JPH0624818B2 - Deodorant film and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a film having an odor eliminating function for converting an offensive odor substance into an odorless substance, and a method for producing the film.

[Conventional technology]

The largest use of the film is for packaging, and there is film packaging in which the package is completely sealed from the outside air, but there are many cases where the film is exposed to the outside air without being sealed. When the package is an off-flavor substance, the package should be sealed, but if it is a package that is exposed to the outside air, the off-flavor is simply inconvenient.
Therefore, it is very convenient if the film has a deodorant function. However, there is no such film.

Malodorous substances in everyday life are, for example, ammonia,
Examples include amines, hydrogen sulfide, mercaptans, indoles and carbonyl compounds. These substances are disclosed in JP-A-55
As described in JP-A-32519, a bioenzyme acts as an oxidation catalyst and is decomposed. Among bioenzymes, metalloporphyrins and metalloporangins are excellent, and they are also advantageous in that they can be obtained relatively easily, as disclosed in, for example, Japanese Patent Application Laid-Open No. 50-54590.

[Problems to be solved by the invention]

The present invention focuses on the deodorizing function of the metal porfrangins described in the above publication, and provides a deodorant film by utilizing this.

[Means for solving problems]

The present inventor has obtained the following findings through research using metal porfurazines as deodorants.

The metal porfurazines have a property of acting as a catalyst for the offensive odors as an oxidation catalyst and decomposing them to make them odorless.
The basic skeleton structure of metal porflange The metal phthalocyanine is particularly excellent in its properties.
For example, the reaction rate is high and the decomposition rate is high, the reaction proceeds at room temperature, the oxygen in the air can be effectively used, and the catalyst life is long in the cycle reaction. . However, since metal phthalocyanine has a planar structure, molecules tend to easily associate with each other. When the molecules are associated with each other, the metal ion M, which is the center of the catalytic activity, is covered and the catalytic activity is weakened.

In contrast, the following formula, which is a derivative of metal phthalocyanine (Wherein, M is a metal, and X is a carboxyl group or an unsubstituted hydrogen group), and the carboxyl ion of the metal phthalocyanine polycarboxylic acid is electrically repelled, and molecular association is difficult.
In addition, the carboxyl group causes steric hindrance and is difficult to associate. In this way, the metal ion M, which is the center of catalytic activity, can be kept exposed and the catalytic action can be sufficiently exerted.

The deodorant film of the present invention made under the above knowledge, a coating layer containing a metal phthalocyanine polycarboxylic acid and a binder resin is formed on at least one surface of the base film,
The amount of the metal phthalocyanine polycarboxylic acid with respect to the base film is 1 × 10 ^{−4 to} 25 g / m ² .

As the base film, a plastic film such as triacetyl cellulose, polyethylene terephthalate, polyvinyl chloride, polypropylene, polystyrene, polycarbonate, polyacrylic, polysulfone, nylon, polyethersulfone, polyetheretherketone, or polyimide can be used.

In the metal phthalocyanine polycarboxylic acid, the central metal M is F
Materials of e, Co, Mn, Ti, V, Ni, Cu, Zn, Mo, W and Os can be used. Preferably Fe or Co, or Fe
And Co are mixed.

As the metal phthalocyanine polycarboxylic acid and the metal phthalocyanine dicarboxylic acid, the metal phthalocyanine tetracarboxylic acid, and the metal phthalocyanine octacarboxylic acid increase in the number of carboxyl groups, the more difficult the molecular association is, the stronger the catalytic activity becomes. Practically preferred is a metal phthalocyanine tetracarboxylic acid represented by the following formula, Or a metal phthalocyanine octacarboxylic acid represented by the following formula Is.

