JPS61138795A - Antibacterial wallpaper - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to wallpaper with antibacterial properties.

Traditionally, wallpaper consists of Western or Japanese paper made from pulp or even waste paper raw materials, typically consisting of a front paper layer and a backing paper JI.
Y! It is made by laminating with W agent.

A problem with using wallpaper is the growth of mold. In other words, it is difficult to prevent the generation of force between the wallpaper and the wall, on the surface of the wallpaper, or inside the wallpaper, especially during the rainy season. The present invention provides a wallpaper that suppresses the growth of mold for many years. That is, the present invention provides a wallpaper that retains metal ions having bactericidal activity through ion exchange. Specific surface area of f or more and Sin, /Ago of 14 or less.

It is an antibacterial wallpaper containing zeolite solid particles having a molar ratio.

In the present invention, the zeolite solid particles having a bactericidal effect are defined as one or more metal ions having a whistle-killing effect on the ion-exchangeable part of a natural or synthetic zeolite made of aluminosilicate. It is maintained at ℃ through ion exchange. Preferred examples of metal ions having a bactericidal effect include AJ, Cu, and Zn. It is therefore possible to use the above-mentioned female-killing metals alone or in combination for the above-mentioned purposes.

Zeolites are generally aluminosilicates with a three-dimensionally developed skeletal structure.
y, -XM2/, OΦA4o, -ySiOl
=ZH20. 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 Z represents the number of crystallized water. Many types of zeolite are known with different composition ratios, pore diameters, specific surface areas, etc.

However, the specific surface area of the zeolite solid particles used in the present invention is 150 m"/? (based on anhydrous zeolite) or more, and the zeolite constituents have a specific surface area of 310, /At2o,
The molar ratio should 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-based particles that hold metal ions at a temperature of 150 m”/9 or more have a specific surface area of 150 m”/9 or more and have a surface area of 310 g.
/A 40g Two conditions must be met: the molar ratio is 14 or less. If not, the target product that achieves effective bactericidal action will not be obtained. This is thought to be due to the fact that the absolute amount of metal ions fixed on the zeolite 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, S i , known as molecular sieve
Zeolites with a large molar ratio of ot/kLto are completely inappropriate in the present invention.

In addition, in a zeolite with an 8101/A403 molar ratio of 14 or less, it is possible to uniformly retain metal ions having a bactericidal effect, and a sufficient bactericidal effect can only be obtained by using the zeolite for this purpose. In addition, the acid and alkali resistance of zeolite with a high silica ratio (S i Ox /A 40 g molar ratio exceeding 14) increases as S i o increases, but on the other hand, its synthesis (also takes a long time). From an economic point of view, it is not advisable to use a zeolite with such a high silica ratio.The above-mentioned natural or synthetic zeolite with S i O, /A40. From the point of view of alkalinity, it can be used satisfactorily, and from an economic point of view, it is inexpensive and a good idea.From this point of view, the molar ratio of 8101/A40s is 14.
Must be less than or equal to

810t/A40 used in the present invention. molar ratio of 1,4
As the zeolite material described below, either natural or synthetic zeolite can be used. For example, anal-cime (3i) is a natural zeolite.
02/A40B = 5b 6~5.6), Chabazite (Chabazite+ 5io1/A403 =
S, 2-6.0 and 64-Z6), clinoptilolite (C1ino-ptilolita+ 5iO
1/A40B-8,5~115), erionite (
Erionite: 5iO1/A403 x 5.8
~7.4), Faujaaita+
5iO1/A401 w 4.2~4.6), mordenite (Mordanitei 5iO1/A403
=&34~1α0), Philli
psite' sio, /ktt 0s-2,6~4
4) etc. These typical natural zeolites are suitable for the present invention. On the other hand, a typical synthetic zeolite is A-Zeolite (Sin).

/Ago, = 1.4-2.4), X-aum zeolite Sio, /A/40. = 2~3), Y
- type zeolite (S io, /A40. -3 to 6),
Examples include mordenite (SiO1/A403 = 9 to 10), and these synthetic zeolites are suitable as the zeolite material of the present invention. Particularly preferred are
These are synthetic A-huang zeolite, x-m zeolite, Yo-type zeolite and synthetic or natural mordenite.

The shape of the zeolite is preferably in the form of fine powder particles, and can be, for example, several microns to several tens of microns or several hundred microns or more.

In the present invention, the wallpaper itself can be any conventionally known wallpaper. For example, it may have a two-layer structure in which a front paper layer and a backing paper layer are bonded together with an adhesive.

The front paper layer is made of high-quality Japanese paper or Western paper, and the back paper layer can contain waste paper as a raw material. A synthetic resin film can also be used instead of the front paper layer or backing paper layer. The wallpaper can also be single layer rather than double layered.

The antibacterial wallpaper of the present invention is composed of zeolite solid particles and conventionally known wallpaper, and at least a portion of the zeolite solid particles retain metal ions having a bactericidal effect. Proportion of zeolite solid particles in the whole (based on anhydrous zeolite) & C1ot~15 weight S≠
The picture ≠ - Saisu Shijuto fight →. If it is less than the above lower limit, the antibacterial effect is unsatisfactory. On the other hand, even if the above upper limit is exceeded, the antibacterial effect remains almost unchanged, and the weight of the wallpaper becomes unnecessarily heavy. From this point of view, a more preferable content range is 0.05 to 10% by weight.

Metal ions undergo an ion exchange reaction (
must be maintained even more. If the zeolite is simply adsorbed or attached without ion exchange, the bactericidal effect and its sustainability will be insufficient.
- Taking seven cases of conversion to AEON/IT, normal people f
- A solution of a water-soluble silver salt such as silver nitrate is used during zeolite conversion, but care must be taken not to increase its concentration too much. For example, A-type or X-type zeolite (sodium-based) ion exchange reaction! When converting to AP-zeolite using ion exchange, if the silver ion concentration is high (for example, when using 1 to 2 MAPNO), the silver ions will replace sodium ions in the same phase and at the same time enter the zeolite solid phase. Silver oxides etc. precipitate out.For this reason, the porosity of 1 zeolite decreases, and the specific surface area has the drawback of significantly decreasing.Furthermore, even if the specific surface area does not decrease significantly, the presence of silver oxides itself In order to prevent the precipitation of excess silver into the zeolite phase, it is necessary to keep the silver solution diluted below the concentration t, for example, CL 5 MAfNO. The concentration is 11M or less.What can be obtained by using AfNO at such a concentration?-The specific surface area of zeolite is almost the same as that of the converted material, zeolite, and the bactericidal effect can be demonstrated under optimal conditions. understood.

Next, when converting to 1Cu-zeolite, the zeolite defined in the present invention, the same phenomenon as in the case of 1'-zeolite described above occurs depending on the concentration of copper salt used for ion exchange.For example, A-type zeolite. Or when converting x-zeolite (sodium-type) to Cu-zeolite by t ion exchange reaction, when using IMCuS04, C
u''+ replaces Na+ in the solid phase, but at the same time, 5 such as Cua(BO2)(OH)+ is added to the zeolite solid phase.
The disadvantage is that the porosity of the zeolite decreases due to the precipitation of basic precipitates, and the specific surface area decreases significantly. What concentration of aqueous pouring steel liquid should be used to prevent such excessive steel precipitation into the zeolite phase? more diluted, e.g. 0.05
It is preferable to keep it below M.

When using a CuSO4 solution with such a concentration, the Cu obtained
-The specific surface area of zeolite is almost the same as that of zeolite, which is the conversion material, and it has been found that it has the advantage of being able to exhibit its bactericidal effect in an optimal state.

It has been mentioned that during conversion to AJ-zeolite and Cu-zeolite, solid matter may be deposited on the zeolite solid phase depending on the concentration of salts used for ion exchange.However, when converting to Zn-zeolite, the concentration of salts used This phenomenon is not observed when the distance is around 2 to 3M. Generally, the Zn-zeolite used in the present invention can be easily obtained by using salts having concentrations around the above range.

