JPH06212136A - Bactericidal adhesive, method for producing the same, and adhesive product - Google Patents

Abstract

(57) [Summary] [Structure] A bactericidal pressure-sensitive adhesive of the present invention, a method for producing the same, and a pressure-sensitive adhesive product provided with the pressure-sensitive adhesive on a substrate are polymers which are dissolved in isothiocyanates or swollen by isothiocyanates. It is characterized in that an isothiocyanate ester is impregnated and held in a pressure sensitive adhesive mainly composed of. [Effects] Isothiocyanic acid esters can be carried at a high concentration, and by utilizing the adhesiveness of the adhesive, in the form of any adhesive product such as sheet, tape, label, etc.
It can be used by appropriately adhering it to a desired site, and has the effect that the bacteriostatic property, bactericidal property, antimicrobial property, etc. of isothiocyanates can be effectively utilized.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides an isothiocyanic acid ester which is efficiently retained by an adhesive to provide antibacterial and bactericidal properties.
The present invention relates to a bactericidal pressure-sensitive adhesive having antibacterial properties and the like, a method for producing the same, and an adhesive product to which the pressure-sensitive adhesive is applied. The present invention relates to a bactericidal pressure-sensitive adhesive for use in the above, a method for producing the same, and an adhesive product.

[0002]

2. Description of the Related Art Isothiocyanic acid esters contained in mustard and horseradish have antibacterial and bactericidal effects, and even if they are synthetic or natural, they are bactericidal and bactericidal even at an extremely minute vapor concentration of 10 to several hundred ppm. It is known that an effect can be obtained. Since the fact that this was reported, isothiocyanates have been industrially adsorbed on porous supports such as clay minerals, or adsorbed on the surface of films and sheets to industrially control the bactericidal and bactericidal activity. Some attempts have been made to utilize the above, and some have been commercialized as, for example, freshness-retaining materials.

[0003]

However, the above conventional methods have not been able to fully utilize the antibacterial and bactericidal action of isothiocyanates. This is because in these methods, due to the high volatility of the isothiocyanates, most of the isothiocyanates are volatilized during the manufacturing process and storage, and an effective amount cannot be supported. In particular, when adsorbing to a porous carrier, since the release rate greatly depends on the temperature, it is necessary to arrange a means to put it in a bag having a sustained release property, and to adsorb it on the surface of the film or sheet. In this case, there are problems that it is difficult to impregnate the isothiocyanic acid ester in an amount sufficient to exert the effect, and it is difficult to control the sustained release property.

[0004]

Means for Solving the Problems As a result of intensive studies by the present inventors, as a pressure-sensitive adhesive, the use of a polymer that dissolves in isothiocyanates or swells with isothiocyanates makes it possible to obtain physical properties as a pressure-sensitive adhesive. The inventors have found that the isothiocyanic acid esters can be effectively impregnated and retained while maintaining the above, and overcome the above problems. That is, the bactericidal pressure-sensitive adhesive of the present invention is characterized in that an isothiocyanic acid ester is impregnated and held in a pressure-sensitive adhesive mainly composed of a polymer which is dissolved in isothiocyanic acid esters or swollen by isothiocyanic acid esters.
Further, the method for producing a bactericidal pressure-sensitive adhesive of the present invention comprises forming a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive mainly composed of a polymer which is dissolved in isothiocyanic acid esters or swelled by isothiocyanic acid ester, and isothiocyanic acid is then added to the pressure-sensitive adhesive layer. It is characterized by being impregnated with esters. Furthermore, the adhesive product of the present invention is characterized in that the bactericidal adhesive is applied to at least one surface of a substrate.

