JPH039133B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to durable antibacterial, antifungal and odor resistant bedding and upholstery materials. Traditionally, bedding and interior decoration products made of synthetic fibers or films have no odor-proofing, anti-bacterial, or anti-mold properties, and can sometimes grow mold or emit odors, so improvements are needed. It was considered to be one of the problems faced by The inventors of the present invention focused on these problems, and as a result of intensive studies, they decided to modify the synthetic resin to impart various properties such as durable antibacterial, anti-fungal, and odor-resistant properties. Successful. That is, the gist of the present invention is to provide a molded article made of polyamide, polyester or polyacrylonitrile resin having acidic groups of 3×10 ^-4 gram equivalent/gram or more of the molded article, which has antibacterial properties and has hydrocarbon groups. A quaternary nitrogen compound having a total carbon number of 12 or more is added to 3.0×
Bedding and interior decoration materials made by reacting 10 ^-5 gram equivalent or more. By adopting such a configuration, the present invention successfully solves the problem of odor and mold generation in bedding or interior decorations that could not be solved with conventional synthetic resin molded products. It has been possible to provide a product that is characterized by good durability in anti-mold performance and particularly excellent washing resistance and cleaning resistance. The polyamide used in the present invention is a copolymer formed by copolymerizing ordinary polyamide polymers such as nylon 6, nylon 6/6, nylon 6/10, and other diamine or dicarboxylic acid components. In other words, it is a polymer that has film-forming or fiber-forming properties. Furthermore, polyester is a copolymer formed by copolymerizing ordinary polyester polymers such as polyethylene terephthalate and polybutylene terephthalate, as well as other dicarboxylic acid or glycol components, and forms films or fibers as described above. refers to something that has the ability. Further, in the case of polyacrylonitrile, as described above, it is a common polyacrylonitrile polymer or a copolymer mainly composed of polyacrylonitrile, and has fiber-forming properties. In the present invention, the above polymer has a weight of 3×10 ^-4 gram equivalent/gram molded product or more, preferably 5.5×10 ^-4
Gram equivalent/gram molded product into which acidic groups have been introduced is applicable. As such acidic groups, carboxylic acids and sulfonic acids are preferable from the viewpoint of the subsequent substitution reaction treatment of the quaternary nitrogen compound. Such acidic groups can be introduced into the above polymer by the following compounds. For example, carboxylic acid groups include acrylic acid, methacrylic acid, derivatives thereof, and unsaturated aliphatic polycarboxylic acids such as itaconic acid and butenetricarboxylic acid, and sulfonic acid groups include styrenesulfonic acid and 2-acrylamide. Examples include 2-methyl-propanesulfonic acid, 2-acrylamido-2-phenyl-ethanesulfonic acid, allylsulfonic acid, and derivatives thereof. Any compound may be used as long as it contains the compound. In addition to the above, in the case of polyamide or polyester, the above-mentioned acid group-containing compound having a functional group such as an amino group, a carboxyl group, or a hydroxyl group that can be copolymerized with these polymers may be used. The introduction of acidic groups may be carried out by copolymerization during the polymerization stage of the above-mentioned polymer, by blending with the polymer at the molding stage, or by graft polymerization into the molded product, and in the present invention, any of these methods may be used. . However, graft polymerization on molded articles is the most common in terms of the physical properties of the molded articles and the ease of production on a quantitative scale. Such graft polymerization methods include radiation irradiation, ozone oxidation, using initiators such as peroxides,
A known method of activating and graft polymerizing the above-mentioned monomers may be used. Furthermore, in addition to the method described above, polyacrylonitrile fibers can be heat-treated with a concentrated alkaline aqueous solution to convert nitrile groups into carboxyl groups. In any case, if the amount of acidic groups introduced or contained in the molded product is less than 3 x 10 ^-4 gram equivalent/gram molded product, a basic nitrogen compound having antibacterial properties will be reacted later. Even if this is done, sufficient antibacterial performance, which is the objective of the present invention, cannot be imparted. Next, the quaternary nitrogen compound having antibacterial properties according to the present invention includes a saturated or unsaturated fatty acid hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group constituting the nitrogen heterocycle of the nitrogen compound. and a fourth consisting of a hydrocarbon group that is a combination of these groups.
It is a nitrogen compound with antibacterial and antifungal properties,
Furthermore, hydrocarbon groups with a total number of carbon atoms of 12 or more, preferably 15 or more are selected. A typical example of the quaternary nitrogen compound of the present invention is a quaternary ammonium salt represented by the following general formula. General formula: Here, R ₁ to _{R 4} are hydrocarbon groups, and when they further have a nitrogen-containing heterocycle, R ₃ in the above general formula,
It takes the structure of the following formula where R ₄ is represented by R ₅ . Here, R ₅ is a hydrocarbon group having 2 or more carbon atoms, preferably 5 or more carbon atoms, and R ₅ may have a structure that further includes the hydrocarbon groups R ₁ to _{R 4} . In either case, the total number of carbon atoms in all hydrocarbon groups is selected to be 12 or more, particularly preferably 15 or more. X represents halogen, particularly preferably chlorine or bromine. Specific examples of compounds represented by the general formula include lauryl dimethyl benzyl ammonium chloride, cetyl dimethyl benzyl ammonium bromide, stearyl trimethyl
Examples include ammonium chloride and cetyl pyridinium chloride. However, compounds in which the total number of carbon atoms in hydrocarbon groups is less than 12, such as hexyl trimethyl ammonium chloride, have the disadvantage of poor antibacterial properties. These basic nitrogen compounds having antibacterial properties may be used alone or in combination of two or more. These basic nitrogen compounds having antibacterial properties are used in an amount of 3.0×10 ^-5 or more gram equivalent, preferably 1.0×10 ^-4 per gram of the above-mentioned acidic group-containing polyamide, polyester, or polyacrylonitrile molded product. React in a range of gram equivalent or more. 3.0×10 ^-5 gram equivalent/gram・
If the molded product is less than 1.0 ×
Even if the reaction exceeds 10 ^-3 gram equivalent/gram molded product, the deodorizing and anti-mold performance will reach equilibrium and no further performance improvement can be expected. The bedding or interior decoration material of the present invention is composed of a molded product having antibacterial properties as described above, and the molded product may be in the form of a fiber, a film, a plate, a rod, etc., which are usually used for bedding or indoor decoration. A form applied as an ornament can be adopted. In addition, these molded products can be manufactured by commonly used known techniques. Examples of such bedding include sheets, duvet covers, pillowcases, etc., and interior decoration items include wallpaper, curtains, chair covers, etc.
Items mainly made of fibers such as tablecloths can be mentioned, but there is no need to limit them to this.For example, accordion curtains (film) for indoor divisions, table cover films, and even items made of film or foam such as bath mats. is also valid. In the present invention, the above-mentioned material may be composed of the antibacterial molded article of the present invention alone, but it may also be composed of a mixture of other resins and fibers. The bedding or interior decoration material of the present invention has excellent deodorizing and anti-mold properties, and is particularly effective in cases where it is necessary to leave the bedding for a long period of time, such as a permanent bed. For example, no odor will be emitted even after one week of use. In addition, in the case of bath mats (foam), mold grows on ordinary mats within one week, but the product of the present invention is characterized in that no evidence of mold is observed at all. Example 1, Comparative Examples 1 and 2 By graft polymerizing methacrylic acid,
A 48-count spun yarn consisting of 6-nylon staple 3D x 76 mm into which 5.3 x 10 ^-2 gram equivalents of carboxyl groups and gram fibers have been introduced is woven into a plain weave fabric, lauryl dimethyl,
15% by weight benzyl ammonium chloride
(% per weight of processed material) containing a bath ratio of 1:
The fabric was immersed in an aqueous solution adjusted to have a concentration of 30° C. and heated at 80° C. for 30 minutes to replace the carboxyl terminals with quaternary ammonium. It was found from the weight change that this product was reacted with lauryl dimethyl benzyl ammonium at 2.8×10 ⁻⁴ gram equivalent/gram fiber. Next, the treated fabrics were made into sheets, and after a practical test for one day, they were washed 10 times.
The mold resistance of these sheets was measured based on JIS-Z-2911 method. The results were as shown in the table below. As comparative examples, sheets made of ordinary 6-nylon (Comparative Example 1) and sheets made of natural cotton (Comparative Example 2) were treated with lauryl and
The table below shows the antifungal properties of samples treated with dimethyl ammonium chloride. The numerical value for determining antifungal properties means the following. 3: No growth of hyphae is observed. 2: Mycelia growth is less than 1/3 of the total area. 1: Mycelia grow over 1/3 of the total area. For washing, use a washing solution consisting of 2 g of a commercially available neutral detergent Zab (Kao Soap Co., Ltd.) and a bath ratio of 1:50 at 40°C for 20 minutes using a household washing machine. Perform two minute overflow washes. Even in this step, the number of washings was set to one.

[Table] Example 2, Comparative Example A spun plain fabric for sheets made of ordinary polyester fibers 2.0 d x 54 mm was treated with 30 g of methacrylic acid/
Benzoyl peroxide 5g/monochlorobenzene
The sample was immersed in a solution containing 10 g/14 mole adduct of nonylphenol and 5 g/14 mole adduct of nonylphenol at a bath ratio of 1:30, and heat-treated at 100° C. for 60 minutes. It was found from the weight change rate that 4.3×10 ^-3 gram equivalent/gram fiber of carboxyl groups were introduced into this product. After washing with water, the mixture was immersed in an aqueous solution containing 4 g of stearyl dimethyl benzyl ammonium bromide at a bath ratio of 1:30, and heat-treated at 80°C for 30 minutes. . This product has 2.1×
Reacted with 10 ⁻⁴ gram equivalents of stearyl dimethyl benzyl ammonium. When this fabric was used as a sheet and tested on actual use, it was found that there was no unpleasant odor even after using it for three consecutive weeks.Furthermore, the anti-mold properties were investigated based on JIS-Z-2911 in the same manner as in Example 1. It was found that the material had excellent wash resistance (this example). For comparison, octyl trimethyl ammonium bromide was used instead of stearyl dimethyl benzyl ammonium bromide in this example.
Chloride (Comparative Example 3) and hexyl pyridinium chloride (Comparative Example 4) were used under the same conditions as in this example, but neither of them had antifungal properties or deodorizing properties.

Claims (1)

[Claims] 1. Molded products made of polyamide, polyester or polyacrylonitrile resins having acidic groups of 3×10 ^-4 gram equivalent/gram or more,
It has antibacterial properties, and the total number of carbon atoms in the hydrocarbon group is
A bedding and interior decoration material obtained by reacting a quaternary nitrogen compound of 12 or more in an amount of 3.0×10 ^-5 gram equivalent or more per gram of the molded product.