The binder resin for fixing the metal phthalocyanine polycarboxylic acid and forming the coating layer is, for example, polyester, vinyl chloride-vinyl acetate copolymer, acrylic resin, urethane resin, vinyl chloride resin, nitrification cotton, butadiene resin, ethylene-vinyl acetate. A resin that is a copolymer and has good adhesion to the base film is used. Additives such as silica, titanium oxide, calcium carbonate, alumina, zeolite, talc, and water absorbents, chitosan, etc. as additives to the coating layer are useful for improving activity.
The surface area can be increased by firing the coating layer or forming fine irregularities. The larger the amount of metal phthalocyanine polycarboxylic acid on the film surface, the better the deodorant performance tends to be, but it does not change so much when the amount exceeds a certain level. If it is too small, the deodorant performance cannot be maintained. From the results of various experiments, the economic effect is taken into consideration, and the amount of metal phthalocyanine polycarboxylic acid is 1 per square meter of the surface area of the film.
A suitable amount is × 10 ^{-4 to} 25 g, preferably 1 × 10 ^{-2 to} 10 g. For example, when it is 1 × 10 ⁻⁴ g / m ² , the thickness of the coating layer containing 0.1% by weight of metal phthalocyanine polycarboxylic acid is 0.1 μm.
You can set it to m. When it is 25 g / m ² , the thickness of the coating layer containing 50% by weight of metal phthalocyanine polycarboxylic acid is 50%.
μm.

The method for producing a deodorant film constituted by the above, a coating solution containing a metal phthalocyanine polycarboxylic acid, a binder resin, and a solvent is applied to the base film, and the solvent is dried to dry the metal phthalocyanine polycarboxylic acid. And a coating layer containing a binder resin is formed. In this case, the metal phthalocyanine polycarboxylic acid is not always used alone, and fibers, paper, pulp, ceramics or the like in which the metal phthalocyanine polycarboxylic acid is adsorbed may be pulverized and mixed. As the solvent for the coating film solution, a solvent suitable for the binder resin is used.

As another method, the metal phthalocyanine polycarboxylic acid is mixed with an emulsion liquid in which a binder resin is dispersed, the mixed emulsion liquid is applied to a base film, and then the metal phthalocyanine polycarboxylic acid and the binder are dried. It is also possible to form a coating layer containing a resin. In this case, as the emulsion liquid in which the binder resin is dispersed, for example, an acrylic ester emulsion, a butadiene emulsion, a vinyl acetate emulsion or the like can be used. Since the metal phthalocyanine polycarboxylic acid is alkaline and soluble, the aqueous solution is prepared alkaline. Therefore, the emulsion liquid is preferably an alkaline and stable emulsion.

As still another method, a binder resin is made into an aqueous solution together with a metal phthalocyanine polycarboxylic acid, and the aqueous binder solution is applied to a base film and then dried to form a coating layer containing the metal phthalocyanine polycarboxylic acid and a binder resin. You can also in this case,
As the binder resin, for example, polyvinyl alcohol, polyethylene oxide, methyl cellulose, alkyd, polyester, acryl, water-soluble modified polymer of epoxy and the like can be used.

The emulsion liquid or the binder aqueous solution is adjusted to be alkaline in order to stably dissolve the metal phthalocyanine polycarboxylic acid. When adjusting with ammonia or an amine-based substance, the activity of the metal phthalocyanine polycarboxylic acid decreases, so it is desirable to make it alkaline with other substances such as sodium hydroxide or potassium hydroxide.

In order to apply the above coating liquid or emulsion mixed liquid to the base film, a continuous processing device such as a Mayer bar coater or a reverse roll coater may be used, or the base film may be immersed in the liquid and then pulled up. It's just good.

[Action]

The metal phthalocyanine polycarboxylic acid, which is the deodorant component of the deodorant film of the present invention, is a metal ion M of the catalytically active center.
Can be kept exposed and the catalytic action can be sufficiently exerted.

The metal phthalocyanine polycarboxylic acid in the coating layer of the deodorant film of the present invention acts on the offensive odor substance in a manner similar to the following bioenzymes and decomposes the offensive odor substance.

Oxidase-like action Oxidation reaction by molecular enzyme (autooxidation action by oxygen in the air).

In the formula, Sub stands for Substrate.

M-paPc: metal phthalocyanine polycarboxylic acid (Sub) H: an off-flavor substance such as H ₂ S, R-SH (mercaptan derivative), R-CHO (aldehyde derivative), R-NH ₂ (amino derivative), R-OH (Alcohol derivative) Sub-Sub: Oxidation product Similar action to peroxidase Oxidation reaction by hydrogen peroxide (*) generated above (
Happens in a chain).

Oxygenase-like action A reaction that oxidatively cleaves malodorous substances composed of heterocyclic compounds such as indole nucleus and pyridine nucleus. The following reactions in the case of indole nuclei.

The product of oxidative cleavage is further decomposed by the above reaction.

〔The invention's effect〕

The deodorant film of the present invention can decompose almost all malodorous substances existing in the daily life of human beings regardless of water solubility or water insolubility by the above-mentioned reactions. The metal phthalocyanine polycarboxylic acid, which is a deodorant component, is firmly fixed by the binder resin in the coating film layer, and is hardly separated due to aging. Moreover, the film itself and the coating layer do not absorb or contain an offensive odor substance and are not consumed in the deodorant reaction system. Therefore, the deodorizing effect can be maintained semipermanently.

Since the method for producing a deodorant film of the present invention applies a coating layer of a metal phthalocyanine polycarboxylic acid and a binder resin by a liquid system, it can be produced efficiently regardless of the shape of the base film. it can. If the base film is in the form of a sheet or chips, it can be processed by batch processing and can be manufactured efficiently even in a relatively small amount. If the base film is in the form of a continuous roll, continuous processing is possible, and in this case, it is suitable for mass production.

When an organic solvent is used in the liquid system for applying the coating layer, the selection range of the binder resin is widened, so that the selection range of the base film can be widened.

When water, that is, an aqueous emulsion or a water-soluble resin binder is used in the liquid system for coating the coating layer, the metal phthalocyanine polycarboxylic acid is dissolved in water and is dispersed at the molecular level in the coating layer. It will be. Therefore, the activation efficiency of the deodorant component is improved. Also, the coating layer becomes transparent,
The deodorant film itself can be made transparent and the color is vividly finished. Using the deodorant film of the present invention as a raw material, any secondary product, such as bags, inside of food storage containers, automobiles, trains, house interiors, diaper cover underlays, food wraps, food packaging materials , Food trays, garbage bags, interior materials for houses, wallpaper, storage wall materials, shoe insoles, bag insoles, clothing covers, calendar with deodorant function, deodorant poster, refrigerator, electronic It can be used for pasting in a microwave oven, etc., and its secondary product will have a deodorizing function.

Also, depending on the application, a higher-performance film can be obtained by laminating this film with various plastic films, non-woven fabrics, paper, fibers, metals, etc., or coating various substances on the surface of this film. .

〔Example〕

Hereinafter, typical examples of the deodorant film to which the present invention is applied will be described.

<< Production of Deodorant Film >> Example 1. A triacetyl cellulose film is used as the base film.

The following composition: Iron phthalocyanine octacarboxylic acid 0.5 part by weight Titanium oxide 1.5 parts by weight Silica 2.5 parts by weight Polymeric water absorbent 1 part by weight Binder (triacetyl cellulose) 12.5 parts by weight Solvent (methylene chloride-methanol) 70 parts by weight in a ball mill Mix and dissolve for 24 hours to obtain a coating solution. This solution is applied to a triacetyl cellulose film using a Mayer bar. It was dried to obtain a deodorant film having a coating layer on the base film. By adjusting the coating amount of the coating solution and setting the thickness of the coating layer to 5 μm,
The amount of iron phthalocyanine octalcarboxylic acid is 0.14 g / m ²
become.

Example 2. A polyethylene terephthalate film is used as the base film.

The following composition: Iron phthalocyanine octacarboxylic acid 1 part by weight Titanium oxide 3 parts by weight Silica 5 parts by weight Polymer water absorbent 2 parts by weight Binder (acrylic polyol type) 19 parts by weight Solvent (ethyl acetate-toluene) 70 parts by weight in a ball mill After mixing for 24 hours, 7 parts by weight of a cross-linking curing agent is added and further stirred to obtain a coating film solution. Polyethylene terephthalate film (thickness: 25 μm)
Apply with a Mayer bar. It was dried and cured at 150 ° C. for 1 minute to obtain a deodorant film having a coating film on the base film. By adjusting the coating amount of the coating film solution and setting the thickness of the coating film layer to 3 μm, the amount of iron phthalocyanine octacarboxylic acid becomes 0.1 g / m ² .