The adhesive mainly composed of a polymer which is dissolved in the isothiocyanates or swollen by the isothiocyanates is (meth) acrylic acid n.
-Butyl, hexyl (meth) acrylate, 2-diethylbutyl (meth) acrylate, isooctyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic One or more kinds of (meth) acrylic acid ester such as acid decyl, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and (meth) acrylic acid, itaconic acid, maleic acid copolymerizable with the ester Acrylic adhesives such as acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, acrylamide, dimethylacrylamide, methylaminoethyl methacrylate, methoxyethyl (meth) acrylate and copolymers with functional monomers , Ethyl vinyl ether,
Propyl vinyl ether, butyl vinyl ether, 2-
Vinyl adhesive such as ethylhexyl vinyl ether,
There are rubber-based pressure-sensitive adhesives containing natural rubber and synthetic rubber such as styrene-isoprene-styrene block copolymer rubber, styrene-butadiene rubber, polybutene rubber and butyl rubber as main components. The above-mentioned acrylic, rubber-based, and vinyl-based pressure-sensitive adhesives can be selectively used, but it is preferable to use the acrylic-based pressure-sensitive adhesives selectively. In particular, a (meth) acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms is used. A copolymer of the monomer and a copolymerizable monomer is preferable,
A cross-linking type is more preferable. In the adhesive, if necessary, a terpene-based resin, a tackifier such as a petroleum-based resin, liquid paraffin, animal and vegetable oil (for example, olive oil, soybean oil, beef oil, ton fat), polybutene, lower isoprene,
Adhesive strength / holding power regulators such as wax, fillers such as titanium oxide, zinc oxide, aluminum metasilicate, calcium sulfate and calcium phosphate, water and emulsifiers (eg sorbitan monooleate, sodium lauryl sulfonate), emulsification aids ( For example magnesium stearate,
Aluminum stearate) or the like can also be added. Further, as long as it is an adhesive that can be impregnated and held with isothiocyanates by being dissolved or swollen in isothiocyanates, adhesives other than those exemplified here can also be used.

As the isothiocyanates, various esters can be used regardless of aliphatic esters such as allyl ester and alkyl ester of isothiocyanate, or aromatic esters, but especially for foods. In this case, it is preferable to use natural isothiocyanates contained in mustard extract and the like.

The isothiocyanic acid ester is preferably impregnated and held in the adhesive in an amount of about 0.1 to 50% by weight, and 0.1 g of the isothiocyanic acid ester is contained.
/ M ² or more is preferably contained and held. When the pressure-sensitive adhesive is impregnated with isothiocyanic acid esters, a solvent or oils and fats having good compatibility with the pressure-sensitive adhesive and isothiocyanic acid esters can be mixed and impregnated. The method of impregnating the isothiocyanate ester into the pressure-sensitive adhesive layer includes gravure coating, Meyer bar coating, spray coating, caten coating, streak coating from nozzles, dipping, etc.
The method is not particularly limited. The impregnating step is preferably performed at a temperature of the atmosphere including the pressure-sensitive adhesive layer at room temperature or below room temperature.

In order to produce the above-mentioned bactericidal pressure-sensitive adhesive, for example, a gas barrier film such as an Al vapor-deposited polyethylene terephthalate film which is a barrier against isothiocyanates can be quickly dissolved by having compatibility with isothiocyanates. Or, it can be produced by applying a swelling adhesive to form an adhesive layer and impregnating it with isothiocyanates, and carrying an amount of isothiocyanates that could not be achieved by conventional techniques without waste. be able to. Incidentally, by sticking a film having permeability to isothiocyanates such as polyethylene or polypropylene on the surface of the pressure-sensitive adhesive layer, the sustained release of isothiocyanates can be easily controlled. Also,
By sticking a gas barrier film on the surface of the pressure-sensitive adhesive layer, isothiocyanates can be retained for a long time. Incidentally, the adhesive product, including the above-mentioned constitution, is basically a bactericidal adhesive applied to at least one surface of the substrate, and in detail, polyethylene terephthalate, polypropylene, vinyl chloride, Resin film and paper such as polyethylene, polycarbonate, vinylidene resin, acrylonitrile, ethylene-polyvinyl alcohol copolymer, etc.
A bactericidal pressure-sensitive adhesive is provided on one or both sides of a substrate such as cloth, synthetic paper, metal foil, etc., which is usually peeled off to protect the pressure-sensitive adhesive layer. A film having a gas barrier property is temporarily attached. Such adhesive products are usually adhesive labels,
It is called an adhesive sheet. Incidentally, one side of the base material was provided with an adhesive layer, the other side was subjected to a peeling treatment, and was made into a roll shape,
The form of so-called adhesive tape is also included in this product. As described above, the sustained release property can be controlled by changing the gas barrier property of the base material. still,
Providing a vapor-deposited layer or a coating layer on the substrate is an optional matter if necessary.

