic acid group-forming group is graft-polymerized and then a carboxylic acid group is formed or an anionic group is introduced. However, there are methods in which carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, etc. are introduced by treatment with cyclic carbonates, sultones, lactones, or phosphorus halides in the presence of Friedel-Crafts catalysts, and molded products blended with polystyrene. A method of blending a 5-sodium sulfoneisophthalic acid polyester oligomer with a normal polyester and shaping it by means of concentrating the oligomer mainly on the surface side; Alternatively, the surface of the molded article may be coated with a polymer having a functional group. The effect is poor when an anionic group is introduced into the polymer itself constituting the molded article by copolymerization.

Examples of graft polymerization methods include heating in the presence or absence of a polymerization catalyst, photoinitiated graft polymerization, plasma polymerization, and the like. Examples of vinyl monomers having anionic groups include acrylic acid, methacrylic acid, maleic anhydride, styrene sulfonic acid, vinylphosphonic acid, etc. These monomers may be used alone, and unsaturated monomers having a polyoxyalkylene chain, and other Vinyl monomers may be co-grafted. When an unsaturated monomer having a polyoxyalkylene chain is co-grafted, there is an advantage that the hydrophilicity is further improved and the antibacterial effect is further promoted.

Furthermore, the antibacterial agent having a quaternary ammonium base used in the present invention includes organopolysiloxane having a quaternary ammonium base,
Organosilicone compounds represented by the following formula [] are preferred, and the latter compound is especially preferred.

(However, R: lower alkyl group, R ₁ : alkylene group, R ₂ , R ₃ : same or different lower alkyl group,
_R4 : _C12-22 alkyl group, X: anion) Particularly preferred are organosilicone compounds represented by the following formula [].

A treatment method using an antibacterial agent containing a quaternary ammonium salt is usually a method in which a treatment solution containing the treatment agent is applied by any method such as spraying, padding, transfer, etc., followed by drying and, if desired, heat setting. Any law is fine. If desired, a stabilizer, an antistatic agent, a stain removability improver, a PH regulator that promotes the adhesion of the treatment agent, salts, and the like can be added to the treatment liquid as appropriate.

The amount of anionic group introduced in the present invention depends on the form of the molded article, etc., but is usually 1 equivalent/ton or more, preferably 3 equivalents/ton or more, and the surface area
It is preferably 0.05 milliequivalent or more, particularly 0.2 milliequivalent or more per 100 cm ² .

Furthermore, the amount of antibacterial agent applied varies depending on the form of the molded product, but when the molded product is particularly fiber or film, 0.02 to 3% by weight is usually sufficient, and preferably 0.1 to 2% by weight. .

The present invention will be explained below with reference to Examples. In addition,
In the examples, the amount of antibacterial agent attached was determined by the following color test.

Promphenol blue 0.4g 10% soda ash 0.2cc Water 1000ml solution was stabilized overnight and diluted to 50 times the volume.
1 g of the sample was placed in a mixed solution of 45 ml and 5 ml of 10% soda ash, shaken for 15 minutes, washed with water, dehydrated, dried, and then evaluated.

Example 1 Acrylic acid was grafted onto the surface of polyester filament taffeta using a plasma polymerization method. In this plasma polymerization, the surface was activated in advance with oxygen plasma for 90 seconds, and then immediately placed in a plasma polymerization chamber and reacted with acrylic acid (gas phase) for 120 seconds under glow discharge. The weight increase due to this was about 0.3% by weight (the amount of carboxylic acid groups introduced was about 5 equivalents/ton). Then Dow
Corning's antibacterial agent DC-5700 After processing for 20 minutes at 60℃ using 1% owf of Cl, bath ratio 1:30, washing with water, drying, and setting (150℃ x 20 seconds).
I went there. As a comparative example, taffeta without plasma polymerization was also treated with DC-5700 under the same conditions.

When the adhesion state of DC-5700 was observed in a color test on the thus obtained treated cloth and the treated cloth after repeated home washing 10 times, it was found that the treated cloth of Example 1 had a better treated cloth than the comparative example. DC−5700 at
The amount of adhesion was large, and the amount of adhesion after 10 washes was also large.

In addition, an antibacterial test using Escherichia coli showed that there is a correlation between the amount of adhesion and antibacterial properties.

Example 2 A 100% polyester staple fabric was treated with an aqueous bath containing methacrylic acid, polyethylene glycol diacrylate, benzoyl peroxide, chlorobenzene, and a nonionic emulsifier to react the methacrylic acid and polyethylene glycol diacrylate. The weight increase rate was 3% by weight, and the amount of carboxylic acid group introduced was 7 equivalents/ton. After this
The antibacterial agent DC-5700 from Dow Corning was treated with 1% OWF at a bath ratio of 1:30 at 60°C for 20 minutes. Thereafter, washing with water, dehydrating, drying, and setting (150°C x 20 seconds) were performed. When the state of adhesion of DC-5700 on this treated cloth was examined by coloration in the same manner as in Example 1, a large amount of antibacterial agent was observed both before and after washing 10 times. In addition, the wicking property of this treated cloth is 3 to 5 seconds, and DC-5700
In the case of treatment only, it took more than 300 seconds, resulting in a water-absorbent and antibacterial treated fabric.

Example 3 Nylon tricot was treated in an aqueous bath containing methacrylic acid and potassium persulfate to produce approximately methacrylic acid.
0.5% by weight (the amount of carboxylic acid groups introduced is approximately 7% by weight/
ton) was reacted with nylon. After this Dow
Treatment was carried out at 60° C. for 20 minutes at a bath ratio of 1:20 using Corning's antibacterial DC-5700 with 1% owf. After this, wash with water,
Deoxidation, drying, and setting (150°C x 20 seconds) were performed.
In addition, as a comparative example, a sample treated only with DC-5700 was also prepared. Looking at the amount of DC-5700 deposited on the sample thus obtained before and after washing (10 times), the nylon of the example showed an overwhelmingly large amount of deposit.

Comparative Example A 100% cationic dyeable polyester (copolymerized with 2.5 moles of 5-sodium sulfoisophthalic acid) fabric was subjected to antibacterial treatment in the same manner as in Example 1. The results of the adhesion weight test on treated fabric were almost the same as regular polyester, and no particular improvement in adhesion was observed.

Claims (1)

[Scope of Claims] 1. A synthetic polymer characterized by introducing an anionic group onto the surface of a synthetic polymer molded article and then treating it with a quaternary ammonium group-containing organosilicone compound having the following general formula [] Processing methods for molded products. [However, R: lower alkyl group, R ₁ : alkylene group, R ₂ , R ₃ : same or different lower alkyl group,
_R4 : _C12-22 alkyl group, X: anionic group]