JP2581235Y2 - Isothiocyanate ester sustained release sheet - Google Patents

Description

[Detailed description of the invention]

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an anti-bacterial property, a bactericidal property, and an isothiocyanate ester that is efficiently held by impregnating and holding an isothiocyanate ester in a pre-formed adhesive layer. The present invention relates to a sustained-release sheet for isothiocyanates having microbial protection and the like, and is widely used for purposes such as building materials, food-related products, shoe insoles, and the like for antibacterial, antifungal, and antimicrobial purposes. And a sustained release sheet for isothiocyanates.

[0002]

2. Description of the Related Art Isothiocyanates contained in mustard and wasabi have a bacteriostatic and bactericidal action, and they are bactericidal and bactericidal even at an extremely small vapor concentration of 10 to several hundred ppm, regardless of whether they are synthetic or natural. It is known that an effect can be obtained. Since this was reported, so far, isothiocyanates have been adsorbed on porous supports such as clay minerals or adsorbed on the surface of films and sheets to industrially control this bactericidal and bactericidal action. Attempts have been made to utilize, and some of them have been commercialized, for example, as freshness retaining materials.

[0003]

However, the conventional methods described above cannot sufficiently utilize the bacteriostatic and bactericidal effects of isothiocyanates. This is because, in these methods, many of the isothiocyanates are volatilized during the production process or storage and cannot carry an effective amount due to the high volatility of the isothiocyanates. In particular, when adsorbing on a porous carrier, it is necessary to provide a means for putting the bag into a bag having a sustained release property because the release rate is greatly dependent on the temperature, and it is also adsorbed on the surface of the film or sheet. In such a case, there are problems that it is difficult not only to impregnate the isothiocyanate in a sufficient amount to exert the effect but also to control the sustained release.

[0004]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have found that an isothiocyanate-impermeable barrier sheet and / or an isothiocyanate-permeable control sheet and a preformed pressure-sensitive adhesive layer Nii
Isothiocyanate impregnated with sothiocyanates
The above problem has been solved by combining an isothiocyanate supporting layer composed of an antacid- containing pressure-sensitive adhesive layer. That is, the isothiocyanate sustained-release sheet of the present invention has an isothiocyanate ester-bearing layer on both front and back sides coated with an isothiocyanate-impermeable barrier sheet and / or an isothiocyanate ester-permeable control sheet. An acid ester sustained release sheet, wherein the isothiocyanate-carrying layer is formed by impregnating and holding an isothiocyanate ester in a pre-formed pressure-sensitive adhesive layer. Further, the isothiocyanate sustained release sheet according to claim 2 is characterized in that the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is a pressure-sensitive adhesive that dissolves in or swells with the isothiocyanate. .

In this case, if one side is covered with the barrier sheet and the other side is covered with the control sheet, or if both sides are covered with the control sheet, the controlled release is controlled by the control sheet and both sides are covered with the control sheet. When coated with a barrier sheet, the sustained release is controlled by the exposed area of the end face of the isothiocyanate supporting layer.

As the isothiocyanate, various esters can be used irrespective of aliphatic esters such as allyl esters and alkyl esters of isothiocyanic acid, and aromatic esters, and particularly for foods. In this case, it is preferable to use natural isothiocyanates contained in mustard extract and the like.

The isothiocyanate-supporting layer is formed by impregnating and holding a preformed adhesive layer with isothiocyanate. In order to impregnate and hold the isothiocyanates in the pressure-sensitive adhesive layer formed in advance , for example, a gas barrier film that blocks the isothiocyanates such as Al-deposited polyethylene terephthalate must have compatibility with the isothiocyanates. A pressure-sensitive adhesive that quickly dissolves or swells is applied to form a pressure-sensitive adhesive layer, which is impregnated with an isothiocyanate, and a polyethylene film, a polypropylene film, an ultrathin polyethylene terephthalate film and other isothiocyanate are permeated therethrough. It can be formed by laminating the obtained films, and can carry an amount of isothiocyanates that cannot be achieved by the conventional technique without waste.

Examples of the adhesive which dissolves in the above-mentioned isothiocyanate or swells with the isothiocyanate include n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-diethylbutyl (meth) acrylate, and the like. (Meth) such as isooctyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and tridecyl (meth) acrylate ) One or more acrylic esters and (meth) acrylic acid copolymerizable with the esters;
Copolymers with functional monomers such as itaconic acid, maleic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, acrylamide, dimethylacrylamide, methylaminoethyl methacrylate, and methoxyethyl (meth) acrylate Acrylic adhesives, vinyl adhesives such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, natural rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene rubber, polybutene rubber, butyl rubber, etc. There is a rubber-based adhesive containing a synthetic rubber as a main component. The above acrylic, rubber, and vinyl adhesives can be selected and used, but it is preferable to select and use an acrylic adhesive. In particular, alkyl (meth) acrylates having 4 or more carbon atoms in the alkyl group can be used. A copolymer of the monomer and a copolymerizable monomer is preferred, and a crosslinked type is more preferred. In the adhesive, if necessary, a tackifier such as terpene resin, petroleum resin, liquid paraffin,
Adhesive strength of animal and vegetable oils (eg, olive oil, soybean oil, beef oil, tongue fat), polybutene, low-grade isoprene, wax, etc., retention agents, fillers such as titanium oxide, zinc oxide, aluminum metasilicate, calcium sulfate, calcium phosphate, etc. , Water and an emulsifier (eg, sorbitan monooleate, sodium lauryl sulfonate), and an emulsifier (eg, magnesium stearate, aluminum stearate) and the like. Adhesives other than those exemplified here can also be used as long as they can be dissolved or swelled in the isothiocyanate to be impregnated with the isothiocyanate.

It is desirable that the isothiocyanate is impregnated and held at about 0.1 to 50% by weight with respect to the pressure-sensitive adhesive. The content of isothiocyanates is 0.1 g / m2.
^It is desirable to keep ^two or more impregnations. However, since the amount of the isothiocyanate to be supported is selected depending on each use, it may be out of the above concentration range.

The isothiocyanate-impermeable barrier sheet used in the present invention includes vinylidene,
There are resin films and metal foils of acrylonitrile, ethylene-polyvinyl alcohol copolymer, polyethylene terephthalate, polycarbonate and the like. Examples of the isothiocyanate permeability control sheet include resin films such as polyethylene, polypropylene, and vinyl chloride, paper, cloth, and synthetic paper. Also, the barrier sheet changes its transmittance by reducing its film thickness, and can be used as a control sheet.

[0011]

The isothiocyanate sustained-release sheet of the present invention not only allows the isothiocyanate to be retained in the sheet at a high concentration and effectively by the above constitution, but also releases the isothiocyanate vapor. It can be controlled freely by selecting the film.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the isothiocyanate sustained release sheet of the present invention will be described with reference to specific embodiments. Example 1 As shown in FIG. 1, an acrylic pressure-sensitive adhesive layer 2 containing 20% by weight of allyl isothiocyanate was formed on a vapor-deposited layer 1a of an aluminum-deposited polyethylene terephthalate film 1 having a thickness of 25 μm, and a polyethylene film 3 having a thickness of 60 μm was formed thereon. A laminated sustained release sheet was obtained. When the release of allyl isothiocyanate was examined, the release rate was 10.6 g /
The release continued for about 1 hour at m ² · h.

Example 2 A sustained-release sheet was obtained in the same manner as in Example 1 except that the polyethylene film of Example 1 was replaced with a polyethylene terephthalate film having a thickness of 16 μm. When the release of allyl isothiocyanate was examined, the release was continued at a release rate of 0.28 g / m ² · h for about 36 hours.

Example 3 A sustained release sheet was obtained in the same manner as in Example 1 except that the polyethylene film in Example 1 was replaced with a polyethylene terephthalate film having a thickness of 50 μm. When the release of allyl isothiocyanate was examined, the release was sustained at a release rate of 0.09 g / m ² · h for about 105 hours.

Example 4 A sustained release sheet was obtained in the same manner as in Example 1 except that the polyethylene film in Example 1 was replaced with a polypropylene film having a thickness of 60 μm. When the release of allyl isothiocyanate was examined, the release rate was 0.83.
The release lasted for about 12 hours at g / m ² · h.

Example 5 A sustained-release sheet was obtained in the same manner as in Example 1 except that the polyethylene film of Example 1 was replaced with an Al-deposited polyethylene terephthalate film having a thickness of 25 μm. When the release of allyl isothiocyanate was examined, the release was continued for about 2900 hours at a release rate of 0.003 g / m ² · h.

[0017]

According to the method of isothiocyanate inclusion in cyclodextrin or adsorption to a porous carrier such as clay mineral, a small amount of isothiocyanate is obtained in the form of a final sheet. Not only did they contain it, but the price was very high. According to the present invention, a large amount of isothiocyanates can be contained, and a sustained release can be achieved. Also, the cost can be kept to a minimum, so that the product is inexpensive.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of one embodiment of a sustained release sheet for isothiocyanates of the present invention.

[Explanation of symbols]

 Reference Signs List 1 Al-deposited polyethylene terephthalate film 1a Deposited layer 2 Acrylic adhesive layer 3 Polyethylene film

──────────────────────────────────────────────────続 き Continuing on the front page (72) Shuzo Nakagawa 5-32-21 Inari, Soka City, Saitama Prefecture (72) Hideaki Okabe 7-7-3 Tsuji, Urawa City, Saitama Prefecture Lintec Urawa Second Dormitory 506 (72 ) Inventor Kazuya Kato 7-7-3 Tsuji, Urawa-shi, Saitama Prefecture Lintec Urawa 3rd dormitory 210 (72) Inventor Hiroshi Nagaki 1-8-2 Kaedigaoka, Hatoyama-cho, Hiki-gun, Hiki-gun, Saitama (56) References JP-A-3-2235 (JP, A) JP-A-62-158672 (JP, A) JP-B-1-32201 (JP, B2) Jikken Sho 57-21700 (JP, Y2) (58) Fields surveyed (58) Int.Cl. ⁶ , DB name) B32B 1/00-35/00

Claims (2)

(57) [Scope of request for utility model registration] An isothiocyanate sustained-release sheet comprising an isothiocyanate-ester-supporting layer coated on both sides thereof with an isothiocyanate-impermeable barrier sheet and / or an isothiocyanate-ester permeable control sheet. Thus, the isothiocyanate supporting layer is formed of isothiocyanates in advance.
A sustained release sheet of isothiocyanates, wherein the pressure-sensitive adhesive layer is impregnated and held. 2. The sustained release of isothiocyanates according to claim 1, wherein the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is an adhesive which dissolves in or swells with isothiocyanates. Sheet.