JPH0561400B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a method for producing functional wallpaper having various functions such as air purification, deodorization, antibacterial, and antifungal effects. (Prior Art) Conventionally, many wallpapers made of vinyl chloride resin are known. This wallpaper is anti-static,
Flame-retardant wallpaper that has been treated to prevent dew condensation is known, but wallpaper that has an air purifying effect is not known. This is thought to be because conventional deodorizing agents such as activated carbon lose their activity when incorporated into wallpaper. (Problem to be Solved by the Invention) Therefore, conventional wallpapers, other than the purpose of satisfying aesthetic sense, only perform ancillary functions such as preventing static electricity and preventing condensation. However, when we took the objective a step further and considered purification (air purification, deodorization, and sterilization) as well as the beautification of living and working environments, we were not necessarily satisfied with the results. (Means for Solving the Problems) The present inventors have conducted various studies in order to overcome the drawbacks of conventional wallpapers, and as a result, they have developed wallpapers made of vinyl chloride resin by adding L-ascorbic acid to iron () compounds. It was discovered that wallpaper having an air purifying function can be obtained by coating or incorporating the combined composition, and based on this knowledge, the present invention was completed. That is, the present invention provides a method for producing functional wallpaper, which comprises coating or mixing a composition formed by combining an iron() compound and L-ascorbic acid (hereinafter referred to as an iron() composition) into a wallpaper material. This is what we provide. There are no particular limitations on the wallpaper material used in the present invention, and conventional and commonly used wallpaper materials can be used. Flame-retardant vinyl chloride resin is most suitable for the surface decorative layer, but the material is not limited thereto, and urethane resin, acrylic resin, polyethylene resin, polypropylene resin, and polyester resin may also be used. Further, the base fabric may be flame retardant paper, synthetic paper, inorganic paper, or woven fabric. In short, iron ()
Any wallpaper material to which the composition can be applied may be used. Among these, a typical example of a particularly preferable formulation of a vinyl chloride resin wallpaper material is shown below. Blend (A) Parts by weight Vinyl chloride resin 100 Plasticizer (including flame retardant plasticizer 60 Foaming agent (ADCA) 5 Stabilizer 3.5 Filler 10 Flame retardant 3 pigments 30 Total 211.5 Blend (B) Part by weight Vinyl chloride resin 100 Plasticizer (Contains flame retardant plasticizer) 55 Blowing agent (OBSH) 2 Stabilizer 2 Filler 50 Flame retardant 3 Pigment 20 Total 232 The iron () composition used in the method of the present invention contains an iron () compound and a small amount of L-ascorbic acid. This active substance will be described in detail below.The ratio of iron () and L-ascorbic acid in the iron () composition is in the range of 1:0.02 to 0.3 (weight ratio). is preferably in the range of 1:0.02 to 0.13. Even if L-ascorbic acid is used exceeding the upper limit of this range, the composition will be colored, the activity will decrease, and it will become uneconomical. less than
The stability of iron () becomes insufficient. It is also preferable to add alum to the iron() composition. The amount of alum added varies depending on the use and form of use of this composition, but it is used up to 100% by weight based on the total amount of iron () compound and L-ascorbic acid, but ranges from 5% to 20% by weight. is preferred. The alum is not particularly limited, but potassium alum, ammonia alum, sodium alum, etc. are preferred, with roasted alum being particularly preferred. The iron () composition is prepared by once dissolving and mixing the above-mentioned components in a predetermined ratio in an aqueous solution. There are no particular restrictions on the form in which it is used. For example, it may be made into an aqueous solution as it is, or it may be processed to form a powder or granules by spray drying or the like. When used as an aqueous solution, it can be applied at any concentration within the solubility range of the iron() compound. Examples of iron() compounds used in iron() compositions include iron() inorganic salts such as ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous bromide, and ferrous iodide. In addition, there are organic salts of iron such as ferrous gallate, ferrous malate, and ferrous fumarate. The iron () compound is not limited to those exemplified above, and any compound can be used as long as it dissolves in water and forms divalent iron ions. This iron() composition is then applied by coating or mixing into the wallpaper. Any coating method may be used, but there are two preferred methods: a method using a gravure printing machine and a method of applying with a doctor knife. The entire process is shown below. (a) How to use a gravure printing machine

[Table] After gravure printing, dry at 120-130℃ for 30-60 seconds. This process is shown in FIG. In the figure, 1 is an unwinder, 2 is wallpaper material, 3 is water-based ink, 4 is a rubber roll, 5 is a mesh roll, 6 is a drying oven, 7
is a rewinder, and 16 is the wallpaper thus obtained. (b) Valley staining method using a doctor knife

[Table] After staining, dry at 130-140℃ for 1-1.5 minutes.
This process is shown in FIG. In the figure, 8 is an unwinder, 9 is a wallpaper material, 10 is an ink fountain, 11 is a doctor knife, 12 is a rubber roll, 13 is a drying oven, 14 is a cooler, and 15 is a rewinder. 17 is wallpaper manufactured in this manner. For such applications, water-based inks containing iron() compositions are used. When used as an iron composition and aqueous solution, the solid content concentration in the iron composition aqueous solution is the highest due to solubility.
Iron in water-based inks (up to 30% by weight)
If the amount of the aqueous composition solution is too large, there is a risk that the aqueous ink will gel, so the amount is 30% by weight or less, preferably 25% by weight or less, and from the viewpoint of processing stability, it is preferably 15 to 20% by weight. The basic composition of the water-based ink can be the same as that of conventional gravure water-based inks. An example of a water-based ink formulation of an iron () composition is shown below. Component Weight part VPA G Medium 90 〃 〃 Color 10 Iron () composition aqueous solution (solid content 20%) 20 Total 120 (Note) VPA G Medium: Resin content (vinyl chloride-acrylic copolymer) 22% VPA G Color: Resin content (same as above) 18-24% Pigment content 3-15% The amount of water-based ink applied is usually 10-40 g/m2, preferably 20-40 g/m ² in the gravure printing method (a) above.
It is in the range of 30g/ ^m2 . Further, in the valley staining method using a doctor knife (b) above, the amount is in the range of 20 to 70 g/m ² , preferably 30 to 50 g/m ² . In this case, if the coating amount exceeds 70 g/m ² , there will be problems with the adhesion of the ink and the stability of the surface hue, and if it is too small, the desired function will not be fully exhibited. Next, in the present invention, the iron () composition may be used in the form of powder. In this case, for example, it can be blended into a base sol of vinyl chloride resin to prepare a coating composition, and this can be diluted to an appropriate concentration or applied to the wallpaper material without being diluted. An example of such a coating composition is shown below. Ingredients Parts by weight Vinyl chloride paste resin 100 Plasticizer 50 Stabilizer 2 Iron () composition powder 20 (ferrous sulfate: L-ascorbic acid = 1:0.03
(Mole ratio) Particle size of several tens of microns) Pigment 20 Total 192 It is necessary to apply strong shearing force (such as passing through a paint roll) to disperse this paint composition, but the paint prepared from this can be used in the same way as ordinary PVC paste sol. In the present invention, steps other than coating by gravure printing or valley smudging methods, such as printing and embossing steps, can be performed in the same manner as in conventional wallpaper production. Furthermore, in the present invention, depending on the type of wallpaper material, powder of the iron () composition may be directly kneaded into the wallpaper material. (Function) The mechanism by which the wallpaper obtained according to the present invention performs the air purifying function is not necessarily clear, but the reaction product between the active ingredient iron () compound contained in the wallpaper and L-ascorbic acid is as follows. This is thought to be because it is working. That is _, due to the action of divalent iron ions in the presence of L-ascorbic acid, as shown in ^the following formula, Fe ()+O ₂ Fe()・O ₂ Fe()・O ₂ ^- Fe()・O ₂ +Fe()Fe()・O ₂・Fe()
Fe()・O ₂ ^- Fe() It is thought that such super ion oxides contribute to purification of the indoor atmosphere, including deodorizing and sterilizing effects. (Effects of the Invention) According to the present invention, an interior material can be obtained which has unique performance (air purification, deodorization, antibacterial, and antifungal) by adhering or containing an L-ascorbic acid-ferrous ion binding substance. I can do it. The major feature of the wallpaper produced by the method of the present invention is that it not only beautifies the interior of the room, but also purifies the surrounding atmosphere and at the same time generates active oxygen, which is very favorable biochemically. In the present invention, the deodorizing effect is one element, but it is not the only factor, and is a measure of each effect based on active oxygen. Further, according to the present invention, by perforating the wallpaper, an excellent effect is achieved in that air purification functions such as deodorizing functions can be maintained. Furthermore, according to the present invention, the iron () composition itself has a flame retardant effect, and the flame retardance of the wallpaper can be further improved. Furthermore, according to the method of the present invention, functional wallpaper can be obtained that maintains its activity to withstand heating such as embossing and foaming. Although the wallpaper obtained by the method of the present invention can be used in the same manner as ordinary wallpaper, it is particularly preferably used in living rooms and toilets of ordinary residences, hospital rooms, nursing stations, and the like. (Examples) Next, the present invention will be described in more detail based on Examples. Example 1 [Preparation of ink] A water-based ink was produced with the following composition, and it was applied onto embossed vinyl chloride resin wallpaper (PVC sol coating thickness: 160 to 200 μm) by the valley staining method using a doctor knife as shown in Figure 2. Coated. Water-based ink (parts by weight) VPA G medium 90 〃 〃 Color 10 Iron () composition aqueous solution 20 Total 120 The coating conditions are as follows. Coating amount: approx. 30 g/m ² Processing speed: 15 m/min Drying temperature: 1 minute at 120°C In addition, the iron () composition aqueous solution is prepared by dissolving 27.5 g of ferrous sulfate heptahydrate (molecular weight 278.03) in water and adding 100 m/min. After that, add and dissolve 0.5g of L-ascorbic acid to prepare a stock solution, and add 10g of roasted alum to 100m of this stock solution.
was added, stirred for 30 minutes, centrifuged and filtered. The following tests () to () show the results of testing the air purifying effect of wallpaper treated in this way.
Shown below. Test (i) In a 25 x 30 cm polyethylene bag, place filter paper (1/4 filter paper with a diameter of 9 cm) impregnated with approximately 0.45 g of each of chemicals such as formalin, artificial perspiration, and ammonia at the following concentrations at the bottom of the bag. The odor intensity in the bag was tested by placing 10 cm ² of treated wallpaper sample. The results are shown in Table 1 as Test No. 1. In addition, the wallpaper sample was further heated at 180℃ for 20 seconds (embossing condition) or
A similar test was conducted for the case of heating at 230° C. for 1 minute (foaming processing conditions), and these are also listed in Table 1 as Test Nos. 2 and 3, respectively. Chemical concentration (1) Formalin 5% aqueous solution (2) Artificial sweat liquid Prepared according to JIS K 6772 (3) Ammonia 1.25% aqueous solution (4) Cresol 1% aqueous solution (5) Hydrogen sulfide Aqueous solution passed through hydrogen sulfide gas for 5 minutes

【table】

[Table] Test (ii) Next, the air purifying effect of this wallpaper was tested after it was left in normal air for a certain period of time. The test was carried out on wallpaper heated at 230°C for 1 minute. The test results are shown in Table 2.

[Table] (Note) Evaluation criteria are the same as in Table 1.
The results of the above sensory tests show that the wallpaper of the present invention has a deodorizing effect on malodorous substances (excluding formalin) generated in daily life, and it was heated (230℃ x about 1 minute).
It is presumed that the effect will not be lost even if the effect is changed over time, and that the effect of changes over time will not be significant and that the effect will remain stable for a considerable period of time. Note that the atmospheric concentration in the above test was so high that it is not normally experienced in daily life, and the fact that it maintains its effectiveness even under these conditions means that it can withstand long-term use. Test (iii) Next, a deodorization test was conducted using the test device assembled as shown in Figure 3. A in the figure is a tetrabag,
B is a flowmeter, C is a column, and P is a pump. Put 5g of wallpaper sample shredded into approximately 5mm squares into C in the figure.
NH ₃ gas with a concentration of 5000 ppm was connected to A, and the concentration was measured after the gas was circulated for 1 hour.
Next, add a new gas (NH ₃ concentration 5000 ppm) to A (change the NH ₃ gas but leave the wallpaper sample as is)
Similar experiments were repeated four times. The results of the four experiments are shown in Table 3.

[Table] Example 2 A paint was prepared by mixing iron () composition powder into a vinyl chloride paste sol with the following composition. (Ingredients) (Parts by weight) PVC paste resin 100 Plasticizer 50 Stabilizer 2 Powder of iron () composition 20 (Particle size number + μ order, ferrous sulfate: L-ascorbic acid = 1:0.03 (mole ratio )) Pigment 20 total 192 Wallpaper was manufactured using this paint as follows. The coating thickness is 200μ.

[Table] For wallpaper made by mixing powder of this iron() composition into a PVC paste sol, it is essential to drill holes on the PVC surface. The purification function of this wallpaper sample was then tested in the same manner as in Example 1. The results are shown in Table 4. Although this product is inferior to wallpaper obtained by the gravure coating method or the valley staining method in its immediate effect, it is expected to have an extremely long-lasting effect.

[Table] Example 3 0.6 to 6% by weight of powder of the same iron () composition used in Example 2 was added to polypropylene,
Molded into a film. The deodorizing properties of this sheet were tested in the same manner as the test () in Example 1, and it was found that it had excellent activity even against high concentration NH ₃ gas. Table 5 shows the deodorization and adsorption test results when 1% by weight of the iron () composition was mixed.

【table】

【table】 [Brief explanation of drawings]

1 and 2 show embodiments of the method of the present invention; FIG. 1 shows a method using a gravure printing machine, and FIG. 2 shows a valley smearing method using a doctor knife. FIG. 3 is an explanatory diagram of the deodorization test device.

Claims (1)

[Scope of Claims] 1. A method for producing wallpaper, which comprises applying or mixing a composition formed by combining an iron () compound and L-ascorbic acid into a wallpaper material. 2 Applying or mixing a composition formed by combining an iron () compound and L-ascorbic acid to the wallpaper material,
A method for producing wallpaper, which comprises making holes with a needle roll.