JPH0317160A - Deodorizing and germicidal molded article of synthetic resin - Google Patents

Abstract

PURPOSE:To obtain the title molded article suitable for building materials such as floor covering material and wall material having both deodorizing performances and antimicrobial performances, capable of developing these performances for a long period of time, comprising a deodorizing and germicidal component containing copper bonded to an anionic functional group and a synthetic resin component. CONSTITUTION:(A) A deodorizing and germicidal component containing copper bonded to an anionic functional group is blended with (B) a synthetic resin component in a ratio to give >=0.01mol copper in 1g molded article. A polymer compound containing carboxyl group or sulfonic group is preferable as the anionic functional group-containing compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a deodorizing and sterilizing synthetic resin molded product.

[Conventional technology]

2. Description of the Related Art Many synthetic resin molded articles having deodorizing and sterilizing properties, such as plastic films, are known as materials for packaging articles that generate various bad odors.

In recent years, as lifestyles have become more sophisticated, there has been a strong demand for maintaining human living spaces in a sanitary manner. There is also a demand for products with deodorizing and sterilizing properties for building materials such as and various containers.

For example, humid areas such as kitchens, washrooms, and bathrooms are prone to the proliferation of bacteria and mold, making them unhygienic and impairing the aesthetics of the room, and there is a strong demand for improvement.

In addition, measures such as using strong air fresheners or increasing ventilation are taken in places where bad odors occur, such as toilets.
It's not enough. Furthermore, odors from products that are closely related to daily life, such as cigarettes and food, are generated everywhere, causing discomfort, but there is currently no solution to this problem.

In response to this current situation, resin molded products mixed with various antibacterial agents and antifungal agents are known. For example, JP-A-64-6
No. 2356 describes a synthetic resin molded article using ferrous salt and aluminum sulfate as deodorizing ingredients. Because the deodorizing ingredients used in some of the shaped products described herein are inorganic substances, they may not be used during use of the shaped product, especially when handling liquids such as water, or in containers where they are generated, in water, or exposed to water. Molded products that are used in close contact with the product have the disadvantage that the deodorizing component elutes and the effect is not maintained for a long period of time.

Furthermore, although this shaped product has a deodorizing effect, it does not have sterilizing performance, so it cannot prevent the growth of bacteria and microorganisms.

Furthermore, JP-A No. 64-66254 discloses that an antifungal agent such as a benzimidazole compound is added to a styrene resin,
A molded article is described in which the anti-mildew agent is blended with a specific anti-mildew surfactant that constantly migrates to the surface of the molded article. When this shaped product is molded, a mixture of resin, fungicide, and surfactant is molded at high temperatures, so the fungicide and surfactant tend to undergo chemical changes, and the molded product may not be placed in water. When used or when used in contact with water, the fungicide will be eluted,
It has drawbacks such as its antibacterial and antifungal effects cannot be maintained for a long period of time.

Furthermore, the antifungal agents described herein cannot be expected to have the effect of eliminating bad odors.

JP-A-1-96244 describes a shaped article in which metallic copper fine particles are mixed with liquid polyester and this mixture is dispersed in a thermoplastic resin.

Since this molded article uses metallic copper fine particles, a special technique is required to uniformly mix the fine particles into the resin molded article, which poses a manufacturing problem.

JP-A-52-92000 describes fibers in which copper ions or silver ions are bonded to some or all of the ion exchange groups. This invention is in the form of fibers, and is suitable for use as clothing, but cannot be used as resin molded products such as flooring, wall materials, or containers.

[Problem to be solved by the invention]

The present invention is a molded material having a form such as a building material such as a flooring material or a wall material, or a container, and which has both deodorizing performance and antibacterial performance, and at the same time has the ability to exhibit this effect over a long period of time. The aim is to provide resin or shaped products that can

[Means to solve the problem]

The present invention provides deodorizing and
A deodorizing agent made from a bactericidal component (I) and a synthetic resin component (n).
It is a sterilizing synthetic resin molded product.

Hereinafter, the deodorizing and sterilizing synthetic resin molded product of the present invention will be explained in detail.

The deodorizing/sterilizing component (f) (hereinafter abbreviated as component I) having copper bound to an anionic functional group of the present invention is a compound having an anionic functional group bound to a copper ion.

The compound having an anionic functional group is a compound having a carboxyl group or a sulfonic acid group, preferably a polymer compound. Such compounds include, for example, single or copolymers of polymerizable monomers having carboxyl groups such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and phthalic acid, allylsulfonic acid, methallylsulfonic acid, and styrene. A single or copolymer of a polymerizable monomer having a sulfonic acid group such as sulfonic acid, carboxymethylcellulose, the above-mentioned polymerizable monomer having a carboxyl group or a sulfonic acid group, and another polymerizable monomer, such as acrylonitrile. , copolymers with methyl acrylate, methyl methacrylate, vinyl acetate, styrene, butadiene, vinyl chloride, vinylidene chloride, ethylene, propylene, etc., polymerizable monomers having the above carboxyl group or sulfonic acid group are used as starch, cellulose , a graft polymer grafted onto a polymer compound such as nylon, polyester, or polyvinyl alcohol, an acid or alkali hydrolyzate of polyacrylonitrile or an acrylonitrile copolymer, and a sulfonated product of polystyrene. The molecular weight of these polymers is not particularly limited, and the content of anionic functional groups is such that the amount of copper bonded to and introduced into the synthetic resin molding is zero.
, 01 m mol/g, preferably 0.5 m mat
/g molded product or more.

As for the amount of copper that is bound to and contained in the above-mentioned compound having an anionic functional group, the higher the content, the better. A molded product having excellent deodorizing and sterilizing effects can be obtained with a smaller mixing ratio of component I, so it is preferable, and it is particularly preferable that the mixing ratio is 0.5 mmol or more per 1 g of the compound.

The amount of copper contained in the molded product of the present invention is 0. 0 1 mm
at/g of the molded product or more, and if it is less than this, the deodorizing and sterilizing effects will hardly be exhibited. On the other hand, there is no upper limit to the upper limit, but if the mixing ratio of the ingredients becomes too large, the shapeability will deteriorate.

Next, the mixing ratio of component I is such that 0.01 mmol or more of copper is contained in the obtained molded product lg. If the mixing ratio is such that the amount of copper contained in 1 g of the molded product is less than 0.01 mn+ol, sufficient deodorizing and sterilizing performance will not be achieved, resulting in poor practicality. On the other hand, the upper limit is 50% by weight or less (% represents weight unless specified), preferably 20% or less, and more preferably 1 to 15% from the viewpoint of practicality such as moldability and strength of the molded product.

Next, the resin component (If) forming the molded article of the present invention is
Polymers having heat-melting properties are particularly preferred, such as nylon, polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polystyrene, polyurethane, and polyester.

Next, a method for producing a molded article according to the present invention will be explained.

Compounds having anionic functional groups, such as polymers having carboxyl groups, can be easily produced by homopolymerization of a polymerizable monomer having carboxyl groups such as acrylic acid or copolymerization of this with other polymerizable monomers. can be obtained.

A polymer having a sulfonic acid group can also be obtained by copolymerizing alone or with another polymerizable monomer having a sulfonic acid group, such as allylsulfonic acid, in the same manner as above. In this case, the other polymerizable monomer may be a compound having a different anionic functional group, or may be a compound having no such anionic functional group, such as acrylonitrile, styrene, vinyl acetate, etc. These polymerizations can be carried out by known methods.

A polymer having a carboxyl group can be obtained by hydrolyzing an acrylonitrile homopolymer or a polymer containing the same as a main component with an acid or an alkali. Furthermore,
Polymers that do not normally have anionic functional groups, such as polyolefin, nylon, polyester, polyvinyl chloride, polyvinylidene chloride, and polyvinyl alcohol, are combined with monomers that have carboxyl or sulfonic acid groups, such as acrylic acid or allyl sulfonic acid. It is also possible to graft molecules.

