JPH0751093A - Adhesive sheet for bacterial inspection and method of the inspection - Google Patents

Abstract

PURPOSE:To obtain an adhesive sheet for bacterial inspection having a high bacterial capturing rate and a good workability, by laminating an adhesive water gel layer containing a water soluble polymer as a major component, and a water permeable support. CONSTITUTION:An adhesive layer 2 is laminated integrally like a sheet on a support 3 to form an adhesive sheet 1. The adhesive layer is a water gel layer which has adhesive property, contains adequate amount of water, and has a homogeneous water absorption property at need. As a water soluble polymer, an acrylic copolymer of an alkoxyalkyl acrylate with an N-vinyllactam is preferable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive sheet which can collect bacteria in an adhesive layer and use the adhesive surface as a medium as it is, and a method for examining bacteria for forming a colony using the adhesive sheet.

[0002]

2. Description of the Related Art Conventionally, in order to estimate the number of bacteria in a test material, it has been applied that one bacterium forms one colony, such as the agar stamp method using a commercially available food stamp. Then, there is a method in which a solid medium such as agar is pressed against the test material to culture the bacterium, and the colonies expressed on the agar plate are visually determined and measured. Also, for example, as in the membrane filter method using a commercially available microorganism / microparticle test membrane filter or the like, the test material is washed with physiological saline or the like and collected with the membrane filter,
There is also a method of forming colonies on the filter by absorbing the liquid medium. Furthermore, medical examination No. 41
Vol. 3, No. 3, p352, 1992, an example in which a film is coated with a medium and a film-coated medium capable of collecting a sample by simply contacting and culturing the film on a test surface is reported.

[0003]

However, in the agar stamp method, the size (area) of the agar medium is limited, and since it can usually be used only once for one treated surface, it depends on the water content of the agar medium. The collection efficiency was often changed, resulting in poor reproducibility. That is, in this method, stabilizing the collection efficiency is an important issue, and as a solution to it,
It is possible to collect the bacteria with an adhesive roller or sheet and transfer them to an agar stamp. However, in this case, it is considered that the number of steps is increased and there is a problem in the transfer efficiency and reproducibility.

In addition, the membrane filter method requires two steps, namely a washing step and a filtering step with a filter, which makes the operation complicated and there is a problem that secondary contamination may occur. That is, in this method, bacteria cannot be directly collected from the test substance, and much labor is required for sterilization work before use, sampling with a cotton swab, preparation of washout liquid, filter filtration, etc., and cost increase is inevitable. . It is an important issue to overcome the drawbacks related to workability.

Further, the film-coated medium announced in the medical examination is limited in its use as a sheet because it cannot be processed into a roller because the bending strength of the agar medium used is small, and it cannot be continuously produced. There are various drawbacks such as insufficient adhesion between the medium and the film.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned drawbacks of the prior art such as high collection efficiency and good workability. That is, the present invention is an aqueous gel layer (adhesive layer) containing an adhesive (water-absorbing) water-soluble polymer containing or not containing a hydrophilic low-molecular substance or a plasticizer.
The present invention relates to a pressure-sensitive adhesive sheet comprising a water-permeable support and a bacterial test method characterized by using the same.

FIG. 1 and FIG. 2 each show one embodiment of the adhesive sheet of the present invention. In the adhesive sheet 1, the adhesive layer 2 is integrally formed in a sheet shape on the support 3. The adhesive layer 2 is a layer made of an aqueous gel containing a water-soluble polymer as a main component, which has an adhesive property, contains an appropriate amount of water, and has a uniform water absorbability as needed. The pressure-sensitive adhesive layer 2 may be one in which the gel itself has an appropriate water permeability, or as shown in FIG.
The thing which secured water permeability can be used by providing. The support 3 may itself be water-permeable, or may be water-permeable by providing a through hole 4.

As the water-soluble polymer that constitutes the adhesive layer,
Agar, carrageenan, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol (PVA), gelatin,
Carboxymethyl cellulose, alginic acid, methyl cellulose, polyacrylic acid-based and / or polyacrylate-based polymer compounds, acrylic copolymers, hydrophilic polyether urethane polymers, stilbazolized polyvinyl alcohol, polysaccharides such as xanthan gum, polyethylene oxide , And acrylamides such as poly (N-isopropylacrylamide) are preferable.

A more preferable water-soluble polymer is an acrylic copolymer composed of an alkoxyalkyl acrylate and N-vinyllactam, from the viewpoint of the growth rate of colonies and separation performance.

The alkoxyalkyl acrylate, which is a monomer component of the acrylic copolymer, has 1 to 1 carbon atoms.
An acrylate having an alkoxy group having 4 carbon atoms and an alkyl group having 2 to 4 carbon atoms or an alkylene glycol group is preferable. Specifically, for example, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 3-methoxypropyl acrylate, 3-methoxybutyl acrylate, 3-ethoxypropyl acrylate, 3-ethoxybutyl acrylate, and Butoxytriethylene glycol, 2-
Examples thereof include alkoxyalkylene glycol acrylates such as (2-ethoxyethyl) ethyl acrylate, methoxytriethylene acrylate, and methoxydipropylene glycol acrylate, and have a low glass transition point, high hydrophilicity, high reactivity, and the like. 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate are preferred.

As the other monomer component, N-vinyllactam, a 5- to 7-membered ring N-vinyllactam is used. For example, N-vinyl-2-pyrrolidone, N-
Examples thereof include vinyl-2-piperidone and N-vinyl-2-caprolactam, and N-vinyl-2-pyrrolidone is preferable in terms of safety and versatility.

The mixing ratio of the alkoxyalkyl acrylate is preferably 60 to 80 based on the total amount of the acrylic copolymer.
%, More preferably 65 to 75% by weight. Mixing ratio of alkoxyalkyl acrylate is 6
When it is less than 0% by weight, the obtained adhesive layer may have low flexibility. On the other hand, if it exceeds 80% by weight, the pressure-sensitive adhesive layer may have high tackiness and low strength.

The blending ratio of N-vinyllactam is
Preferably 20 to 40% by weight of the total acrylic copolymer
And more preferably 25 to 35% by weight. N
-If the blending ratio of vinyllactam is less than 20% by weight, the strength and water absorption capacity of the obtained adhesive layer may be low. On the other hand, when it exceeds 40% by weight, the obtained adhesive layer has low flexibility, and the acrylic copolymer may dissolve in water to cause flow.

Vinylcarboxylic acid may be added to the acrylic copolymer in order to improve the water absorption capacity. Examples of vinyl carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid,
Examples include maleic acid half ester and fumaric acid half ester. Among them, acrylic acid is preferable from the viewpoint of reactivity and versatility.

The blending ratio of vinylcarboxylic acid is preferably 10% by weight or less, more preferably 5% by weight or less, based on the whole acrylic copolymer. If the blending ratio of vinylcarboxylic acid exceeds 10% by weight, the water-absorbing ability of the adhesive layer tends to be high, and the flexibility tends to be low.

Further, an acrylic copolymer obtained by blending 0.01 to 1% by weight of a polyfunctional acrylate or methacrylate and copolymerizing them is also useful.

Examples of the polyfunctional acrylate or methacrylate used in the present invention include 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol diacrylate,
Alkyl type diacrylates or dimethacrylates such as 1,6-hexanediol diacrylate and 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol 200 Diacrylate, polyethylene glycol 400 Diacrylate, polyethylene glycol 600
Diacrylate, polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 dimethacrylate, polyethylene glycol 600 dimethacrylate, polyethylene glycol 1000 dimethacrylate, polypropylene glycol 400 diacrylate,
Alkylene glycol type diacrylates or dimethacrylates such as polypropylene glycol 400 dimethacrylate, ester type diacrylates or dimethacrylates such as hydroxypivalic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate,
Ethoxylated trimethylolpropane triacrylate,
Trimethylolpropane type tri- and tetraacrylates such as ditrimethylolpropane tetraacrylate or trimethacrylate, pentaerythritol triacrylate, pentaerythritol type tri- and tetraacrylates such as pentaerythritol tetramethacrylate or tri- and tetramethacrylate, tris (acryloxyethyl) isocyanate Isocyanurate type triacrylate or trimethacrylate such as nurate, tris (methacryloxyethyl) isocyanurate,
Examples thereof include bisphenol A-type diacrylates such as ethoxylated bisphenol A diacrylate and ethoxylated bisphenol A dimethacrylate, and dimethacrylates. From the viewpoint of hydrophilicity and safety, alkylene glycol type diacrylates or dimethacrylates are preferable, and crosslinking is preferable. From the point of proper performance, polyethylene glycol 600 dimethacrylate, polyethylene glycol 4
00 dimethacrylate is more preferred.

In this acrylic copolymer, the proportion of the polyfunctional acrylate or methacrylate is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5, based on the total weight of the acrylic copolymer. % By weight. If the amount of this component is less than 0.01% by weight, the crosslinking tends to be insufficient, the strength tends to decrease, and the composition tends to be water-soluble. On the other hand, when it exceeds 1% by weight, flexibility and adhesiveness are lowered, hydrophilicity is remarkably lowered, and whitening tends to occur after water absorption.

The water-soluble polymer of the present invention can be produced by a method known per se.

For example, the acrylic copolymer may be produced by any copolymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and photopolymerization. Solution polymerization is carried out by heating and stirring the monomer mixture in the presence of a medium and a polymerization initiator. Examples of the solvent include water, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, ethylene glycol monoalkyl ether, and the like. These may be used alone or in combination of two or more. Can be used. Examples of the polymerization initiator include benzoyl peroxide, cumene hydroperoxide,
Examples thereof include diisopropyl peroxydicarbonate and azobisisobutyronitrile, which may be used alone or in combination of two or more. The polymerization initiator is preferably 0.01 parts by weight or more and 5 parts by weight or less, and more preferably 0.1 parts by weight or more and 0.5 parts by weight or less with respect to 100 parts by weight of the monomer.

The acrylic copolymer can also be polymerized by photopolymerization by irradiating the monomer mixture with UV light in the presence of a photoinitiator. Photopolymerization is performed by sufficiently substituting a mixture of a monomer other than a polyfunctional acrylate or methacrylate and a photoinitiator with nitrogen, and then irradiating with a certain dose of UV light, and the resulting partially polymerized syrup is, if necessary, polyfunctional acrylate or Apply a mixture of methacrylate and a plasticizer described below or cast it in a frame, and then add sufficient U
A copolymer is obtained by irradiating with V light. Alternatively, after the mixture of the monomer, the photoinitiator, and, if necessary, the plasticizer is sufficiently replaced with nitrogen, a certain dose of UV light is irradiated, and the resulting partially polymerized syrup is applied or cast in a frame. A method of obtaining a copolymer by irradiating sufficient UV light is preferable.

In this case, the total irradiation dose during partial polymerization is 20
mJ / cm²Above 300mJ / cm ²The following is preferable,
Total irradiation dose at complete polymerization is 1000 mJ / cm²Above 1
0000mJ / cm²The following is preferable and 2000 mJ /
cm²Above 5000 mJ / cm²The following is more preferable
Yes.

The photoinitiator is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-.
Methyl-1-phenylpropan-1-one, 1- (4-
Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)-
2-hydroxy-2-methylpropan-1-one, 4-
(2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 and the like. Acetophenone photoinitiators, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal and other benzoin photoinitiators, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone , Hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, benzophenone-based photoinitiators such as 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone, 2-quat Ruthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone And other thioxanthone photoinitiators. Although the photoinitiator varies depending on the extinction coefficient and the like, the polymerization proceeds preferably at 0.005 parts by weight or more and 0.5 parts by weight or less with respect to 100 parts by weight of the monomer, and 0.01
More preferably, it is not less than 0.2 parts by weight.

In this case, a photoinitiation aid may be added if necessary. Examples of the photoinitiating aid include triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Ethyl, (n-butoxy) ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate,
2-Ethylexyl 4-dimethylaminobenzoate and the like can be mentioned, and these can be used alone or in admixture of two or more. Photoinitiator aid is monomer 10
Polymerization proceeds preferably in an amount of 0.01 parts by weight or more and 1 part by weight or less, and more preferably 0.02 parts by weight or more and 0.5 parts by weight or less, relative to 0 parts by weight.

If desired, a plasticizer may be added to the water-soluble polymer. By adding a plasticizer,
The flexibility and tackiness can be further improved. More conveniently, absorption of water from a liquid or solid medium reduces stickiness and allows grown colonies to be easily transferred to other media. As the plasticizer, it is desirable to use a compound that has good compatibility with the water-soluble polymer used and is hydrophilic.

For example, when a plasticizer is added to the acrylic copolymer, the plasticizer is preferably 5 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the acrylic copolymer.
More preferably, it is from 30 parts by weight to 30 parts by weight. When a plasticizer is added to another water-soluble polymer, the plasticizer is preferably 5 parts by weight or more and 500 parts by weight or less, and more preferably 10 parts by weight or more and 300 parts by weight or less with respect to 100 parts by weight of the water-soluble polymer. preferable.

When the amount of the plasticizer exceeds 40 parts by weight with respect to 100 parts by weight of the acrylic copolymer, the properties of the acrylic copolymer such as a decrease in cohesive force are lost, and the radiation such as electron beam described below is lost. In some cases, it may be difficult to insolubilize with a chemical crosslinking agent, or it may be difficult to insolubilize with a polyfunctional acrylate or methacrylate. From these perspectives,
The plasticizer is 40 per 100 parts by weight of the acrylic copolymer.
It is more preferable that the amount is not more than parts by weight. Further, in order to further improve flexibility and tackiness, it is preferable that the plasticizer is 5 parts by weight or more with respect to 100 parts by weight of the acrylic copolymer.

Examples of the plasticizer used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, 2,3-butanediol, 1,2-butanediol, 3-methyl-
1,3-butanediol, 3-methyl-1,3,5-pentanetriol, 2-ethyl-1,3-hexanediol and other low molecular weight polyhydric alcohols, having an average molecular weight of 10
Polyethylene glycol, polypropylene glycol, polyoxyethylene butyl ether, polyoxyethylene, polyoxypropylene, polyoxypropylene glyceryl ether, polyoxypropylene glycol, polyoxypropylene sorbitol, polyoxyethylene polyoxypropylene pentaerythritol ether, etc. Among them, the average molecular weight is particularly preferably 20 because excellent flexibility, tackiness and hydrophilicity are obtained.
0 to 800 polyoxypropylene glyceryl ether, average molecular weight of 200 to 800 polyoxypropylene glycol, average molecular weight of 200
Polyoxypropylene sorbitol having a content of 800 or more and the like is preferable.

Further, a hydrophilic low molecular weight substance may be added in order to maintain an appropriate water content. Examples of the hydrophilic low molecular weight substances include high boiling point liquid substances and / or deliquescent inorganic salts. A high boiling point liquid substance has a boiling point of 10
Compounds at 0 to 400 ° C, preferably 200 to 350 ° C are preferred. Specific examples thereof include polyhydric alcohols and sugar alcohols, and the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, and the like, and sugar sugars such as sorbitol. Is mentioned. Further, specific examples of the deliquescent inorganic salts include lithium nitrate,
Examples thereof include lithium chloride.

The amount of the hydrophilic low molecular weight substance used is preferably 20 to 300 parts by weight based on 100 parts by weight of the water-soluble polymer, and this ratio is particularly preferable in the polyacrylic acid type polymer compound. . When the amount of the hydrophilic low-molecular substance used is 20 parts by weight or less, no remarkable moisture absorption effect or moisturizing effect can be obtained, and when it is 300 parts by weight or more, the viscosity of the aqueous composition is too high and workability is poor, which is not preferable. Is.

The above-mentioned water-soluble polymer, water-soluble polymer and plasticizer and / or hydrophilic low-molecular substance are added with water and a crosslinking agent as required, and mixed and stirred to form a gelled product.
Alternatively, it may be used as a frozen / thawed gel like PVA. Further, gelation due to irradiation and cross-linking of electron beam or γ-ray is also included. UV photopolymerization is particularly effective in the case of an acrylic copolymer.

Preferred cross-linking agents include compounds having at least two epoxy groups in the molecule, such as polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin triglycidyl ether and triglycidyl isocyanurate. These cross-linking agents are particularly preferable for polyacrylic acid type polymer compounds.

Examples of the cross-linking treatment method include insolubilization by irradiation cross-linking with electron beam or γ-ray.
In this case, the irradiation dose of radiation depends on the degree of water solubility of the acrylic copolymer, for example,
It is desirable to be not less than kGy and not more than 50 kGy. In particular, if it also serves as sterilization, it is desirable to set it to 25 kGy or more and 50 kGy or less. When the dose is 25 kGy or less, sterilization cannot be guaranteed, and when the irradiation dose is 25 kGy or more, the sterilization can be combined with the sterilization specified by medical regulations. 50 kG
When it exceeds y, the modification such as coloring is remarkable and the use is limited.

Also, when the water solubility is increased by adding a plasticizer to the acrylic copolymer, insolubilization by cross-linking treatment may be necessary.

Furthermore, when the plasticizer is added to the above-mentioned acrylic copolymer, the blending ratio of the acrylic copolymer is
In the total amount of the acrylic copolymer and the plasticizer, 60% by weight or more includes the case of only the acrylic copolymer, that is, the case of 100% by weight of the acrylic copolymer. Achieving insolubilization of copolymers,
In some cases, it is necessary to achieve shape retention.

The water content of the aqueous composition is 5 to 9
5% by weight is preferable, and the water content of the gel layer after solidification and curing is usually preferably kept in the range of 5 to 80% by weight. This moisture content is a preferable moisture content particularly in the polyacrylic acid type polymer compound. The pH of the gelled product can be adjusted as necessary, but is usually preferably in the range of 6.5 to 7.5.

The support used in the present invention must be water permeable. For example, water-permeable paper, woven fabric, nonwoven fabric, porous film, or the like, or water-impermeable paper, woven fabric, nonwoven fabric, porous film, or the like that is provided with through holes to make it water-permeable. used. For example, polyethylene laminated paper, polypropylene laminated rayon, non-woven fabric such as polyester and cotton, sizing treated paper, or a hydrophilically treated film is used to form a hole from the support side with a perforating roller after forming a gel layer. Finally, the water-permeable one is used.

The adhesive sheet of the present invention is manufactured by a method known per se.

For example, an aqueous solution of a water-soluble polymer substance (aqueous composition) containing a plasticizer, a hydrophilic low molecular weight substance and / or a cross-linking agent is applied to a support and dried at 10 ° C to 200 ° C. When the support is impermeable to water, it is manufactured by making holes in the support. The gel layer formed into a thin film by drying may be post-treated at a temperature of 10 ° C to 100 ° C if necessary. The formed gel layer is provided with appropriate tackiness and moisture content.

In particular, since the acrylic copolymer has excellent thermoplasticity, it can be processed into a sheet by extrusion molding. This extrusion molding can use any generally known method such as inflation molding, T-die molding, lamination molding, etc., but since it can be extruded at high temperature and rapidly cooled, a film or sheet having excellent optical properties can be obtained, and the cooling efficiency is high. Therefore, the T-die molding is preferable from the viewpoints that the production speed can be increased and the sheet thickness can be easily adjusted. The extruder may be either a single-screw extruder or a twin-screw extruder. The thickness of the film or sheet can be adjusted by appropriately controlling the molding conditions such as the molding temperature, the die lip width, the extrusion speed and the take-up speed. In this case, the molding temperature is preferably 140 ° C or higher and 180 ° C or lower, and more preferably 150 ° C or higher and 170 ° C or lower. Molding temperature is 14
When the temperature is lower than 0 ° C, non-melted matter is often mixed and the quality may vary. On the other hand, when the temperature is higher than 180 ° C, film breakage and air bubble entrapment may occur, which is not preferable.

Further, as a method for forming the film and sheet, a method such as a calendering method or a casting method can be used. However, when the polymerization method is photopolymerization, a monomer mixture containing a photoinitiator, or a partially polymerized syrup thereof, or a monomer mixture containing a photoinitiator and a plasticizer, or a partially polymerized syrup on a peelable film made of a polyester film or the like. The composition is cast and coated at a constant thickness, and then covered with a transparent peelable film, and then UV light is sufficiently irradiated in an inert atmosphere, whereby polymerization and film formation are simultaneously performed. The film and sheet thus obtained can be cut into an arbitrary shape and used as an adhesive sheet, and can be used by laminating with an arbitrary support.

Furthermore, an acrylic copolymer can be obtained by radical polymerization of a mixture of a monomer, a solvent and a polymerization initiator constituting the acrylic copolymer of the present invention by a usual operation. A film may be formed by casting a solution of the system copolymer. This film has a thickness of 10-75μ
m, preferably 20 to 50 μm is adjusted, and if this thickness exceeds 75 μm, impurities and residual monomers cannot be sufficiently removed, or it is not preferable because it remarkably foams during drying described later, On the other hand, 1
If it is less than 0 μm, the amount of water absorption is small, and the desired strength may not be obtained, which is not desirable. The obtained film can be dried under a certain condition to obtain a film-like pressure-sensitive adhesive from which a solvent and the like (solvent and / or prepolymer, hereinafter simply referred to as impurities) and residual monomers are removed.

In this case, the drying conditions differ depending on the thickness of the film and the drying conditions such as reduced pressure drying and atmospheric drying.
0 to 75 μm, 110 to 150 ° C. for 30 seconds to 20 minutes,
Particularly, it is desirable to set the temperature at 120 to 140 ° C. for 1 to 15 minutes.

As described above, the impurities and residual monomers are removed by drying the film formed of the present polymer, resulting in stable quality and elimination of adverse effects on microorganisms due to the impurities and residual monomers. You can

Except for the method of casting the above-mentioned acrylic copolymer with a solvent, the film-like or sheet-like pressure-sensitive adhesive of the present invention has a thickness of 10 μm or more, preferably 20 μm or more and 2000 μm or less, more preferably 3 μm or more.
It is preferable that the thickness is set to 0 μm or more and 1000 μm or less. If this thickness is less than 10 μm, a film breakage phenomenon often occurs, which is not preferable, and if it exceeds 2000 μm, the water permeability is poor and it is meaningless to increase the thickness.

In the present invention, the water-soluble polymer is formed into a film or sheet and then electron beam or γ
Crosslinking can also be performed by irradiating radiation such as rays. This radiation crosslinking is particularly effective for acrylic copolymers. The crosslinking treatment can be performed under the same conditions as described above.

The pressure-sensitive adhesive sheet of the present invention can be kept in a sterilized state by enclosing it in a bacteria-blocking packaging material in a sterilized state. As the sterilization method, it is preferable to use the EOG (ethylene oxide gas) method, the electron beam method, or the γ-ray method. That is, after the above-mentioned pressure-sensitive adhesive sheet is sealed in a bacterium-blocking packaging material to make it in a form capable of maintaining a sterile condition, irradiation with an electron beam or γ-rays is applied to carry out crosslinking and sterilization treatment to obtain the present invention. The polymer and the pressure-sensitive adhesive sheet using the polymer can be distributed.

In this case, the irradiation dose of radiation such as electron beam or γ-ray varies depending on the hydrophilicity of the polymer, but the crosslinking treatment can be performed under the same conditions as described above.

The gel layer of the pressure-sensitive adhesive sheet thus obtained is preferably tacky and has a uniform water absorption property. That is, the gel layer has a peeling adhesive strength (according to JIS K6854) in the 180 ° direction at a speed of 300 mm / min on the SUSBA430 plate of 5 to 500 g /
20 mm, preferably 100-400 g / 20 mm.

Further, among the polymers of the present invention, those having a 24-hour water absorption of 20% by weight or more and 5000% by weight or less are particularly desirable.

Here, the water absorption means that the polymer is formed into a film or sheet, cut into 1.5 cm × 1.5 cm, the weight before water absorption is measured, and then each cut piece is subjected to phosphate buffering. It was immersed in 135 ml of physiological saline (pH 7.4, 32 ° C.) for 24 hours. After that, each cut piece was taken out, the surface water was wiped off, the weight after water absorption was measured, and the value was calculated from the increased weight.

As the water absorption rate increases, the flexibility and the stress relaxation property increase. However, when the water absorption rate exceeds 5000% by weight, the gel strength becomes low and becomes brittle, or the water tends to be dissolved, which is substantially Not usable, but with a water absorption of 5000
A gel state having a strength that can be substantially used can be obtained at a content of not more than wt%, and a gel state having a strength that can be effectively used can be obtained at a content of not more than 3000 wt%.
On the other hand, if the water absorption rate is less than 20% by weight, the water permeability will be poor and the absorption of water and nutrients from the support will be poor.

A method for conducting a bacteria test using the adhesive sheet of the present invention will be described. For example, a roller having the adhesive sheet of the present invention is pressed against a test substance such as a floor or a wall and cleaned to collect bacteria and fungi attached to the test surface on the roller. Cut an adhesive sheet to which bacteria or fungi adhere to a predetermined size and drop it onto an absorbent pad, or onto an agar medium, a solid medium such as an aqueous gel containing or impregnated with a liquid medium, the sheet. The support side is contacted, the adhesive layer is set up, and the plate is placed in a sterile petri dish and cultured in an incubator. FIG. 3 shows an example of the culture method. With the adhesive layer 2 of the adhesive sheet 1 having the bacteria 8 adhered thereon, the absorbent pad 7 containing the liquid medium and the support 3 of the sheet 1 were placed in contact with each other, and the petri dish 6 was used.
Put in. When a liquid medium is used, the liquid medium will adhere to the adhesive layer (gel layer) of the adhesive sheet due to capillary action during culturing.
And further diffuses to the surface of the adhesive layer through the water in the gel as a medium to express colonies. At this time, if a liquid medium is impregnated with a specific antibacterial agent or antibiotic at a predetermined concentration, only colonies of antibiotic-resistant bacteria such as MRSA can be grown and a detection function is imparted. As the liquid medium used in the present invention, a standard agar medium, LB medium or the like is used depending on the fungus to be detected.

The liquid medium may contain an antibacterial agent or an antibiotic depending on the purpose of detecting resistant bacteria such as MRSA. Antibacterial agents and antibiotics that can be used include alcohols, glutaraldehyde, iodine, povidone iodine, benzalkonium chloride, benzethonium chloride, alkylpolyaminoethylglycine, cyclohexidine gluconate,
Benzisothiazoline, cyclic compounds containing organic nitrogen, organic nitrogen-sulfur compounds, organic nitrogen-sulfur halogen compounds, pyridine oxide compounds, cephems, second-generation cephems, third-generation cephems antibiotics (cephalosin, cephaloridine, etc.) , Penicillin antibiotics (methicillin, ampicillin, penicillin G etc.), tetracycline antibiotics (tetracycline etc.), peptide antibiotics (vancomycin etc.), aminoglycoside antibiotics (arbekacin, streptomycin, kanamycin etc.).

As an example of the application of the adhesive sheet of the present invention, when the adhesive sheet is used as a roller, colonies are adhered to the adhesive surface only by contacting the sheet on which bacteria are adhered and captured with a pad on which liquid medium is absorbed. It can be expressed and can be used for in-hospital environmental surveys, etc., in which the cleanliness of a test substance is simply measured. In addition, by adding a specific antibacterial agent or antibiotic such as methicillin to the liquid medium, MR
It can also be used for detecting resistant bacteria such as SA. Furthermore, by using the adhesive sheet of the present invention or a roller manufactured from the sheet, an absorbent pad, a culture medium, an antibacterial agent, a petri dish and the like as a set kit, a set of environmental research tools that anyone can do anywhere Can be provided.

[0056]

EXAMPLES Next, the present invention will be described more specifically by showing examples.

Example 1 100.5 g of commercially available polyacrylic acid (10H manufactured by Nippon Pure Chemical Industries, Ltd., having an average degree of polymerization of 40,000) is dissolved in 84 g of water. Further, 86 g of polyacrylic acid (10LP manufactured by Nippon Pure Chemical Industries, Ltd., having an average degree of polymerization of 40,000) and glycerin 217
g is heated and dissolved. Next, 35 g of NaOH was added and mixed to obtain a sodium polyacrylate / glycerin mixed aqueous solution having a saponification degree of 60 mol%. Triglycidyl isocyanurate as a cross-linking agent is dissolved in water and added to this mixed solution so as to be 0.31% by weight to obtain an aqueous solution having a concentration of sodium polyacrylate of 20% by weight. The aqueous solution has a thickness of 8
It is coated with a fountain coater to a thickness of 30 μm on 0 μm polypropylene laminated cotton non-woven fabric,
After being dried in a drying oven at 100 ° C. for 2 minutes and continuously wound up, the adhesive sheet of the present invention was obtained by curing at 50 ° C. for 2 hours. The adhesive sheet was laminated on a roller surface obtained by perforating polypropylene and the bacteria were collected by reciprocating once on the bed sheet with the same adhesive surface (circumferential part). The sheet was cut along perforations, and an absorption pad having an appropriate amount of m-TGE Broth containing 12.5 μg / ml of methicillin absorbed therein was placed in a petri dish and the support side was placed in contact therewith. When this was cultured in an incubator at 32 ° C. for 24 hours, 32 methicillin-resistant bacterial colonies were detected.

