JPH08243265A - Antibacterial folding paper - Google Patents

Abstract

PURPOSE: To provide an antibacterial folding paper having little decoloration, a sufficient antibacterial property, and a higher sanitary property, by coating a silver inorganic antibacterial agent including the zirconium phosphate as a cirrier, on one side or both sides of the paper. CONSTITUTION: This antibacterial folding paper is manufactured by coating a silver type inorganic antibacterial agent including zirconium phosphate as a carrier, 0.002 to 0.03g/m<2> in the solid part, on one side of both sides of the paper. A conventional organic type antibacterial substance is pointed out that it is liable to be eluted in a partial condition, and it is difficult to used because the present manufacture process of the folding paper is in the water system. On the other hand, an inorganic type antibacterial agent can exercise the effect by adding an antibacterial metal to an inorganic ion exchanger, a porous body, or the like, but it is most suitable to add the silver in respect of the safety and the antibacterial effect. Of the material available to the carrier, the material suitable to the folding paper, having an excellent weatherability, and having small elution amount of the silver, is the zirconium phosphate silver. Consequently, the silver type antibacterial agent including the zirconium phosphate as the carrier is applied.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to origami used as toys, and more particularly to an antibacterial origami that is safe and has excellent antibacterial properties and weather resistance.

[0002]

2. Description of the Related Art It has been well known that silver and copper have a bactericidal action. For example, silver is widely used as a disinfectant in the form of an aqueous solution of silver nitrate (Ag ⁺ ). It is also known that silver or a compound thereof is adsorbed on an adsorbing substance such as activated carbon, alumina, silica gel, or zeolite and used for the purpose of sterilization. As above,
JP-A-62-241939, JP-A-62-238
There is one disclosed in Japanese Unexamined Patent Publication No. 900, which is a polyolefin resin molded body and a paper containing zeolite which holds a metal having a bactericidal action in an ionic state.
Further, as disclosed in JP-A-62-70221, there is no antibacterial and / or bactericidal action represented by the formula M ₂ O.Al ₂ O ₃ .SiO ₂ (where M is silver, etc.). There is a regular aluminosilicate. In addition, 5-12
As disclosed in Japanese Patent No. 0690, at least one selected from the group consisting of silver, copper, lead, zinc, tin and bismuth having an antibacterial action on N-long chain acylamino acids attached to the surface of synthetic resin particles or inorganic particles. There is an antibacterial material in which two metals are combined.

[0003]

The silver nitrate conventionally used is limited in the form of an aqueous solution, and it is inconvenient to handle because it is in the form of a solution. Therefore, it has a drawback that its use is limited. The compounds disclosed in JP-A-62-241939 and JP-A-62-238900, and those disclosed in JP-A-62-70221 have an antibacterial action and a bactericidal action, but The metal having an antibacterial property to be used is oxidized by light (especially ultraviolet rays) and discolors, so that there is a problem that the entire substance is discolored. Furthermore, the sterilizing metal used is
Since it is easily ionized, when it comes into contact with a liquid substance or the like, it tends to flow out and there is a problem in safety. In recent years, with increasing interest in antibacterial specifications in terms of safety and hygiene, the present inventors have conducted earnest research on origami regarding selection of antibacterial agents and processing methods.

(1) Processing method: The required quality of origami, that is, no change in color,
It is required that the color does not fade and that the quality required for the antibacterial paper is effective, that is, it is effective with a small amount of addition, and that it does not cause unnecessary loss or impair safety. Also, ease of manufacture must be considered. (2) Regarding the surface on which the antibacterial agent is added (coating) The effect of the antibacterial agent is basically the same whether the antibacterial agent is applied to the front or back of the base paper. That is, which of the pigment-coated surface and the non-pigment-coated surface is to be coated is arbitrarily determined. However, in the method of applying the antibacterial agent to the non-pigment coated surface, if the amount of the binder is increased so as not to fall off, the surface of this surface will be covered.
Will be bigger. Moreover, since the pigment coating liquid has different solid contents, binder blending ratios, coating amounts, etc. for each color, it may be difficult to adjust the curl.

Moreover, if the antibacterial agent is completely coated with the binder, the antibacterial effect is weakened, and it is difficult to balance the curl, which leads to an increase in the required amount of the antibacterial agent added. Therefore, the addition of the antibacterial agent to the pigment coating solution is the most preferable method in operation because the production process can be the same as that of ordinary origami paper. However, when it is desired to have antibacterial properties on both sides, or in the case of double-sided coated paper, an antibacterial agent can be added to both sides of the base paper in an arbitrary ratio. However, when an antibacterial agent is added to the pigment coating surface, compatibility with organic and inorganic pigments, binders, and other auxiliaries (smoothing agents, defoaming agents, etc.) is particularly important, and the coating liquid It is important to select a material that does not cause agglomeration during the preparation, coating and drying.

[0006] The specific problems for functioning as an antibacterial origami are (1) safety. (2) It has weather resistance, and especially in origami, since coloring is important, it is excellent in light resistance.

The most important target quality of the present invention is to achieve both safety as origami paper, maintenance of weather resistance, and imparting stable antibacterial property. Therefore, as a result of earnest trial and error, the inventors of the present invention found the possibility of achieving both target qualities by determining the selection and concentration of the antibacterial agent, as well as the policy for fixing the antibacterial agent. That is, the use of a silver-based inorganic antibacterial agent having zirconium phosphate as a carrier, which has been highly evaluated as an antibacterial agent, is to mix and apply the antibacterial agent in a coating solution.

The selection of the binder is important in order to maximize the effect of the antibacterial agent. Examples of binders that can be used for coated paper include PVA, water-soluble polymers such as starch, SBR,
Latex such as MBR, acrylic, vinyl acetate,
Examples include various emulsions such as vinyl chloride type and epoxy type. However, when considering the performance as an origami paper, water-soluble polymers such as PVA and starch have strength when dried but have poor water resistance and are easily eluted, and the combined use of water-proofing agents may cause discoloration over time. . SBR is satisfactory in strength and water resistance but is inferior in light resistance.
The present invention considers workability during coating, production of double-sided coated product,
Acrylic emulsion with a small amount of sufficient strength, excellent safety as an origami paper (no elution), maximizing the properties of antibacterial agents, and excellent operability as a coating material. Adhesive was selected. It has good miscibility with pigments and very little foreign matter is generated due to aggregation.

[0009] Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide an antibacterial origami having a low antibacterial property, safety, and a low discoloration property.

[0010]

As a means for achieving the above object, the present invention provides a silver-based inorganic antibacterial agent having zirconium phosphate as a carrier in a solid content of 0.002 to 0 on one or both sides. 0.03 g / m ^{2 is} applied. It has been pointed out that the conventional organic antibacterial substances (2-4 thiazolyl-benzimidazole) are likely to be eluted under some conditions, and the manufacturing process of origami is currently water-based,
Difficult to use. In addition, organic antibacterial agents generally have limited heat resistance, and some of them volatilize and decompose. Furthermore, as for thiabendazole (TBZ), trimethoxysilylpropyl octadecyl ammonium chloride, and oxybisphenoxyarsine, the safety (LD- ₅₀ mouse) is TBZ 3600 mg / kg, and the others are 120
It was 0 to 2000 mg / kg (rat), and it was judged to be a somewhat strong drug for origami.

However, an inorganic antibacterial agent exerts its effect by adding an antibacterial metal to an inorganic ion exchanger, a porous body or the like, but its antibacterial activity varies depending on the kind of the metal. Generally, the antibacterial action becomes weaker in the order of mercury, silver, lead, copper, nickel, zinc and cadmium. Among the above metals, silver is the most suitable from the viewpoint of safety and antibacterial activity. And what can be used as a carrier of the present invention, zeolite,
Examples thereof include hydroxyapatite, silica gel, silica / alumina, zirconium phosphate and the like. Among these, zirconium phosphate silver or apatite silver having excellent weather resistance is suitable for origami. Furthermore, in terms of the amount of silver dissolved in water, zirconium phosphate silver is significantly smaller than apatite silver.

[0012]

The essence of the present invention is to use a silver-based inorganic antibacterial agent having zirconium phosphate as a carrier, which has significantly improved discoloration, which is a drawback of conventional silver-based inorganic antibacterial agents, and to apply the antibacterial agent in the coating amount. Is defined in a specific range to form safety, weather resistance and stable antibacterial properties. This will open the way to the application of the silver-based inorganic antibacterial agent treatment using zirconium phosphate as a carrier to origami, which has hitherto been highly evaluated for safety and a wide range of antibacterial properties.

