JPH0230340B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for antimicrobial treatment of polymeric molded articles, and more particularly to improved processing of organosilicone with quaternary ammonium bases.

Microorganisms such as various molds and bacteria live in the atmosphere and have harmful effects on textile products and the human body. For example, human sweat, food and beverages, etc. adhere to a wide range of textile products, including not only clothing and bedding, but also interior and exterior products.
The components in these serve as a nutrient source for culturing molds and bacteria. These microorganisms and their discharged substances cause discoloration, embrittlement of the fibers themselves, and the generation of bad odors, causing serious hygienic problems. Especially in socks, underwear, casual wear, bedding sheets, covers, interior materials for aviation, ships, vehicles, etc., the growth, reproduction, and spread of bacteria attached to the fibers are harmful to human health. Of course it is harmful.

Conventionally, in order to solve such problems, methods of treatment with an organotin compound, an organic mercury compound, a halogenated phenol compound, a method of treatment with a cationic surfactant containing a quaternary ammonium base, a method of treatment with a cationic surfactant containing a quaternary ammonium base,
A method of treating with a vinyl polymer having a class ammonium base is known.

However, when using these known methods, there are problems of toxicity to the human body, pollution of treated waste liquid,
The reality is that no satisfactory method is known due to problems such as lack of durability and discoloration due to processing. Particularly because there are fewer problems such as toxicity, the 4th
Cationic polymers having ammonium bases have attracted attention (for example, Japanese Patent Publication No. 45485/1985). However, these processing agents are also durable,
Not only does it have problems with texture, but it also has the disadvantage of easily decreasing whiteness.

The inventors of the present invention have conducted intensive research on a method for efficiently obtaining a processed product that does not have these drawbacks but has excellent durability and antibacterial properties, and as a result, they have arrived at the treatment method of the present invention. That is, the present invention provides a polymer molded article,
When processing with organosilicones containing quaternary ammonium bases, organic and/or
Alternatively, it is characterized by the addition of inorganic salts.

When using the method of the present invention, excellent antibacterial properties are imparted due to the presence of a quaternary ammonium base, and the durability of antibacterial properties is improved, as well as treatment efficiency, so that it is effective with a small amount of treatment agent. It has the characteristics of being able to obtain In particular, it is a great advantage that high reaction efficiency can be obtained due to increased affinity even for hydrophobic polymers with low reaction efficiency or adhesion of processing agents, and the use of this type of processing agent can be greatly expanded. It also becomes.

The organosilicone having a quaternary ammonium base used in the present invention is
An organosilicone having a structure obtained by quaternizing a diorganopolysiloxane having a siloxane unit having a nitrogen-containing group such as a dialkyl-substituted aminoalkyl group, and having the general formula (R) ₃ Si—R′—N (R″) _o (R ) _3~o × (However, R: alkoxy group, halogen atom, acyl group,
One may be a hydroxyl group.

R′: Number of carbon atoms that may have substituents
It may be a divalent hydrocarbon group of 20 or less, or a divalent hydrocarbon group of 20 or less carbon atoms containing an oxygen atom or a nitrogen atom.

R″: lower alkyl group, R: number of carbon atoms is 1
~20 alkyl, alkenyl, cycloaliphatic hydrocarbon, aromatic, aralkyl or alkaryl groups.

n: a positive integer of 1 to 3, X: anion, such as a chlorine atom or a bromine atom. ) is exemplified. Furthermore, preferred compounds of the latter include is exemplified. These compounds form a water-resistant film on fibers, and the latter compound in particular reacts with active hydrogen present in polymer molded products to introduce quaternary ammonium cations, making them highly effective against various molds and bacteria. It has antibacterial and bactericidal effects.

To name a few, molds such as black mold, blue mold, Aspergillus aspergillus, chaetomium, spider mold, Bacillus enterica, Staphylococcus aureus, Corynebacterium, gram-negative rods, Bacillus sp., Bacillus sp.
It exhibits bactericidal and bactericidal effects against many bacteria such as the genus Coccus.

Polymer molded products to which the present invention is applied include, for example, natural polymers such as cellulose and protein-based polymers;
Fibers, synthetic paper, etc. made of semi-synthetic polymers such as cellulose acetate, synthetic polymers such as polyester, polyamide, polyvinyl alcohol, polyurethane, polyclar, polyolefin, etc.
Examples include films, foams, other molded products, and composite products thereof. It is particularly effective when applied to fibers. Fibers include loose hair, yarn, sliver,
This includes knitted fabrics, non-woven fabrics, rugs, tapes, sewn products, etc. It may be a composite or a mixture of polymer fibers and inorganic fibers.

The fibers may be made of not only a single material but also composite materials of various fibers, mixed materials, etc.

The organosilicone used in the present invention, especially the organosilicone represented by the above general formula, is applied to a polymer molded article by any method such as a dipping method, a spray method, a pad method, etc. It bonds covalently or ionically with anionic groups, but generally when the polymer has many active groups, such as cellulose fibers such as cotton, hemp, regenerated cellulose, and copper ammonium rayon, the reactivity is high, with a reactivity of 80%. Although the above reactions are relatively easy to obtain,
For other fibers with less active groups and less swelling, the degree of reactivity is
It will be less than 50%.

If the degree of reactivity is low, not only will the efficiency of using the treatment agent be low, but it will also lead to insufficient durability, increased chemical costs, and problems with waste water.

When using the method of the present invention, the treatment agent is effectively adsorbed onto the polymer molded article by adding salts to the treatment solution, and the adsorption efficiency of the treatment agent is improved, so a dilute solution with a large bath ratio is used. Even with the immersion treatment, there are advantages such as excellent utilization efficiency, improved reactivity, and improved durability.

Improvements in durability can also be achieved by the pad dry method, pad steam method, etc.

The organic and inorganic salts used in the present invention are not particularly limited as long as they are water-soluble, but in particular halides of mono- to trivalent cations, sulfates, nitrates, phosphoric acid, carbonates, and acetic acid. salts, tartrates, etc., specifically sodium chloride, sodium sulfate, sodium carbonate, sodium acetate, magnesium chloride, barium chloride,
Examples include magnesium nitrate, zinc nitrate, aluminum sulfate, ammonium chloride, diammonium phosphate, ammonium acetate, ammonium tartrate, and propanolamine hydrochloride.

To explain the treatment method of the present invention in more detail, it is preferable to immerse the organosilicone in an aqueous solution containing salts and optionally other treatment agents, auxiliary agents, etc. After impregnating or applying the treatment solution, drying is performed. Alternatively, a method of steaming treatment, etc. may be used. The treatment temperature in the dipping treatment is usually room temperature to 80°C, preferably 40 to 70°C.

After treatment, it is usually preferable to remove liquid, dry, and finish setting.

The amount of organosilicone applied is usually 0.1 to 3%, preferably 0.5 to 1%, based on the weight of the molded product. Although the amount of salts used depends on the processing method, it is preferably about 3 to 30% based on the weight of the molded product.

The present invention will be explained below with reference to Examples.

Example 1 Using a jet dyeing machine, a washed polyester knit was rotated in water at a bath ratio of 1:15, and 1.0% owf of an organosilicon quaternary ammonium salt represented by the following formula was added thereto, and the dye was uniformly dyed. After mixing,
After adding 5% owf of anhydrous sodium sulfate, the temperature was raised to 65° C. over 15 minutes, and the mixture was treated at that temperature for 20 minutes.

Next, after centrifugal dehydration, it was dried and heat set at 160°C to perform antibacterial treatment. In addition, as a comparative example, a sample to which mirabilite was not added was also prepared. These reactions were measured by residual bath colorimetry using bromophenol blue color reaction.

Antibacterial properties were tested using the mold resistance test method of JIS Z 2911-1976.

As a result, the reactivity of the present invention treated with antibacterial treatment by adding Glauber's salt was 90%, which was 3 times higher than the 31% of the comparative example without the addition of Glauber's salt.

Furthermore, there was a clear difference between the two in the antibacterial test, and the effect of the present invention was clearly recognized.

Furthermore, the treated fabric according to the present invention was also significantly superior in durability.

Example 2 Using a paddle dyeing machine, dyed nylon pantyhose were added with 0.8% OWF of the same organosilicon quaternary ammonium salt as in Example 1 in water at a bath ratio of 1:30, and heated to 40°C. After raising the temperature, ammonium sulfate (6% owf) was added, the temperature was subsequently raised to 60°C, and the mixture was treated at that temperature for 30 minutes. Next, after centrifugal dehydration, it was placed in a foot mold and steam set at 115°C x 5'.

For comparison, a sample without ammonium sulfate was also prepared.

As a result of testing the reactivity and antibacterial properties in the same manner as in Example 1, the reactivity of the organosilicon quaternary ammonium salt with ammonium sulfate added was 85%, which is 2.5 times that of the unadded salt. There was also a clear difference in antibacterial properties between the two.

Example 3 Dyed polyester/cotton (50/50) blend milling knit was mixed with the same organosilicon quaternary ammonium salt as in Example 1, 1.5% OWF and 20% common salt, in water at a bath ratio of 1:20 using a wince dyeing machine. After adding owf, the temperature was raised to 65°C in 20 minutes, treated at that temperature for 45 minutes, washed with water for 5 minutes, centrifugally dehydrated, dried, and subjected to antibacterial treatment. For comparison, a sample to which no salt was added was also prepared. The degree of reactivity was determined by observing the state of adhesion of the organosilicon quaternary ammonium salt reacted to the treated cloth by observing the coloration of bromophenol blue.

As a result, it was observed that in the antibacterial treated fabric without the addition of salt, the finishing agent was almost exclusively attached to the cotton, whereas in the fabric treated with salt, the finishing agent was uniformly attached to both the polyester and cotton. did it.

Claims (1)

[Scope of Claims] 1. An antibacterial treatment method characterized by adding organic and/or inorganic salts to the treatment solution when treating a polymer molded article with an organosilicone having a quaternary ammonium base. 2 An organosilicone with a quaternary ammonium base has the formula The antibacterial treatment method according to claim 1, which is a compound represented by: