JPH02164368A - Antibacterial aromatic film and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide excellent antibacterial and aromatic properties to different base material for a long period of time under environment wherein moisture and sweat are easy to attach, by forming film-formed resin containing a metal- containing antibacterial agent and an aromatic through a hardening process using electron beam irradiation to corresponding monomer and/or oligomer composition. CONSTITUTION:An antibacterial and aromatic film is fabricated by coating the base with a liquid composition containing a minor amount of metal- containing antibacterials agent and an aromatic and radiation co-polymerizing monomer and/or oligomer, and by irradiating electron beam onto this coating film followed by hardening process. When forming film solely, the base shall preferably consist of paper, film, or flat plate with good exfoliating property. As copolymerizing monomer, compound having vinyl group is suitable, in particular methacryloyl group or acryloyl group containing compound. The copolymerizing oligomer, on the other hand, preferably gas a molecular weight of several tens thru hundreds of thousands including a plurality of methacryloyl groups or acryloyl groups per molecule, wherein the main chain is suitably epoxy chain.

Description

[Detailed description of the invention] (b) Industrial application fields The present invention relates to an antibacterial/fragrant membrane and a method for producing the same.

More specifically, the present invention relates to an antibacterial agent and fragrance-containing film formed on the surface of various substrates desired to have antibacterial properties and aromatic properties, and a method for producing the same. The antibacterial and aromatic membrane of this invention is
! It is useful as a surface coating film for substrates that are prone to growth and bad odors.

(B) Conventional technology In each type of base material, such as wall materials, clothing accessories, and shoe insoles, which are exposed to moisture and sweat at a suitable temperature, various microorganisms such as bacteria and fungi can They tend to breed and cause foul odors due to such breeding. The proliferation of such microorganisms and the generation of bad odors cause discomfort and are undesirable from a sanitary standpoint, and it is desirable to prevent this as much as possible.

(c) Problems to be solved by the invention For this reason, for example, if the base material is a synthetic resin, an antibacterial agent may be added by mixing it before molding to prevent or suppress the growth of microorganisms on its surface. There are known ways to do this.

Apart from this, it is also common practice to apply a perfume to the surface of a base material or to microcapsule the perfume and contain it in the base material to prevent bad odors.

However, the former method of containing an antibacterial agent is uneconomical as it requires the use of more antibacterial agent than is necessary to impart antibacterial properties to the surface. It was difficult to do so. Furthermore, the latter method using fragrances does not fundamentally solve the problem because it basically cannot prevent the proliferation of microorganisms. Moreover, when microencapsulated, the release of the fragrance is insufficient, and when applied to the surface, it is dispersed in a short period of time, making it difficult to prevent the generation of bad odors over a long period of time. Ta.

In this regard, in order to impart antibacterial properties and aromatic properties,
Although it is possible to incorporate both an antibacterial agent and a fragrance into the synthetic resin base material, it is difficult to impart appropriate sustained release properties to the fragrance as described above, and it is also disadvantageous from an economic point of view. there were.

Furthermore, it has been difficult to impart antibacterial and aromatic properties to the surface of paper materials, leather materials, etc. other than synthetic resin base materials simply and over a long period of time.

This invention was made under such circumstances, and provides antibacterial and aromatic properties that can impart excellent antibacterial properties and aromatic properties over a long period of time to various base materials in environments where moisture, sweat, etc. are likely to come into contact with them. The aim is to provide a membrane.

(d) Means for Solving the Problems From the above perspective, the present inventor has conducted intensive research and has developed a liquid composition that uses radiation-polymerizable monomers and/or oligomers as raw materials, and mixes a metal-containing antibacterial agent and fragrance. After applying the material to the substrate, it is cured by irradiating it with an electron beam.
The inventors have discovered the fact that it is possible to impart excellent antibacterial properties to the surface of a substrate over a long period of time and to efficiently form a resin film that has an appropriate sustained release property for perfume, and has thus arrived at the present invention.

Thus, according to the present invention, a metal-containing antibacterial agent and a fragrance are contained in a film-like resin, and this film-like resin is formed by curing treatment by electron beam irradiation on a corresponding monomer and/or oligomer composition. Provided is an antibacterial/fragrant membrane made of

The antibacterial/fragrant film of the present invention is usually in the form of being coated on the surface of a substrate to which antibacterial properties and aromatic properties are to be imparted. However, in some cases, it may be in the form of an independently manufactured product as an antibacterial/fragrant film. Substrates that are intended to be imparted with antibacterial properties and aromatic properties include various substrates in environments where they may come into contact with moisture and sweat, such as various interior paper materials, wall materials, handbags, slippers, and hats. Examples include insole, fashion goods such as shoes and insoles, and daily necessities such as toilet goods and cosmetic cases.