[0013]

【Example】

Example 1 Unit: g Coating liquid 1 Water 52 Acrylic binder-24 Color pigment A 24 A silver-based inorganic antibacterial agent having zirconium phosphate as a carrier (Toagosei Co., Ltd., trade name: Novalon AG300 (the following examples. In the above, it is simply referred to as an antibacterial agent.)) 0.040 ───────────────────────── 100.040 A coating liquid 1 was obtained with the above composition. High quality base coated base paper 5
13 g / m ² using a Mayer bar for 2.3 g / m ^2.
Apply ² (WET). (As an antibacterial agent,
0052 g / m ² ). This is dried at 105 ° C. for 1 minute, and after conditioning the humidity, it is used as a service sample.

Example 2 Unit: g Coating liquid 2 Water 52 Acrylic binder-24 Colored pigment A 24 Antibacterial agent 0.201 ───────────────────── ──── 100.201 As in Example 1, coated paper of fine paper base 52.3 g /
Using a Mayer bar for m ² , the coating is performed so as to be 13 g / m ² (WET). (0.0261g / m as an antibacterial agent
² ). This is dried at 105 ℃ for 1 minute, after conditioning the humidity,
Use as a sample to be served.

Example 3 Unit: g Coating liquid 3 Water 64.04 Acrylic binder 14.80 Color pigment B 21.16 Antibacterial agent 0.040 ──────────────── ────────── 100.040 As in Example 1, 52.3 g / of base paper coated with fine paper base
Using a Mayer bar for m ² , the coating is performed so as to be 13 g / m ² (WET). (0.0052g / m as an antibacterial agent
² ). This is dried at 105 ℃ for 1 minute, after conditioning the humidity,
Use as a sample to be served.

Example 4 Unit: g Coating liquid 4 Water 78.75 Acrylic binder 10.63 Color pigment C 10.62 Antibacterial agent 0.040 ──────────────── ────────── 100,040 52.3 g / based coated base paper of high-quality paper base as in Example 1
Using a Mayer bar for m ² , the coating is performed so as to be 13 g / m ² (WET). (0.0052g / m as an antibacterial agent
² ). This is dried at 105 ℃ for 1 minute, after conditioning the humidity,
Use as a sample to be served.

Example 5 Unit: g Coating liquid 5 Water 79.00 Acrylic binder 12.22 Color pigment C 8.78 Antibacterial agent 0.040 ─────────────── ────────── 100.040 As in Example 1, 52.3 g / of base paper coated with fine paper base
Using a Mayer bar for m ² , the coating is performed so as to be 13 g / m ² (WET). (0.0052g / m as an antibacterial agent
² ). This is dried at 105 ℃ for 1 minute, after conditioning the humidity,
Use as a sample to be served.

Example 6 Unit: g Coating liquid 6 Water 49.90 Acrylic binder 23.40 Color pigment C 26.7 Antibacterial agent 0.040 ──────────────── ───────── 100.040 Similar to Example 1, 52.3 g / of coated base paper of high-quality paper base
Using a Mayer bar for m ² , the coating is performed so as to be 13 g / m ² (WET). (0.0052g / m as an antibacterial agent
² ). This is dried at 105 ℃ for 1 minute, after conditioning the humidity,
Use as a sample to be served.

Comparative Example 1 Unit: g Coating liquid 7 Water 52 Acrylic binder-24 Color pigment A 24 ──────────────────────── 100 Fine paper-based coated base paper 52.3 g /
Using a Mayer bar for m ² , the coating is performed so as to be 13 g / m ² (WET). This is dried at 105 ° C. for 1 minute, and after conditioning the humidity, it is used as a service sample.

Comparative Example 2 Fine paper-based coated base paper 52. used in Examples and Comparative Examples.
3 g / m ² itself (without coating) was used. Example 1
The antibacterial treated paper obtained in No. 6 and the non-antibacterial treated papers obtained in Comparative Examples 1 and 2 were used as a control, and a SEK nylon standard cloth was used as a shoe.
It was measured by the Kuflask method, and the results shown in Table 1 were obtained.

[0021]

[Table 1] As described above, Examples 1 to 6 all showed sufficient antibacterial properties against Staphylococcus aureus and Escherichia coli.