Next, after processing the above-mentioned polymer having anionic functional groups into powder or granules or into fibers, the polymer is neutralized with an alkali metal hydroxide, such as an aqueous solution of sodium hydroxide, or Copper can be bonded to anionic functional groups by treatment with an aqueous copper salt solution such as copper sulfate or copper chloride without neutralization. In this case, it is better to bond copper to all anionic functional groups because the amount of the deodorizing and sterilizing component mixed in is small, which makes it easier to obtain molded products with excellent deodorizing and sterilizing effects. It is also preferable.

The method of mixing the above-mentioned deodorizing/sterilizing component and other synthetic resin components of the present invention is a method of mixing powdered materials of both components, and a method of mixing each component into particles of appropriate particle size. If the deodorizing/sterilizing component is in the form of fibers, there is a method of cutting it into appropriate lengths and mixing it with powder or granules of other resin components.

Moldings can be produced from these mixtures by a commonly known molding method, such as melt extrusion or molding.

The deodorizing/sterilizing ingredients mentioned above and other synthetic resin ingredients should be as similar in properties as possible, such as compatibility and heat meltability, from the viewpoint of ease of molding and quality of molded products. A combination of things is preferred. Further, when the deodorizing/sterilizing component is in the form of fibers, the fibers act as a reinforcing material for the molded product. Furthermore, when producing a molded article from the above mixture, a foaming agent can be mixed to produce a foamed or shaped article. As the blowing agent used in this case, a conventionally known blowing agent can be used. Conventionally known methods can also be used for the molding method.The shaped article of the present invention is shaped into a plate-shaped article, a container, etc. by means such as melt extrusion molding, and can be used for floors, walls, It can be used as a building material for ceilings, etc., and as a container for odor-generating substances.

〔Example〕

The present invention will be explained below using examples. In the examples, % represents weight unless otherwise specified.Example 1 Acrylonitrile and acrylic acid were polymerized in an aqueous medium using acidic sodium sulfite and ammonium persulfate as catalysts. The obtained polymer was washed with water, neutralized with a 5% aqueous sodium hydroxide solution at 20°C, and treated with a 10% aqueous copper sulfate solution at 20°C. This polymer was thoroughly washed with water and dried in hot air at 80°C.

The composition and copper content of the obtained copper-containing polymer are shown in Table 1.

Next, the above copper-containing polymer and polyethylene were mixed in the proportions shown in Table 1, and extruded at 175° C. from a commonly known extruder to produce a plate-like product having a thickness of 4 mm and a width of 500 mm. Cut this plate-like material into a size of 50 mm in length and width,
It was processed into a tile-like shape and pasted on the bathroom wall, and was used for ■years.

For comparison, a polyethylene plate without any copper-containing polymer was produced, similarly attached to a bathroom wall, and used for one year.

As a result, no mold growth was observed on the surface of the plate-like product of the present invention, but mold growth was clearly observed on the surface of the comparative plate-like product.

The following Margin Example 2 Using the copper-containing polymer used in Experiment Nα5 shown in Table 1 of Example 1, it was mixed with polyethylene at the mixing ratio shown in Table 2, and molded at 175°C using a commonly known molding machine. inner diameter 1
0cm, height approx. 7. A 75 am cylindrical container was manufactured. In addition, a lid for the container was manufactured in the same manner, resulting in a container with a lid that can be sealed.

Each of the obtained containers was filled with air containing ammonia and hydrogen sulfide at the concentrations shown in Table 2, sealed, and left at 25° C. for 2 hours. After that, the reduction in ammonia and hydrogen sulfide in the air inside each container was investigated. The results are shown in Table 2.

(The following is a blank space) [Effects of the Invention] The molded product of the present invention is a molded product that has both the function of preventing bad odors and the sterilization performance, and exhibits excellent effects in preventing bad odors and bacterial growth.

Claims (1)

[Claims] 1. A deodorizing and sterilizing synthetic resin molded product comprising a deodorizing and sterilizing component (I) having copper bonded to an anionic functional group and a synthetic resin component (II).