[0009]

The bactericidal pressure-sensitive adhesives and pressure-sensitive adhesive products impregnated with isothiocyanates according to the present invention not only enable the isothiocyanates to be retained in a high concentration and effectively but also have By utilizing the advantage of adhering to all things, it is possible to utilize the vapor emission of isothiocyanates without the need for special equipment.Therefore, sterilization, sterilization, microbial protection and freshness of isothiocyanates are possible. It can be widely used in various fields of effects such as retention. Further, by using a method of impregnating the isothiocyanic acid ester into the pressure-sensitive adhesive layer after forming the pressure-sensitive adhesive layer, it is possible to form the pressure-sensitive adhesive layer after the isothiocyanic acid ester is contained in the pressure-sensitive adhesive in advance. By comparison, a much higher concentration of isothiocyanates can be retained in the adhesive layer.

[0010]

EXAMPLES Next, the bactericidal pressure-sensitive adhesives and pressure-sensitive adhesive products of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 An ethyl acetate solution containing a copolymer of 97% by weight of 2-ethylhexyl acrylate and 3% by weight of acrylic acid in a ratio of 40% by weight was prepared. To this, 1% by weight of an isocyanate cross-linking agent was added, and this was applied onto a polyester film on which Al was vapor-deposited, and dried at 100 ° C for 2 minutes, so that the pressure-sensitive adhesive layer had a thickness of 30 μm. Was prepared. Further, at room temperature, the stock solution of allyl isothiocyanate is impregnated into the pressure-sensitive adhesive layer to prepare a pressure-sensitive adhesive sheet containing 10% by weight of allyl isothiocyanate in the pressure-sensitive adhesive.
An adhesive product with a release paper laminated with an Al vapor-deposited polyester film having one surface treated with silicone was obtained.

Example 2 An adhesive product with release paper was obtained in the same manner as in Example 1 except that the adhesive contained 0.1% by weight of allyl isothiocyanate.

Example 3 An adhesive product with release paper was obtained in the same manner as in Example 1 except that 25% by weight of allyl isothiocyanate was contained in the adhesive.

Example 4 An adhesive product with release paper was obtained in the same manner as in Example 1 except that 50% by weight of allyl isothiocyanate was contained in the adhesive.

Example 5 Styrene-isobutylene-styrene block copolymer (Califlex TR110 manufactured by Shell Chemical Co., Ltd.)
7) 100 parts, liquid paraffin 60 parts, tackifier (Arakawa Chemical Co., Ltd. Alcon P100) 150 parts were dissolved in toluene, this solution was applied to an Al vapor-deposited polyester film, and dried at 100 ° C for 2 minutes. Thus, an adhesive sheet having an adhesive layer thickness of 30 μm was prepared. further,
A stock solution of allyl isothiocyanate was impregnated at room temperature into a pressure-sensitive adhesive layer to prepare a pressure-sensitive adhesive sheet containing 5% by weight of allyl isothiocyanate, and an Al vapor-deposited film having a release treatment on one side and a pressure-sensitive adhesive product with a release paper were obtained. .

Example 6 The same ethyl acetate solution of 2-ethylhexyl acrylate acrylic acid copolymer as in Example 1 was applied onto the release surface of an Al vapor-deposited polyester film treated with a single-sided release paper.
Dry at 100 ° C for 2 minutes, the thickness of adhesive layer is 25μ
A pressure-sensitive adhesive sheet of m was prepared and laminated with a non-woven fabric.
Further, a pressure-sensitive adhesive layer having a thickness of 25 μm was formed on the release surface of the Al vapor-deposited polyester film which had been separately subjected to one-side release treatment, and this pressure-sensitive adhesive layer was impregnated with allyl isothiocyanate at room temperature. Next, the non-woven fabric surface of the non-woven fabric to which the adhesive sheet was attached and the adhesive face of the adhesive sheet impregnated with allyl isothiocyanate were attached to obtain a double-sided adhesive product containing 10% by weight of allyl isothiocyanate.