Example 7 A light resistance test was performed on 20 colors of antibacterial paper. The composition of the coating liquid is as shown in Table 2, and the same as in Example 1, 52.3 g / m ² of base paper for coating high-quality paper was used with a Mayer bar.
Coat to g / m ² (WET). However, the application amount of the antibacterial agent is 0.0052 g / m ² , N
It was set to 0.0104 g / m ² at o11 to 20. This one
It is dried at 05 ° C for 1 minute, and after conditioning the humidity, it is used as a service sample. Test conditions: Fluorescent lamp 5000LUX 1 month Measurement method Color difference meter (Nippon Denshoku Z-1001DP)
Is used to measure L, a, and b for untreated and treated products. Evaluation method Here, the measured values of the treated products are L ₁ , a ₁ , b
₁ , ΔE is calculated by the following equation, where L ₂ , a ₂ and b ₂ are the measured values of the untreated product. ΔE1 = ((L ₁ −L ₂ ) ² + (a ₁ −a ₂ ) ² + (b
_1- b ₂ ) ² ) ^{1/2 The} results are shown in Table 4.

Example 8 A heat resistance test was conducted on a sample prepared by the same method as in Example 7. Test conditions: Dryer 60 ° C. 1 month Measurement and evaluation were performed in the same manner as in Example 7. The results are shown in Table 5.

Example 9 A moisture resistance test was conducted on a sample prepared by the same method as in Example 7. Test conditions: constant temperature and humidity 35 ° C.-85% RH 1 month Measurement and evaluation were performed in the same manner as in Example 7. The results are shown in Table 6.

[0025]

[Table 2]

[0026]

[Table 3]

Comparative Example 3 A light resistance test was conducted on 20 colors of non-antibacterial paper. The composition of the coating liquid is as shown in Table 3, and as in Comparative Example 1, 52.3 g / m ² of base paper for coating high-quality paper was used with a Mayer bar.
Coat to 3 g / m ² (WET). This is 10
Dry at 5 ° C. for 1 minute, adjust the humidity, and use as a sample to be served. However, No. 19 “white” is uncoated paper (base paper). Test conditions: Fluorescent lamp 5000LUX 1 month Measurement method Color difference meter (Nippon Denshoku Z-1001DP)
Is used to measure L, a, and b for untreated and treated products. Evaluation method Here, the measured values of the treated products are L ₁ , a ₁ , b
₁ , ΔE is calculated by the following equation, where L ₂ , a ₂ and b ₂ are the measured values of the untreated product. ΔE2 = ((L ₁ −L ₂ ) ² + (a ₁ −a ₂ ) ² + (b
_1- b ₂ ) ² ) ^{1/2 The} results are also shown in Table 4.

Comparative Example 4 A heat resistance test was conducted on a sample prepared by the same method as in Comparative Example 3. Test conditions: Dryer 60 ° C. 1 month Measurement and evaluation were performed in the same manner as in Comparative Example 3. The results are also shown in Table 5.

Comparative Example 5 A moisture resistance test was conducted on a sample prepared by the same method as in Comparative Example 3. Test condition: constant temperature and humidity 35 ° C.-85% RH 1 month Measurement and evaluation were performed in the same manner as in Comparative Example 3. The results are also shown in Table 6.

[0030]

[Table 4]

[0031]

[Table 5]

[0032]

[Table 6]

Tables 4, 5 and 6 also show the values of ΔE1-ΔE2. When ΔE1-ΔE2 is a positive value, it indicates that the discoloration of the antibacterial treated paper is larger than that of the non-antibacterial treated paper.
A negative value of ΔE2 indicates that discoloration of non-antibacterial treated paper is larger than that of antibacterial treated paper. Depending on the color of the origami,
Although there are differences in tendency, antibacterial treated paper and non-antibacterial treated paper show almost the same tendency of discoloration under light resistance, heat resistance, and humidity resistance, and a silver-based inorganic antibacterial agent using zirconium phosphate as a carrier. It can be seen that when applied to colored paper, it has sufficient weather resistance under normal environmental conditions.

[0034]

EFFECTS OF THE INVENTION The antibacterial origami of the present invention does not discolor, as can be seen from the above test results, and further, the bacterial reduction rate after the lapse of 3 hours by the Toa shake flask method is 26% or more. . Therefore, it is possible to provide a more hygienic origami paper that has sufficient antibacterial properties.

Claims (1)

[Claims] 1. A silver-based inorganic antibacterial agent having a carrier of zirconium phosphate as a solid content of 0.00 or more on one side or both sides of paper.
An antibacterial origami coated by ² to 0.03 g / m ² .