When carrying out the ion exchange reaction by the bunch method in the conversion to the above-mentioned A2-zeolite, Cu-zeolite and Zn-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, the number of batch treatments may be increased. On the other hand, zeolite material is prepared using a column method using a salt bath solution having the above-mentioned concentration. During treatment, the desired metal-zeolite can be easily obtained by filling an adsorption tower with zeolite material and passing a salt solution through it.

The amount of metal in the above metal-zeolite (based on anhydrous zeolite) is 130 wt. CL5~1chi, 1~3 against strong awakening
% is sufficient.

On the other hand, regarding the copper and zinc used in the present invention, the action of steel is generally 1/7 that of silver, and that of zinc is 1/13 the same.
It is necessary to use a larger amount than silver.

In addition, the coexistence of metal ions other than silver, copper, and zinc, such as sodium, potassium, calcium, or other metal ions, does not impede the stimulant effect, so the residual or coexistence of these ions is not a problem. do not have.

As a method of incorporating the thus obtained zeolite containing sterilizing metal ions into wallpaper, zeolite can be mixed, for example, into an adhesive used for laminating the surface paper layer and the white paper layer. Alternatively, the adhesive can be applied to the paper layer and then sprinkled thereon. It can also be mixed with or sprayed on adhesives used to attach wallpaper to walls.

Alternatively, it can be included in a cosmetic application.

Alternatively, zeolite 11 containing bactericidal metal ions can be uniformly mixed into the paper raw material during any of the paper making processes. Since the bactericidal metal ions are firmly bound to the zeolite, they will not fall off during the process (and will not lose their bactericidal effect).The method of incorporating the zeolite in this way is to or backing paper, or -J-
It can also be done for structural wallpaper.

The bonding force between the zeolite defined in the present invention and antibacterial metal ions such as silver, copper, and zinc is extremely large, unlike a method in which the zeolite is held by an adsorbent substance such as activated carbon or alumina simply by physical adsorption. Therefore, the strong bactericidal ability of the polymer containing such metal zeolite and its long-term durability should be noted as the characteristic advantages of the present invention. AJ with Cu
It also has the advantage of high reactivity with Zn. For example, A
Ion-exchangeable metal ions (Na
``) easily performs ion exchange with Af+, Cu''+ or Zn''+, retains sterilizing metal ions in the zeolite matrix, and has a high retention ability. are Af”, Cu”+ and z
The fact is that even if the wallpaper containing zeolite particles of the present invention gets wet due to dew condensation, At'', Cu'', and Zn'' remain stable for a long period of time in the zeolite matrix. This means that the bactericidal power is maintained for a long period of time.

In addition, the zeolite defined as in the present invention has a large exchange capacity and has the advantage of holding a large amount of AP, Cu, and Zn, which have bactericidal properties.

Another advantage is that the amounts of AP, Cu, and Zn contained in the zeolite solid particles can be easily adjusted by ion exchange depending on the environment in which the antibacterial wallpaper of the present invention is used.

Moreover, the physical properties of the zeolite material paper defined in the present invention are less likely to be deteriorated.

Furthermore, since the wallpaper of the present invention also has the original functions of zeolite, it can be used in conjunction with the anti-female properties and the original functions of zeolite. For example, zeolite's inherent moisture absorption and adsorption effects help prevent wallpaper from becoming wet.

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

Example ■ A-type zeolite (composition 0, 94N) as antibacterial wallpaper zeolite
a20-A401 ・t925iO1-xHlo,
Using an average particle diameter of t1μ, a moisture content of 140% by weight when dried at 100°C, and a specific surface area of 664mm/f), this was repeatedly impregnated with a 11M silver nitrate water bath solution or a 0.05M sulfur #lt steel aqueous solution to obtain a 2.6-weight: l1% (based on anhydrous zeolite) silver or 8.
A surface paper consisting of 73% by weight of wood pulp and 27% by weight of inorganic chemicals, inorganic minerals, organic adhesives and organic flame retardants was obtained. The adhesive used to bond the two layers of the backing paper was mixed with zeolite containing rust &O%'g in the amount shown in Table 1 below, and the adhesive was 759
Zeolite is used in an amount of 7 m'' and contains zeolite in the table! (4) is the amount relative to the adhesive.
A surface cosmetic material containing vinyl acetate as a main ingredient in the amount specified in
% 75 f/lyl.