Example 3. A polycarbonate film is used as the base film.

The following composition: Iron phthalocyanine tetracarboxylic acid 0.5 part by weight Titanium oxide 1 part by weight Silica 3 parts by weight Polymeric water absorbent 1 part by weight Binder (polyester type) 15 parts by weight Solvent (methyl ethyl ketone-toluene) 80 parts by weight Ball mill for 24 hours Mix to obtain a coating solution. This solution was applied to a polycarbonate film (thickness 100 μm) using a coater to obtain a deodorant film having a coating layer on the base film. The amount of iron phthalocyanine tetracarboxylic acid is adjusted to 0.05 g / m ² by adjusting the coating amount of the coating solution and adjusting the thickness of the coating layer to 2 μm.

Example 4. A biaxially oriented polypropylene film is used as the base film.

The following composition: Cobalt phthalocyanine octacarboxylic acid 0.5 part by weight Silica 2 parts by weight Calcium carbonate 1 part by weight Binder (urethane type) 15 parts by weight Solvent (ethyl acetate-toluene) 70 parts by weight are mixed in a ball mill for 24 hours to obtain a coating solution. . This solution is biaxially stretched polypropylene film (thickness 100 μm)
Was coated with a coater to obtain a deodorant film having a coating layer on the base film. By adjusting the coating amount of the coating solution and setting the thickness of the coating layer to 4 μm, the amount of cobalt phthalocyanine octacarboxylic acid becomes 0.11 g / m ² .

Example 5. A polyester film is used as the base film.

2 g of iron phthalocyanine octacarboxylic acid is uniformly dissolved in 10% -NaOH. To this, 89 g of acrylic ester emulsion binder (solid content 45%) was added and stirred to obtain a coating film solution. This solution is applied to a polyester film using a Mayer bar. After drying it once, 0.
Neutralize by immersing in 1N-HCl. It was washed with water and dried to obtain a deodorant film having a coating layer on the base film.

By adjusting the coating amount of the coating film solution and setting the film thickness of the coating film layer to 10 μm, the amount of iron phthalocyanine octacarboxylic acid becomes 0.5 g / m ² .

Example 6. 250 g of the cut polyester film is immersed in 50 g of the same coating solution as in Example 5 while stirring to uniformly adhere the film. After it is once dried, it is immersed in 0.1N-HCl for neutralization. It was washed with water and dried, and a deodorant film having a one-sided amount of iron phthalocyanine octacarboxylic acid or a coating layer of 0.15 g / m ² on the cut base film was obtained.

Example 7. A polyester film is used as the base film.

1 g of iron phthalocyanine tetracarboxylic acid is uniformly dissolved in 10% -NaOH aqueous solution. To this, 200 g of 10% aqueous solution of completely saponified polyvinyl alcohol was added and stirred to obtain a coating solution. This solution is applied to a polyethylene terephthalate film that has been subjected to an easy-adhesion treatment using a Mayer bar.
It is dried at 80 ° C. for 2 minutes and at 180 ° C. for 3 minutes.
After that, it is immersed in a mixed aqueous solution of sodium sulfate 200 g / 1, sulfuric acid 150 g / 1 and formaldehyde 30 g / 1 at 50 ° C. for 30 minutes, washed with water and dried.

Thus, a deodorant film having a coating layer on the base film was obtained. By adjusting the coating amount of the coating solution and adjusting the thickness of the coating layer to 7 μm, the amount of iron phthalocyanine tetracarboxylic acid becomes 0.35 g / m ² .

<< Characteristics Evaluation >> Catalytic Activity Test by Warburg Pressure Gauge Mercaptan (RSH), which is one of the malodorous gases, becomes RSSR and becomes odorless in the following reaction due to the catalytic action of metal phthalocyanine polycarboxylic acid.

Therefore, the catalytic activity of the metal phthalocyanine polycarboxylic acid, that is, the deodorizing property can be measured by quantifying the consumed O ₂ .

The outline of the test apparatus is shown in FIG. The reaction vessel 1 is
It is composed of a main chamber 1a and a side chamber 1b, and is connected to the manometer 3. The reaction container 1 is placed in constant temperature water and the whole is shaken by a shaker (not shown). Into the main chamber 1a of the reaction vessel 1, 1 m of H ₂ O and a precisely weighed sample (deodorant film of each example) are put, and about 0.5 mol / liter 2-mercaptoethanol aqueous solution is put in 1 m of the side chamber 1b. After the reaction container 1 was kept at a constant temperature, the reaction was started and the O ₂
Read the quantity from the scale on the manometer 3. After pyrolyzing the sample, the metal phthalocyanine polycarboxylic acid is quantified by an atomic absorption photometer. Based on this quantitative result and the amount of O ₂ consumed, 1 m of metal phthalocyanine polycarboxylic acid in the sample
Calculate how many RSSRs are generated per ol. The results of the catalytic activity of the deodorant films of Examples 1 to 5 are the second.
It is shown in the figure.

Deodorization performance test with gas detector tube This deodorization performance test measures the gas removal rate of offensive odor gases, ammonia and methyl mercaptan. Ammonia is measured as follows. Put a sample of deodorant film (150 x 150 mm) in the fixed quantity container of 2, and set the initial concentration to 120PPM.
Fill with ammonia gas. A small amount of this gas is taken out at regular time intervals and the concentration of residual ammonia is measured by a gas detector tube. The graph of the measurement results for Example 2 is the third
It is shown in the figure. The test is conducted at room temperature 25 ° C and humidity 75%. Do the same for methyl mercaptan. However, in the case of methyl mercaptan, the initial concentration of gas is 10
It was measured at 0 PPM. The measurement results are shown in FIG.

The amount of iron phthalocyanine octacarboxylic acid mixed in the coating solution of Example 1 was adjusted to change the amount of iron phthalocyanine octacarboxylic acid in the coating layer between 0.08% by weight and 50% by weight. The thickness of the layer was changed from 0.08 μm to 50 μm, and the amount of iron phthalocyanine octacarboxylic acid per unit area of the film was 0.64 × 10 ⁻⁴ g / m _{2 to} 25 g /
Make many samples of m ² deodorant film. A sensory test is conducted by wrapping 1 kg of chicken feces with 1 m ² of each sample film. As a result, it was found that the deodorizing effect appears when the amount of iron phthalocyanine octacarboxylic acid is about 1 × 10 ⁻⁴ g / m ² or more.

In addition, for the samples of each example, natural odorous substances such as manure, fish cotton, and sewage sludge are packaged, and a sensory test is also conducted by monitoring whether they are actually deodorized. Has been obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing a deodorant performance testing device, and FIGS. 2 to 4 are diagrams showing results of performance tests of deodorant films.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Keisuke Matsunaga, 89, Oeda, Oeda, Kasukabe, Saitama 3-24-204 Takesato housing complex (56) References JP-A-63-57669 (JP, A) JP-A-55 -32519 (JP, A)

Claims (3)

[Claims] 1. A coating layer containing a metal phthalocyanine polycarboxylic acid and a binder resin is formed on at least one surface of a base film, and the amount of the metal phthalocyanine polycarboxylic acid relative to the base film is 1 × 10 ^{−4 to} 25 g / m ² . A deodorant film characterized by being present. 2. A coating film solution containing a metal phthalocyanine polycarboxylic acid, a binder resin and a solvent is applied to a base film and the solvent is dried to form a coating film layer containing the metal phthalocyanine polycarboxylic acid and a binder resin. A method for producing a deodorant film, which comprises forming the film. 3. A base film is coated with an aqueous solution in which a metal phthalocyanine polycarboxylic acid and a binder resin are dissolved, or an emulsion solution in which a binder resin is dispersed in an aqueous metal phthalocyanine polycarboxylic acid solution,
A method for producing a deodorant film, which comprises forming a coating layer containing a metal phthalocyanine polycarboxylic acid and a binder resin by drying.