Example 2 Stilbazolized polyvinyl alcohol (average degree of polymerization
2300, saponification degree 99.5 mol%, Sbq introduction rate 0.
5 mol%) in 12.5 wt% aqueous solution 70 parts by weight
Sodium xymethylcellulose (average molecular weight 100,000-
110,000), 30 parts by weight of 6.5% by weight aqueous solution, sorbitol
The final concentration of water-soluble polymer is 40 parts by weight.
A 7.6% by weight aqueous solution is obtained. The aqueous solution has a thickness of 80 μm
On polypropylene porous film with a thickness of 30 μm
Coating with a fountain coater at 100 ° C
Output in 2 minutes after drying in a drying oven for 2 minutes
1000 mJ / cm on one side with KW UV lamp ²Both
Γ-rays (illuminated with cobalt 60 as a radiation source)
The adhesive sheet of the present invention by irradiating with a radiation dose of 2.5 kGy)
Got The water absorption of the obtained adhesive sheet was measured.
The amount was 60.4% by weight. Roll the adhesive sheet
-Processed into the same adhesive surface (circumferential part) made of synthetic resin
The surface was reciprocated once to collect bacteria. Cut off the sheet
Circularly draw along the line and in a circular petri dish, nutrient agar medium
Was laid under and the support side was contacted and installed. Hatch this
When cultured at 32 ° C for 24 hours in an egg container, 120
Ronnie is detected.

Example 3 Water was added to polyvinyl alcohol (average degree of polymerization: 1700, degree of saponification: 99.5 mol%) so that the concentration became 15% by weight, and the mixture was completely heated by heating at 110 ° C. for 2 hours in an autoclave. After dissolution, cool to room temperature and 15 wt% PVA
An aqueous solution was prepared. The liquid was immediately frozen in a freezer at -20 ° C for 12 hours to obtain a frozen product. This was left to stand in a constant temperature bath at 5 ° C. for about 10 hours to obtain PVA hydrogel.
The gel solution was cast-coated on a polyethylene laminated paper having a thickness of 70 μm so as to have a thickness of 40 μm using an applicator, and transfer-formed on a perforated polypropylene sheet to obtain an adhesive sheet of the present invention. The water absorption of the obtained adhesive sheet was measured and found to be 40.2% by weight. The adhesive sheet was pressed against the painted wall surface to collect bacteria. The sheet was punched into a circle and m-TGE Broth containing 20 μg / ml of tetracycline in a petri dish.
An absorbent pad having a proper amount of was absorbed was placed underneath and the support side was brought into contact with the absorbent pad. When this was cultured in an incubator at 32 ° C for 24 hours, 20 tetracycline-resistant bacterial colonies were observed.
Individually detected.

Example 4 56 parts by weight of 2-methoxyethyl acrylate and 24 parts of N-vinyl-2-pyrrolidone were placed in a closed reactor equipped with a stirrer.
1 part (0.05 parts by weight) of 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one as a photoinitiator was charged, and the atmosphere was replaced with nitrogen at a flow rate of 10 ml / min for 2 hours. Irradiation with UV light having a dose of about 50 mJ / cm ² resulted in a syrup partially photopolymerized. 20 parts by weight of polyoxypropylene glyceryl ether (average molecular weight 400) was added to this syrup as a plasticizer, and the mixture was stirred under a nitrogen stream for 1 hour. This was cast in a 1.2 mm thick silicon mold frame applied on a silicon-treated releasable PET film, and covered with a similar releasable PET film from above, and then under an inert atmosphere, The total dose is 3000 mJ / cm ² with air cooling as appropriate.
UV light was uniformly irradiated on the front and back sides so that After further drying this at 130 ° C. for 30 minutes, it was irradiated with γ rays having a dose of 25 kGy to obtain a transparent adhesive layer having a thickness of 500 μm. The water absorption of this adhesive layer was 1240% by weight. The pressure-sensitive adhesive layer was transferred onto a polyethylene laminated paper having a thickness of 70 μm and then perforated to obtain the pressure-sensitive adhesive sheet of the present invention. Ampicillin-resistant Escherichia coli was planted on the adhesive sheet, and the support side was placed in contact with LB medium containing 12 μg of ampicillin, and cultured at 25 ° C. for 2 days,
The growth of ampicillin-resistant Escherichia coli was observed. On the other hand, in the case where normal (ampicillin-sensitive) Escherichia coli was planted on the adhesive sheet, the growth of Escherichia coli was not observed due to lack of resistance.