In Table 1, the zeolite content (4) is predominant in weight relative to the surface cosmetic containing 40% solids.

Table 1 N11 1
1 2 2
2NIL5 5
5N14 (L5
t5 5 1
2 ■ Antibacterial power test The antibacterial power of the test sample against bacteria and mold was tested.

2 Test method Antibacterial activity of sample against Escherichia coli and Aspergillus niger t1
Halo Test and AATCC TestMethod
100-1981.

(1) Presence or absence of growth inhibition zone (halo)■ Bacterial strain used Escherichia coli IID 0-55
(Escherichia coli) Aspergillus niger I
FO4414 (Koji mold) ■ Preparation of test bacterial solution For Escherichia coli, a normal bouillon culture medium was diluted with sterilized physiological saline to a concentration of about 10'/d, and this was used as a bacterial solution. The Aspergillus niger was cultured on a potato dextrose agar slant medium until sufficient spores were formed, and then suspended in cL005ts sodium dioctylsuccinate sterilized water to adjust the number of spores to about 10S/-.

■ Approximately 20 ml of agar plate media, Yusei Trigton'i Agar (TSA) and Potato Dextrose Agar (PDA), were poured into a petri dish and allowed to solidify. #Cracked bacterial fluid α1-t
1 E. coli was smeared on a TSA plate, and Aspergillus niger was smeared on a PDA plate.

■ Approximately 45 IIX 4 cm on each agar plate subjected to test procedure l5lIW.
Place the sample piece cut into the size of E. coli at 35℃, 2
After culturing for 4 hours, Koji niger mold was incubated at 25℃ for 4 days,
The presence or absence of a growth inhibition zone was observed.

(2) AATCCTe5t Method 100
- Test according to 1981 ■ Bacterial strain used gscherichia calf rID 0-55
(Escherichia coli) Aspargillus nlger I
FO4414 (Koji Mold) ■ Preparation of Test Bacterial Solution Escherichia coli was cultured in AATCCbroth-Night culture t1 K. K. black mold was allowed to form sufficient spores in PDA slant medium, and then Q, 1% tritonX-100 sterilized physiological saline? This solution was diluted to a bacterial count of approximately 10 5 /d using the following methods.

■Test operation Sample 5 cut into a size of approximately 5 cm x 5 cns
A 0.5-mL bacterial solution was inoculated onto each plate, and the number of viable bacteria for Escherichia coli was measured immediately after inoculation and after being left at 55°C for 6 hours, and for Aspergillus niger, the number of viable bacteria was measured immediately after inoculation and after being left at 25°C for 24 hours.

The raw W number was measured as follows. 〇 Namely, the test sample was shaken out for 1 minute in 5 CDLP broth medium 100-, and the number of viable bacteria in the shaken out solution was t1.
Agar medium t, Aspergillus niger was measured by a pour plate culture method using a GPLP agar medium.

V. Test results (1) Table 2 shows the results of the presence or absence of a growth inhibition zone (halo). -41-Table-2 Anti-violation power of the sample +: Width of growth inhibition zone 5 ■ or less + 10: Width of growth inhibition zone 5 to 10 ■ (2) AATCCTe5t Method 100
-1981, the test results are shown in Tables 3 and 4. The reduction rate was calculated using the following formula.

Table-3 Escherichia coli The pot reduction rate was calculated using the value immediately after inoculation of No. 5.

Although the inoculation amount was tOX105 or more, the low number of viable bacteria immediately after inoculation is probably because they died immediately. In addition, in the blank, the number of cells increased to about 106 after 6 hours.

Table 4: Black Koji Mold As is clear from Tables 2 to 4 above, the wallpaper of the present invention exhibits a remarkable anti-cold effect.

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 wallpaper. 2. The wallpaper 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 wallpaper according to claim 1, wherein the metal ion having a bactericidal effect is one or more metal ions selected from the group consisting of silver, copper, and zinc. 4. The wallpaper according to claim 1, wherein the content of zeolite solid particles (based on anhydrous zeolite) is 0.01 to 15% by weight based on the total weight of the wallpaper.