Comparative Example 1 A silicone adhesive was used to form an adhesive layer of 30 μm on Al.
It was formed on a vapor-deposited polyester film, and an undiluted solution of allyl isothiocyanate was applied to the pressure-sensitive adhesive layer at room temperature to obtain a pressure-sensitive adhesive product with an Al vapor-deposited film that had been subjected to a single-sided fluorine-based peeling treatment and a laminated release film.

Comparative Example 2 A double-sided adhesive product was obtained in the same manner as in Example 6 except that the adhesive layer was not impregnated with allyl isothiocyanate.

Next, the adhesive strength (JIS Z0237) of the adhesive products obtained in Examples 1 to 5 and Comparative Example 1 was measured, and the results shown in Table 1 below were obtained.

[0019]

[Table 1]

As is apparent from Table 1, Examples 1 to 5
The adhesive product obtained in 1. has adhesiveness even when it contains allyl isothiocyanate in a high concentration, and is formed into a sheet,
It can be seen that it can be attached to or adhered to an adherend. On the other hand, when a silicone adhesive that is soluble in allyl isothiocyanate or does not swell with allyl isothiocyanate is used as the adhesive, the adhesive isothiocyanate remains in a liquid state on the adhesive surface and the release film surface to improve the adhesiveness. It turns out that they do not have it.

Next, the residual rate of allyl isothiocyanate was measured when the pressure-sensitive adhesive product with release paper obtained in Example 1 was allowed to stand at room temperature, and the results shown in Table 2 below were obtained.

[0022]

[Table 2]

As is clear from Table 2, even when left at room temperature, by taking the form as in Example 1, it is possible to significantly reduce volatilization.

Next, using the double-sided adhesive products obtained in Example 6 and Comparative Example 2, two 5 mm-thick plywood boards were pasted together and allowed to stand in an atmosphere of 25 ° C. × 70% Rh to propagate mold. Was observed over time. As a result, almost no mold was observed even after one month in the case of using the double-sided adhesive product of Example 6, whereas in the case of using the double-sided adhesive product of Comparative Example 2, it partially occurred after 1 week. Mold developed on the surface, and after 2 weeks the mold had spread to almost the entire surface.

Next, the release film of the adhesive product with release paper obtained in Examples 1, 3, and 4 was peeled off so that the surface of the adhesive did not come into contact with the inner wall of the container in a 500 cm ³ stainless container. After allowing to stand, the atmospheric concentration of allyl isothiocyanate in the container was measured over time by gas chromatography. As a result, as shown in FIG. 1, it is found that each adhesive product can promptly release allyl isothiocyanate and keep the allyl isothiocyanate concentration in the sealed container constant.

Example 7 An ethyl acetate solution containing a copolymer of 97% by weight of 2-ethylhexyl acrylate and 3% by weight of acrylic acid in a ratio of 40% by weight was applied to a polyester film having a thickness of 38 μm at 100 ° C. It was dried for 1 minute to form a 30 μm pressure-sensitive adhesive layer. Next, at room temperature, allyl isothiocyanate was gravure-coated (gravure mesh: lattice 120 mesh manufactured by Asahi Roll Co., Ltd.) on the pressure-sensitive adhesive layer to contain allyl isothiocyanate in the pressure-sensitive adhesive layer, and the thickness was 50 μm. A sheet containing allyl isothiocyanate was prepared by laminating the sheet with the polyethylene film of.

Example 8 After an acrylic pressure-sensitive adhesive layer having a thickness of 30 μm was formed on a polyester film having a thickness of 38 μm in the same manner as in Example 7, allyl isothiocyanate was coated on the pressure-sensitive adhesive surface using a Meyer bar. Then, allyl isothiocyanate was contained in the pressure-sensitive adhesive layer, and this was bonded to a 38 μm-thick release-treated polyester film to prepare an allyl isothiocyanate-containing pressure-sensitive adhesive sheet.

Comparative Example 3 An ethyl acetate solution containing 40% by weight of a copolymer of 97% by weight of 2-ethylhexyl acrylate and 3% by weight of acrylic acid was added with 20 parts of allyl isothiocyanate per 100 parts by weight of the solution. Add by weight, and apply this to a 38 μm thick polyester film, dry for 1 minute at 80 ° C. to form a 30 μm pressure-sensitive adhesive layer, and attach this to a 50 μm thick polyethylene film, containing allyl isothiocyanate Created a sheet.

Comparative Example 4 An emulsion solution containing a copolymer of 97% by weight of 2-ethylhexyl acrylate and 3% by weight of acrylic acid in a ratio of 65% by weight was added with 32 parts of allyl isothiocyanate per 100 parts by weight of the solution. Add 5 parts by weight and apply this to a polyester film having a thickness of 38 μm.
A pressure-sensitive adhesive layer having a thickness of 30 μm was formed by drying at 1 ° C. for 1 minute, and the pressure-sensitive adhesive layer was bonded to a polyester film having a thickness of 38 μm, which was treated with release, to prepare a sheet containing allyl isothiocyanate.

Next, Examples 7 and 8 and Comparative Example 3
When the contents of allyl isothiocyanate of 4 and 4 were measured, the measurement results shown in Table 3 below were obtained. still,
The content is cut to a size of 20 cm × 10 cm from the sample sheet, and is dried at 10 Torr, 40 by using a vacuum dryer.
Allyl isothiocyanate was left to stand at 48 ° C for 48 hours, and the content was determined from the weight change and the amount of adhesive applied.

[0031]

[Table 3]

[0032]

As described above, according to the bactericidal pressure-sensitive adhesive and the method for producing the same of the present invention, isothiocyanates can be carried at a high concentration, and the adhesiveness of the pressure-sensitive adhesive can be utilized to
In the form of any adhesive product such as sheet, tape, label, etc., it can be used by appropriately adhering it to a desired site, and the effect of effectively utilizing the bacteriostatic property, bactericidal property, antimicrobial property, etc. of isothiocyanates Have.

[Brief description of drawings]

FIG. 1 is a characteristic diagram showing the release characteristics of allyl isothiocyanate of a bactericidal adhesive of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Yuichi Mizukami 3-2-1-1-62-907 Nakamachi, Minatojima, Chuo-ku, Kobe-shi, Hyogo Prefecture (72) Shuzo Nakagawa 5-32-21 Inari, Soka-shi, Saitama Prefecture (72) ) Inventor Hideaki Okabe 7-7-3 Tsuji, Urawa-shi, Saitama Lintec Urawa No. 2 Dormitory No. 506 (72) Inventor Kazuya Kato 7-7-3 Tsuji, Urawa-shi, Saitama Lintec Urawa No. 3 Dormitory No. 210 ( 72) Inventor Hiroshi Nagaki 1-8-2 Kaedagaoka, Hatoyama-cho, Hiki-gun, Saitama Prefecture

Claims (4)

[Claims] 1. A bactericidal pressure-sensitive adhesive characterized in that an isothiocyanate is impregnated and held in a pressure-sensitive adhesive mainly composed of a polymer that is dissolved in isothiocyanate or swelled by isothiocyanate. 2. The adhesive is an acrylic polymer and is a copolymer of a (meth) acrylic acid alkyl ester monomer having an alkyl group having 4 or more carbon atoms and a monomer copolymerizable with the monomer. The bactericidal pressure-sensitive adhesive according to claim 1, wherein 3. A pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive mainly composed of a polymer that is dissolved in isothiocyanate or swells with isothiocyanate, and is then impregnated with isothiocyanate. And a method for producing a bactericidal adhesive. 4. A pressure-sensitive adhesive product obtained by applying the bactericidal pressure-sensitive adhesive according to claim 1 or 2 to at least one surface of a substrate.