Further, its shape is not limited to a planar shape, but may be a fibrous shape such as a nonwoven fabric or a woven fabric, or a porous body such as a foam. In the case of a foam, the inner surface may be coated. The surface of these substrates may be coated with an electron-irradiated resin film that is the material resin for the antibacterial/fragrant film of the present invention.

The metal-containing antibacterial agent in the present invention refers to an antibacterial substance containing heavy metals such as zinc, copper, silver, tin, etc. as an antibacterial active ingredient, either as is or in the form of ions, or bound in a compound. The compound may be an inorganic compound or an organic compound. Specifics of such antibacterial agents 1
Examples include heavy metal fine powder, easily water-soluble heavy metal salts (e.g.
heavy metal sulfates, etc.), Yoiki metal compounds (e.g., ziram,
zineb, maneb, fentin hydroxide, etc.)
Examples include. These antibacterial agents may be in the form of suitable carriers and fillers, such as metal oxides such as aluminum oxide, silicon oxide, calcium oxide, etc., or may be in the form of wettable powders, and may contain at least It is acceptable as long as it contains heavy metals as an antibacterial active ingredient.

Such antibacterial agents are non-volatile substances that do not decompose or retain their antibacterial properties even if decomposed by electron beam irradiation; therefore, their antibacterial properties are substantially inhibited by the curing treatment of the film-like resin. There isn't.

The fragrance in this invention may be a natural fragrance such as a vegetable fragrance or an animal fragrance (or may be a synthetic fragrance, and various fragrances known in the art can be used. Examples include scents secreted by various animals, essential oils of plants, and various synthetic fragrances such as terpene-based, aromatic, alcohol-based, aldehyde-based, ester-based, ketone-based, lactone-based, phenol-based, and oxide-based fragrances.

The antibacterial/fragrant film of the present invention is produced by applying a liquid composition containing a radiation-polymerizable monomer and/or oligomer, a small amount of a metal-containing antibacterial agent, and a fragrance onto a substrate, and then irradiating the applied film with an electron beam. It can be manufactured by curing the coating film. At this time, the substrate may be the object to be treated, but when forming the film alone, it is suitable to use paper, film, or a flat plate with good patternability.

As the polymerizable monomer, a compound having a vinyl group is suitable, and it is particularly preferable to use a compound containing a methacryloyl group or an acryloyl group. Examples of such monomers include (meth)acrylic acid lower alkyl ester, styrene, divinylbenzene, N-vinylpyrrolidone, phenyl (meth)acrylate, polyethylene glycol (meth)acrylate, 1,3-butylene glycol di(meth) ) acrylate, polybrobylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, 2,6-hexanethiol di(meth)acrylate, ethylene glycol di(meth)acrylate, meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dibrobylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,3
-Butanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, phenylene di(meth)acrylate
Acrylate etc. are suitable. Among these, it is more preferable to use aliphatic or aromatic, difunctional or trifunctional (meth)acrylates.

On the other hand, as the above-mentioned polymerizable oligomer, one having a molecular weight of tens of thousands to hundreds of thousands (number average molecular weight) having multiple methacryloyl groups or acryloyl groups in the molecule is suitable, and its main chain is an epoxy chain or a polyester chain. , polyurethane chains, etc. are suitable.

Such oligomers include, for example, a polyfunctional oligomer (No.

5007). Such oligomers help provide flexibility, weather resistance, toughness, etc. to the membrane.

In this invention, it is possible to use both the polymerizable monomer and the polymerizable oligomer, but the polymerizable monomer and the polymerizable oligomer are particularly advantageous in terms of shape retention and appropriate flexibility of the obtained film-like molded product. Monomer 50-100
It is suitable to use a single monomer as a mixture of 50% to 0% by weight of the polymerizable oligomer.

The amount of metal-containing antibacterial agent contained in such a liquid composition is
The amount is set within a range that does not impede the durability of the resin film, and in consideration of its antibacterial effect and economical efficiency, the amount is usually adjusted to 0.5 to 5% by weight in the resin film.
It is preferably 1 to 3% by weight. Similarly, the amount of fragrance to be contained is similarly small, and usually 0,
It is suitable to adjust it to 5 to 5% by weight, and 1
The content is preferably 2% by weight.

Incidentally, such a liquid composition may contain a solvent or a plasticizer as necessary. In particular, a plasticizer is added as appropriate from the viewpoint of flexibility of the resulting film and control of shrinkage of the coated film. Examples of such plasticizers include phthalic acid esters such as diethyl phthalate and dioctyl phthalate, and fatty acid esters such as diisobutyl adipate. Further, it is preferable that the blending amount of these components is within 20% by weight in terms of shape retention of the film.

Such a liquid composition can be applied by any method (brushing,
(dipping, spinner, etc.), and the coating thickness is preferably from a, aal to 0,1■ in terms of providing sufficient long-term antibacterial and aromatic properties and from the economical point of view. 0. It is preferable to set QO1 to 0.03x shoulder.

The amount of electron beam irradiated to such a coating film is 0.1 to 0.1 to 100% from the viewpoint of film durability, sustained release of antibacterial agents and fragrances, and cost.
A value of 10 Mrad is suitable. In order to prevent side reactions other than polymerization and crosslinking reactions of monomers and oligomers, such electron beam irradiation is performed in a low-oxygen atmosphere with an oxygen concentration of 500 ppI11 or less, or with the coating surface covered with an appropriate sealing film. It is suitable to do so.

The antibacterial and aromatic membrane of this invention obtained in this way is
The gelation rate is preferably 60% or more, and the mechanical strength of the film can be adjusted by increasing the electron beam irradiation dose, and the gelation rate is preferably 85 to 100%.

(e) Action Electron beam irradiation causes polymerization and crosslinking of monomers and/or oligomers, thereby curing the coating film, and as a result, the antibacterial agent and fragrance are encapsulated within the polymer matrix. As a result, the antibacterial agent is difficult to dissipate even in the presence of water or moisture, and the surface antibacterial properties are maintained for a long period of time.Also, the fragrance is also provided with sustained release properties and maintains its aromatic properties for a long period of time. A durable coating will be formed.

(f) Examples Example 1 Polyester acrylate LR as a polymerizable monomer
-3566 [trade name of electron beam curable resin manufactured by Toyo Ink Mfg. Co., Ltd.] was used, and Zeomic as a metal-containing antibacterial agent [(manufactured by Aminshinanen New Ceramics; zinc, copper and silver in a ratio of approximately 1:0) was used. .2: 11% by weight of an inorganic antibacterial agent contained in 0.6 and rose oil [(
1.5% by weight was added and sufficiently stirred to obtain a liquid composition, which was used as a base material to make shoe insoles [commercial product; non-woven synthetic resin molded product: approximately 8 x 25 cm] (film thickness: 5μIi).

Next, the insole was made waterproof by irradiating the coated surface with 3 Mrad of 150 KeV electron beam using an electron beam irradiation device (EBC-200-20-15) manufactured by Nissin High Voltage Co., Ltd. An antibacterial and aromatic film with a thickness of approximately 5 μm was formed.

Culture solutions of Aspergillus niger and Pseudomonas aeruginosa were applied to the thus obtained insole and the insole without the antibacterial/aromatic film formed, respectively, and changes in the number of bacteria were measured at room temperature. . The results are shown in the table below.

Thus, it was confirmed that the antibacterial/fragrant membrane of the present invention significantly suppresses the growth of microorganisms. It was confirmed that the antibacterial properties were maintained even after 100 days.

On the other hand, the above-mentioned antibacterial/fragrant film does not cause any discomfort by masking the sweaty odor even when the insole is used due to the aromatic properties of the fragrance, and this aromatic property remains after 6 months of use. It was confirmed that the same was maintained.

Example 2 Polyester acrylate LR as a polymerizable monomer
-3574 [trade name j of electron beam curable resin manufactured by Toyo Ink Manufacturing (Aji), 1% by weight of the antibacterial agent Zeomic used in Example 1, and cypress oil as a fragrance [manufactured by Yomen Fragrance Co., Ltd.] 1 % by weight was added and mixed, and this was applied to the surface of decorative wallboard paper [picture pattern: 15 x 18 cm] to a thickness of about 10 μm. A 150 KeV electron beam was applied to this coated surface at 5 Mr.
By irradiating with AD, a water-resistant, antibacterial and aromatic film with a thickness of about 10 μm was formed.

This decorative paper is commonly used in 7.1.
0 to 80% RH), and its surface was observed over time. As a result, no black spots due to mold growth were observed on the surface of the decorative paper after 6 months, confirming that cleanliness was maintained. It was also confirmed that the aroma of cypress wood remained good even after 6 months.

(G) Effects of the Invention According to the antibacterial/fragrant membrane of the present invention, antibacterial properties and aromatic properties are exhibited over a long period of time. The film itself has excellent water resistance and durability. Therefore, it is extremely useful as a film for imparting antibacterial properties and aromatic properties to various substrates, especially substrates that are susceptible to microbial growth due to contact with moisture or sweat.

Furthermore, since the antibacterial/fragrant film of the present invention does not require the application of heat during formation, antibacterial agents and fragrances are less likely to decompose or escape during formation, resulting in improved usage efficiency.

Claims (1)

[Claims] 1. A metal-containing antibacterial agent and a fragrance are contained in a film-like resin, and this film-like resin is cured by curing the corresponding monomer and/or oligomer composition by electron beam irradiation. An antibacterial and aromatic film is formed. 2. A liquid composition containing a radiation-polymerizable monomer and/or oligomer and a small amount of a metal-containing antibacterial agent and a fragrance is applied onto a substrate, and the coating film is cured by irradiating the coating film with an electron beam. A method for producing an antibacterial and aromatic membrane characterized by: