JPS61138658A - Antifungal polyurethane film - Google Patents

Abstract

PURPOSE:The titled film that is composed of a urethane polymer containing specific zeolite solid particles bearing metal ions with fungicidal activity by ion exhange, thus being suitable for use as tapes for wrapping injuries or as a film for preventing leak in sanitary bands. CONSTITUTION:Zeolite solid particles with a specific surface area over 150m<2>/g and a SiO2/Al2O3 molar ratio less than 14 such as A-type zeolite, X-type zeolite, Y-type zeolite or mordenite are allowed to hold metal ions having bactericidal action, at least one selected from siliver, copper and zinc by ion exchange. Then, 0.01-50wt%, preferably 0.05-40wt% of the zeolite particles are added to a polyurethane and the composition is made into a film. Or zeolite solid particles, before ion exchange, are mixed with polyurethane, formed into a film, then ion exchange is effected to allow the film to bear the metal ions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane film with antibacterial properties.

The polyurethane film of the present invention is used in fields where hygiene is required, such as wound tape, leakage prevention films for sanitary belts and diaper covers, and waterproof laminate clothing.

Polyurethanes have traditionally been used to make wound tapes, anti-leak films, and waterproof laminate clothing, but the conditions in which such articles are used present hygienic problems as they present conditions suitable for bacterial growth. The present invention provides a polyurethane film that has significant antibacterial properties against bacteria and mold.

That is, the present invention provides a foamed or non-foamed antibacterial polyurethane film made of urethane containing porous zeolite solid particles having gas adsorption ability that retain metal ions having a bactericidal effect through ion exchange. do.

In the present invention, the film may be the film itself, a film laminated with a knitted fabric, or an intermediate adhesive layer of a laminated article.

In the present invention, zeolite-based solid particles having a bactericidal effect are those made by ion-exchanging and retaining one or more types of metal ions having a bactericidal effect in the ion-exchangeable portion of natural or synthetic zeolite made of aluminosilicate. It is something that exists. Preferred examples of metal ions having a bactericidal effect include Mug, Ou, and Zn. It is therefore possible to use the above-mentioned metals, which have bactericidal properties, alone or in combination for the above-mentioned purpose.

Zeolite is generally an aluminosilicate with a three-dimensionally developed skeleton structure, and is generally based on A403, XMVnO・mu/, Os@7day1pseudo・ZH,
It is represented by O. M represents an ion-exchangeable metal ion, usually a monovalent to divalent metal, and n corresponds to this valence. On the other hand, X and y represent the coefficients of metal oxide and silica, respectively, and 2 represents the number of crystal water. Many types of zeolites are known, differing in their composition ratio, pore diameter, specific surface area, etc.

However, the specific surface area of the zeolite solid particles used in the present invention must be 150 m''/r or more (based on anhydrous zeolite), and the molar ratio of 81 to A40 g of the zeolite constituents must be 14 or less, preferably 11 or less.

The solution of water-soluble salts of metals having a bactericidal action, such as silver, copper, and zinc, used in the present invention easily undergoes ion exchange with the zeolite defined in the present invention, so the solution is prepared by taking advantage of this phenomenon. It is possible to hold the above metal ions alone or in a mixed form in a zeolite stationary phase, but the zeolite particles holding metal ions must have a specific surface area of 150 m"/or more and sto,
Two conditions must be met: /A/, o, and the molar ratio is 14 or less. If this is not the case, the object of achieving effective bactericidal action cannot be obtained. This is considered to be because the absolute amount of metal ions fixed in zeolite K is insufficient in a state where the effect can be exerted.

In other words, this is considered to be due to the physicochemical properties of the zeolite, such as the amount of exchange groups, exchange rate, and accessibility.

Therefore, StO, known as molecular sheep
, /mu1xos A zeolite having a large molar ratio is completely unsuitable for the present invention.

810 again! /ml*oa In a zeolite with a molar ratio of 14 or less, it is possible to uniformly retain metal ions that have a bactericidal effect, and for this reason, when such a zeolite is used, a sufficient bactericidal effect can be obtained for the first time. . In addition, zeolite 5ioR/A/, os
The acid resistance and alkali resistance a of zeolites with a high silica ratio exceeding 14 increase as the molar ratio increases to 81, but
On the other hand, the synthesis thereof also takes a long time, and from an economic point of view, it is not advisable to use such a zeolite with a high silica ratio.

The aforementioned natural or synthetic zeolite with 81 to/ml*os≦14 can be used satisfactorily in the fields of application in which the present structure is normally considered, in terms of acid resistance and alkali resistance, and is also economical. It's cheap and a good idea. E from this meaning? The 10x/A40g molar ratio must be 14 or less.

As the zeolite material having a molar ratio of 810m/AjtOs of 14 or less used in the present invention, either natural or synthetic zeolite can be used. For example, natural zeolite is anarsin (munax-01me:
sto, /Al, oa-5-6~a6), chabafite: 1on/A40m-
52~&0 and 44~. y, 6), clinoptilolite (Olino-ptilOllte: 810.
/mu gaol-A5~1 (L5), erionite (
1! rionite: 8101/A/, Oa=5
．． 8-7.4), 7 Faujaait
e: Sing/A4 false-4,2~4.6), mordenite: 81%/At@
OH co & 34~1 (LO), Phillip site (Phi
llipsite: 8101 /At@O@=
2.6 to 4.4), etc. These typical natural zeolites are suitable for the present invention. On the other hand, a typical synthetic zeolite is A-type zeolite (StO
.

/At, O@ -1,4~2.4), X-type zeolite (sio, /*z, o, = 2~s), Y-type zeolite (Eli01/A/, 01-5~6) , mordenite (81017A110g -9 to 10), etc., and these synthetic zeolites are suitable as the zeolite material of the present invention. Particularly preferred are synthetic A-type zeolites, X-type zeolites, Y-type zeolites and synthetic or natural mordenites.

The shape of the zeolite is preferably fine particles, preferably 20 microns or less, preferably 5 microns or less, particularly 2 microns or less.

In the present invention, the polyurethane is obtained by reacting organic polyisocyanates with water, an active hydrogen-containing compound such as a polyamine or a polyol, as is known. Organic polyinsyanates contain at least two isocyanate groups per molecule. Preferably, the selected incyanate mixture has an incyanate functionality of from 2-0 to 50. Useful incyanates are aromatic polyisocyanates, either alone or mixed with aliphatic, cycloaliphatic or heterocyclic polyincyanates.

Suitable organic polyisocyanates include, for example, n-butylene diisocyanate, methylene diisocyanate, methylene diisocyanate,
-xylyl diisocyanate, p-xylyl diisocyanate, cyclohexyl-1,4-diisocyanate,
Dicyclohexylmethane-4,4'-diisocyanate, m-phenylene diinocyanate, p-phenylene diinocyanate, 3-(alpha incyanatoethyl)
-phenylinocyanate, 2,6 Jz thylbenzene-1,4-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, ethylidene diincyanate, propylene-1,2-diincyanate, cyclohexylene-1,2 -Diincyanate, 2.4-
) luene diinocyanate, 2,6-toluene diisoquanate, 3,3'-dimethyl-41-biphenylene diinocyanate, 3,3'-dimethoxy-4,4'
-biphenylene diisocyanate* -t, s, s'-cyx
Nilu 4,4'-biphenylene diisocyanate), 4
14'-biphenylene diisocyanate, s, s'-cyclo-4.4'-biphenylene diisocyanate, 1
．． Included are 5-naphthalene diisocyanate, influorone diisocyanate, m-xylylene diisocyanate, triazine triisocyanate, triketotrihydrotris(incyanato7enyl)triazine and tris(incyanatophenyl)methane.

Furthermore, a modified polyurethane modified with a polyamino acid can also be used as the polyurethane referred to in the present invention (see JP-A-59-53786).

In the present invention, the polyurethane may be foamed. In addition to water, the foaming agent is approximately -40°C to +40°C.
Certain halogen-substituted aliphatic or cycloaliphatic hydrocarbons having a boiling point between
-Fluoroethane + low-boiling hydrocarbon, for example n-propane, cyclopropane, butane, isobutane, pentane, hexane, cyclohexyl, and mixtures thereof.

Further, a catalyst may be used during the reaction for forming the film, and known catalysts such as tertiary amines and metal compounds can be used.

The antibacterial polyurethane film of the present invention is composed of zeolite solid particles and polyurethane, and at least a portion of the zeolite solid particles retain metal ions having a bactericidal effect. The proportion of zeolite solid particles in the whole is 101 to 50% by weight (based on anhydrous zeolite). If it is less than the above lower limit, the antibacterial effect is unsatisfactory. On the other hand, even if the above-mentioned upper limit is exceeded, the antibacterial effect remains almost unchanged, and the physical properties of one film change significantly, which limits the use of the film. From this point of view, the content range is preferably from 1.05 to 40% by weight, and more preferably from 105 to 10% by weight.

Metal ions must be retained in the zeolite solid particles through an ion exchange reaction. If it is simply adsorbed or attached without ion exchange, the bactericidal effect and its sustainability will be insufficient. The present inventors have previously discovered that two methods are possible for retaining metal ions. The first method is to add and mix metal-zeolite with bactericidal properties to polyinocyanates and then form it into a film.The second method is to add and mix zeolite to polyicanates and form it into a film. This is a method in which the molded material is subjected to ion exchange treatment to cause the polyurethane zeolite to retain metal ions that have sterilizing power.

First, the first method will be explained. In this method, a metal-zeolite having bactericidal activity is first produced, and the Kinoh-zeolite can be prepared using an ion exchange reaction as described above.

Taking as an example the case where each woodcutter zeolite defined in the present invention is converted to the whip zeolite of the present invention, a solution of a water-soluble silver salt such as silver nitrate is normally used when converting the whip zeolite. Care must be taken not to increase the concentration of

For example, when converting A-type or
When MAfM is used) silver ions replace sodium ions in the solid phase by ion exchange, and at the same time, silver oxides etc. are precipitated in the zeolite solid phase. This rounding has the disadvantage that the porosity of the zeolite is reduced and the specific surface area is significantly reduced. Furthermore, even if the specific surface area does not decrease significantly, the bactericidal activity decreases due to the presence of silver oxide. In order to prevent such excess silver from being deposited on the zeolite phase, it is necessary to maintain the concentration of the silver solution in a more dilute state, for example, below 0.5M PNoa. The safest concentration of AfM% is 1
It is 1M or less. It has been found that when using the htwoap solution at such a concentration, the specific surface area of the At-zeolite obtained is almost the same as that of the converted material zeolite, and that the bactericidal effect can be exhibited under optimal conditions.

Next, when the zeolites defined in the present invention are converted to Ou-zeolite, the same phenomenon as that for At-zeolite described above occurs depending on the concentration of the copper salt used for ion exchange. For example, when converting A-type or At the same time, basic precipitates such as cua (E104) (OH) are precipitated in the zeolite solid phase, resulting in a decrease in the porosity of the zeolite and a significant decrease in the specific surface area. In order to prevent such excessive copper precipitation into the zeolite phase, it is preferable to keep the concentration of the aqueous preparation used in a well-diluted state, for example, below (105M). It was found that the specific surface area of Ou-zeolite is almost the same as that of zeolite, which is the conversion material, and that it has the advantage of being able to exhibit its bactericidal effect in an optimal state.

It has been mentioned that during the conversion to Muda zeolite and CLt-zeolite, the concentration of salts used for ion exchange causes precipitation of solids on the Niji zeolite solid phase.
When converting to n-zeolite, the salts used are 2
This phenomenon is not observed in the vicinity of ~3M. Generally, the Zn-zeolite used in the present invention can be obtained more easily than K by using salts having concentrations around the above range.

Mudar zeolite, Cu-zeolite and z
When carrying out the ion exchange reaction in a batch process for conversion to n-zeolite, the zeolite material may be immersed in a salt solution having the above-mentioned concentration. In order to increase the metal content in the zeolite material, K may be used by increasing the number of patch treatments. On the other hand, when treating a zeolite material by a column method using a salt solution having the above-mentioned concentration, it is easy to fill an adsorption tower with the zeolite material and pass the salt solution through it. is obtained.

The amount of metal in the above metal-zeolite (based on anhydrous zeolite) is not more than 30% by weight for silver;
The preferred range is (LOOI ~ 5% by weight).On the other hand, for the copper and zinc used in the present invention, the amount of copper or zinc in the metal-zeolite (based on anhydrous zeolite) is 35% by weight or less, and the preferred range is is a, 01-15
It is in weight%. It is also possible to use silver, copper and zinc ions in combination, in which case the total amount of metal ions is 35% of the metal-zeolite (based on anhydrous zeolite).
It may be less than 1% by weight, and the preferred range depends on the composition ratio of metal ions, but is approximately (LOO 1 to 15% by weight).

Furthermore, even if metal ions other than silver, copper, and zinc, such as sodium, potassium, calcium, or other metal ions, coexist, the bactericidal effect is not hindered, so the residual or coexistence of these ions is not a problem.

Next, such metal ion-containing zeolite is added and mixed to the organic polyinsyanate mixture in the above-mentioned content to obtain a polyurethane film at room temperature or under heating. Metal-
Amount of metal with bactericidal action relative to the total weight of zeolite (as AVt%) and metal relative to the total weight of the film
The amount of zeolite (Bwt%) is related to the bactericidal effect; if the amount of zeolite is high, less B is needed;
It is necessary to increase the number of In order to effectively exhibit the bactericidal effect, it is desirable to adjust the value of M×B so that it is a,01 or more in the case of silver-zeolite, and α1 or more in the case of copper or zinc-zeolite.

Next, the second method for producing the film of the present invention will be explained. Although the second method differs in the timing of the ion exchange treatment, it is basically similar to the first method in many ways. The defined zeolite is added and mixed into an organic polyisocyanate mixture without ion exchange treatment.The content range of zeolite is the same as in the first method.The timing and method of addition and mixing are not particularly limited. ,
If it is necessary to dry the zeolite, the method described above can be followed. In the second method, the zeolite-containing polyisocyanate mixture thus obtained is formed into a film and then subjected to an ion exchange treatment. The method of ion exchange treatment is basically similar to the method of ion exchange treatment of zeolite described above, in which the zeolite-containing film is treated with a solution of water-soluble salts of metals having a bactericidal effect. In this case, the concentration range of the metal salt is preferably 13M or less in the case of MutWO, preferably (105M or less in the case of LIM or less, fi, 0usO, etc.). If the amount is too high, basic precipitates of silver oxides and copper will precipitate, reducing the bactericidal effect. Zinc salts do not exhibit this phenomenon, so they should be treated at a concentration of around 2 to 3M. Both batch and continuous processing methods are possible.In order to increase the amount of metal ions retained, the number of batch treatments can be increased, or in the case of continuous processing, the processing time can be increased. .

This second method is based on the fact that the film-supported zeolite still retains its ion-exchange capacity and that, by appropriate ion-exchange treatment, it can be made to retain metal ions with a bactericidal capacity. ing. Since the antibacterial power of the antibacterial film of the present invention is thought to depend mainly on the metal ions near the surface of the film,
Not only is there no problem even if only the zeolite near the surface retains bactericidal metal ions, but the second method is an efficient method from the viewpoint of the utilization rate of bactericidal metal ions. In any case, the proportion of the metal having a bactericidal effect relative to the total amount of zeolite (based on anhydrous zeolite) may be 30% by weight or less for silver, and the preferable range is 1001 to 5% by weight. In the case of copper or zinc, it is 35% or less, and the preferred range is 0.0
It is 1 to 15% by weight. When silver, copper and zinc ions are used in combination, the total amount of metal ions is 1001
A range of 15 to 15% by weight is preferred. Further, there is no problem with the remaining or coexistence of other metal ions.

Zeolite content in zeolite particle-containing film (
3 wt%) and the amount of metal ions retained in the zeolite by ion exchange treatment relative to the metal-zeolite (mu wt%).
As mentioned in the first method, t%) is related to the magnitude of the bactericidal effect; if there is a lot of B, less A is needed, and conversely, if there is less B, it is necessary to use more A. be. It is desirable to adjust the value of AXB to 001 or more in the case of silver, and 111 or more in the case of copper or zinc.

The antibacterial film of the present invention may contain a third component other than metal zeolite. Examples include polymerization catalysts, stabilizers, matting agents, brighteners, organic or inorganic pigments, inorganic fillers, and various plasticizers.

The bonding strength of the antibacterial metal ions of the zeolite group copper and zinc defined in the present invention is extremely large, unlike the method of simply holding them by physical adsorption on an adsorbent substance such as activated carbon or alumina. Therefore, the strong bactericidal ability of the film containing such metallic zeolites and its long-term persistence are noteworthy as characteristic advantages of the present invention. The zeolite defined as in the present invention has the advantage of high reactivity with AP, Ou and Zn, which have bactericidal properties. For example, ion-exchangeable metal ions (Na”) in A-type zeolite, x-type zeolite, Y-type zeolite, and chabasite.
is easily KAt+, Cu! + or zrp+ to retain sterilizing metal ions in the matrix of zeolite, and has a high ability to retain them. Moreover, the zeolites limited as in the present invention are Mut+, Ou"+ and zr?+
It has the advantage of high selective adsorption to. This fact means that even if the urethane containing zeolite particles of the present invention gets wet during use, mu t+, a+, and z+ are stably retained in the zeolite matrix for a long period of time, and the bactericidal activity is maintained for a long period of time. are doing.

In addition, the zeolite defined as in the present invention has a large exchange capacity and has the advantage of being able to retain a large amount of Ou and Zn to A, which has bactericidal activity.

Further, depending on the purpose of use of the antibacterial film of the present invention, there is an advantage that the amounts of Muf, Ou and Zn contained in the zeolite solid particles can be easily adjusted by ion exchange.

Furthermore, the zeolite defined in the present invention rarely deteriorates the physical properties of the film.

The antimicrobial polyurethane film of the present invention can be in the form of a film alone, a laminate laminated with a woven or nonwoven fabric, or an intermediate adhesive layer of a laminated article. Since the film of the present invention has a remarkable effect of inhibiting the growth of bacteria and mold, it can be advantageously used in fields where hygiene is an issue. Examples include wound tape, sanitary belts, and leak prevention films for diaper covers. Also,
Since waterproof laminated clothing is prone to mold growth after use, the film of the present invention can be used as a laminating film or as an intermediate adhesive layer.

Moreover, since the zeolite particle-containing film of the present invention also has the functions inherent to zeolite, it is possible to utilize both antibacterial properties and the functions inherent to zeolite. For example, the combined effect of zeolite's original functions of moisture absorption and adsorption and antibacterial effects can be utilized.

Next, embodiments of the present invention will be described, but the present invention is not limited to the embodiments unless the gist thereof is exceeded.

Example ■ Production of antibacterial film A-type zeolite (composition 194 Na
1O@muIHOB ・t 92 EiiOl ・x bird 0
, average particle size 1.1. /J, 100℃ dry moisture content 1&0
% by weight, specific surface area 664 m"/l), and was repeatedly impregnated with a 0.1 M silver nitrate aqueous solution and a 105 M sulfuric acid steel sulfuric acid solution to obtain 16% by weight (based on anhydrous zeolite) of silver and &0% by weight (same). A bactericidal metal-containing zeolite containing copper was obtained.

Next, a polyurethane skin film and a laminated adhesive layer film were made as shown below.

Summer Epidermal Film Two epidermal mixtures with the following compositions: (a) General hard-to-change polyisocyanate solution* 100 parts by weight dimethylformamide (I) MIF) 20 #Methyl ether ketone (MKK) 50 #Bactericidal metal-containing zeolite 1, 2 ．． Or 3 parts by weight *Trademarked Lisbon NB-650 (manufactured by Dainippon Ink and Chemicals) Solid content 30 soil 1%, viscosity 55,000-5Q, 0OOc
ps.

Solvent DMI! P/MIIIK-2/1 +1)l Non-yellowing polyisocyanate solution 100 parts by weight DMF
10#MBK
2Qz Germicidal metal-containing zeolite 1.2 or 3% by weight *Trademark Honey x-x
(Honey Kasei), solid content 25±1%, viscosity IS, 00
0~25.0000pa %solvent DMIF/乍ICIC
Apply approximately 70p of Proverb 1/1 onto release paper and dry in dryer 2 at approximately 1aac.
A film was formed by passing the film for 1.5 minutes at a speed of 15 mm/min.

fa) and (t) 1% each, 100% modulus 65-7
0 to 97 degrees, 40 to 45 Yu/α8, light fastness 50H
, 3rd grade, and 200H5 grade films were obtained.

1 Laminated adhesive layer film On the skin film (a) formed on the release paper, a two-component urethane adhesive compounded liquid with the following composition: Crisbon 4QID* 100 parts by weight Crisbon NX (curing agent) 10 N Crispon IBM (promoted) agent) spI) MIF
20 1 MIK
30s
Bactericidal metal-containing zeolite 0 or 2 weight Uguri Lisbon (trademark) 401D: solid content 50 soil 1%, viscosity g
o, ooo~5Q, 0OOapa, solvent TOL/Ml
! : To! After applying 50μ of 6/4 and drying to remove the solvent, apply the base fabric (
Combine with polyester tape (7) and press with a heating roll to form a laminate under the following conditions.

Heating roll temperature: 90°C Press pressure: sokg7'ju8 Processing speed
15 false/min Adhesive volume (dry*) 2 at/-z The resulting film is peeled off the laminate from the 100 skin film of 261C11I/cm process.

It is suitable for use as sanitary material or clothing.
If necessary, softening treatment and water repellent treatment can be applied.

... Antibacterial activity test 1, Test purpose Test the antibacterial activity against bacteria and mold of the following six types of films of the present invention obtained in ① above Test method The antibacterial activity against Staphylococcus aureus and Escherichia coli was
! 'Co Te5t Method 100-1981
The antibacterial activity against black koji mold was tested according to Jx8 Z 2911 textile wet method.

(1) Antibacterial activity test against bacteria ■ Bacterial strain used (Staphylococcus aureus) (Escherichia coli) ■ Preparation of bacterial solution Too broth (Baato-pepton)
e 1%, Beef l1fxtraatα5%%80
(lium Chloride O, 5%) - Staphylococcus aureus was cultured in AATOCbroth, Escherichia coli was cultured in sterile physiological saline (11% triton
00 addition) so that the number of viable bacteria is approximately 1, and use this as a bacterial solution.

(2) Test procedure 10 specimens each having a size of approximately 3 cW1 x 3 cI11 were inoculated with bacterial solution α5-, and the number of viable bacteria was measured immediately after inoculation and after being left at 35°C for 6 hours.

That is, the sample was mixed with 8CDL1' broth medium 100-
The solution was shaken for 1 minute, and the number of viable bacteria in the shaken solution was counted by a pour plate culture method using 801) LP agar medium, and the number of viable bacteria for the sample used was calculated.

(2) Antibacterial activity test against mold■ Bacterial strain used: Muspergi11us niger IPO4414
(2) Preparation of Spore Suspension After sufficient spores were formed on an agar slant medium, the spores were suspended in sterilized water containing o, oos% sodium dioctyl sulfosuccinate to prepare a spore suspension.

■ Test procedure Place a sample piece cut into 1 cm 50 vm x 50 H size on top of a flat plate, sprinkle spore suspension 1-K evenly over it, cover with a lid, and keep at a temperature of 28 ± 2°C. The cells were cultured for 2 weeks.

Bacteria formed on the surface of the sample piece after culturing The growth state of the threads was observed with the naked eye.

Composition of shell plate medium Purification Water 100100O Chloride Karizem 125? Ammonium nitrate &O1 Ferrous sulfate α002 f Potassium sulfate 1. Of Kanten 25? Magnesium sulfate 9mm IIL5f Test results (1) The details of the results of antibacterial activity against bacteria are shown in Tables 1 and 2. In addition, the reduction rate was calculated using the following formula and is shown in Table 3 and Table 4.

Table-1 Staphylococcus aureus m: No test conducted Table-2 Escherichia coli m: No test conducted Table-3 Staphylococcus aureus Table-4 Escherichia coli (2) Antibacterial power against mold Table showing test results and how to display them. 5 and 61C were shown.

Table 5 Mold resistance test results Table 6 Method of displaying test results As is clear from the above Tables 1 to 5, laminates 1 to 3 containing bactericidal metal-containing zeolite in a polyurethane skin film according to the present invention, The laminates B-1 to S, which also contain bactericidal metal-containing zeolites in the polyurethane/adhesive film, exhibit significant antibacterial properties.

Claims (1)

[Claims] 1. Contains zeolite solid particles having a specific surface area of 150 m^2/g or more and a SiO_2/Al_2O_3 molar ratio of 14 or less, which retain metal ions having a bactericidal effect through ion exchange. Antibacterial polyurethane film made of urethane. 2. The film according to claim 1, wherein the zeolite solid particles are composed of A-type zeolite, X-type zeolite, Y-type zeolite, or mordenite. 3. The film according to claim 1, wherein the metal ion having a bactericidal effect is a species or two or more metal ions selected from the group consisting of silver, copper, and zinc. 4. Claim 1, in which the content of zeolite solid particles is 0.01 to 50% by weight (based on anhydrous zeolite)
The film described in section.