Example 5 In a closed reactor equipped with a stirrer, 70 parts by weight of 2-methoxyethyl acrylate, 30 parts by weight of N-vinyl-2-pyrrolidone, and azobisisobutyronitrile as a polymerization initiator were added.
175 parts by weight and 250 parts by weight of a distilled water-methanol-isopropanol mixed solvent (weight ratio = 16: 23: 1) were charged, and after nitrogen substitution was performed at a flow rate of 10 ml / min for 2 hours, the inside of the reactor was heated to 60 to 62 ° C. Stir for 1.5 hours while maintaining. Subsequently, the reaction was completed by stirring at 75 ° C. for 2 hours and then cooled to room temperature to obtain a solution of an acrylic copolymer. Polyoxypropylene glyceryl ether (average molecular weight 400) as a plasticizer
20 parts by weight was added and stirred for 1 hour. A solution of this acrylic copolymer is applied to a release paper at a constant thickness and then dried at 130 ° C. for 5 minutes to remove the solvent and unreacted monomers, and a transparent water-soluble polymer having a thickness of 50 μm. I got a film. The amounts of 2-methoxyethyl acrylate and N-vinyl-2-pyrrolidone in this film were 10 ppm by weight or less and 200 ppm by weight, respectively.
Met. After encapsulating this film in a bacterial resistant packaging,
An adhesive layer was obtained by irradiating a γ ray having a dose of 27.7 kGy. The water absorption of this adhesive layer was 800% by weight. The pressure-sensitive adhesive layer was transferred onto a nylon filter having a pore size of 1.3 μm and a thickness of 100 μm to obtain a pressure-sensitive adhesive sheet of the present invention. After the adhesive sheet was attached to an aluminum toilet handrail, it was placed in a circular petri dish with the LB medium placed underneath and the nylon filter side in contact. 32 ° C
After culturing for 24 hours, 54 colonies were detected.

Example 6 The sample of Example 4 before γ-ray irradiation was transferred to a PET non-woven fabric, enclosed in a bacterial resistant packaging material, and then irradiated with γ-rays at a dose of 30.2 kGy to give the adhesiveness of the present invention. Got the sheet. After sticking the adhesive sheet taken out from the packaging material to the pillow cover, put it in a sterile petri dish and put it on LB medium with PET.
When the non-woven fabric side was contacted and cultured at 32 ° C. for 24 hours, 20 colonies were detected.

[0063]

The pressure-sensitive adhesive sheet of the present invention comprises a water-permeable support and a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer has a bacteria-collecting function due to the pressure-sensitive adhesive property, and also has an appropriate water content and a uniform water absorption property. Since it has, the gel itself functions as a medium, and the bacteria collected on the adhesive surface can be cultured as they are by absorbing the liquid medium through an absorption pad or the like. Therefore, the collection efficiency of bacteria and the like is high and a complicated process is not required. Further, when inspecting an environment having a relatively high degree of cleanliness, the inspection range may be expanded with the same adhesive surface, and it can be collected economically and labor-savingly as compared with the agar stamp method or the membrane filter method.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an embodiment of an adhesive sheet of the present invention.

FIG. 2 is a cross-sectional view showing another embodiment of the adhesive sheet of the present invention.

FIG. 3 is an explanatory view showing an example of a bacterial culture method using the adhesive sheet of the present invention.

[Explanation of symbols]

 1 Adhesive Sheet 2 Gel Layer 3 Support Layer 4 Through Hole 5 Through Hole 6 Petri Dish 7 Absorption Pad 8 Bacteria

Front page continuation (72) Inventor Tetsuji Sugii 1-2-2 Shimohozumi, Ibaraki, Osaka Prefecture Nitto Denko Corporation (72) Inventor Junichi Saito 1-2-2 Shihohozumi, Ibaraki, Osaka Nitto Denko Stock In the company

Claims (7)

[Claims] 1. An adhesive sheet comprising an adhesive aqueous gel layer containing a water-soluble polymer as a main component and a water-permeable support. 2. The pressure-sensitive adhesive sheet according to claim 1, wherein the water-soluble polymer is an acrylic copolymer composed of an alkoxyalkyl acrylate and N-vinyllactam. 3. The adhesive sheet according to claim 1, wherein the water-soluble polymer contains a hydrophilic low molecular weight substance. 4. The adhesive sheet according to claim 1, wherein the water-soluble polymer contains a plasticizer. 5. The pressure-sensitive adhesive sheet according to claim 1 is pressure-bonded to a test substance, and the collected bacteria are directly cultured by absorbing a liquid medium or a solid medium on the pressure-sensitive adhesive sheet. A bacterial test method characterized by growing a colony. 6. A colony is grown by placing a support of a sheet in which the bacteria are collected in contact with an absorbent pad containing a liquid medium or a solid medium, and culturing the support. Bacteria test method described. 7. The medium is a selective medium of MRSA,
7. The method for detecting bacteria according to claim 5, wherein the colony is a colony of MRSA.