JPH0699591B2 - Deodorant film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a film having a deodorant function of changing a substance that emits an offensive odor into an odorless substance.

[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.

On the other hand, the malodorous substances in the daily life are, for example, ammonia, amines, hydrogen sulfide, mercaptans, indole, carbonyl compounds and the like. As described in JP-A-55-32519, a bioenzyme acts as an oxidation catalyst to decompose these substances. Among the bioenzymes, metalloporphyrins and metalloprazines are excellent, and can be artificially synthesized as disclosed in, for example, JP-A No. 50-54590, and are relatively easy to obtain. Is.

[Problems to be solved by the invention]

The present invention focuses on the deodorizing function of the metal porfurazines 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 porfrazines as deodorants.

Metal porfurazine acts as an oxidation catalyst on all off-flavor substances, and decomposes malodorous substances into odorless substances. The basic skeleton structure of metal porfurazine 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, which are extremely advantageous properties as a deodorant. . 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 on the basis of the above-mentioned findings is obtained by adding a metal phthalocyanine polycarboxylic acid 0.1 to 20 to a polymer substance.
The film is formed by mixing wt%.

The polymer substance forming the film is, for example, cellulose acetate, polyethylene terephthalate, cellophane, polyvinyl alcohol, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polycarbonate, polyacrylic, polyimide, polysulfone, nylon, polyethersulfone, polyether. Ether ketone, polyvinylidene chloride, fluororesin, ethylene-vinyl acetate copolymer and the like 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, the metal phthalocyanine polycarboxylic acid, the metal phthalocyanine tetracarboxylic acid, and the metal phthalocyanine octacarboxylic acid increase in the number of carboxyl groups, the molecular association becomes difficult and the catalytic activity becomes strong. Practically preferred is a metal phthalocyanine tetracarboxylic acid represented by the following formula (1) or a metal phthalocyanine octacarboxylic acid represented by the following formula (2).

The larger the amount of the metal phthalocyanine polycarboxylic acid mixed with the polymer substance, the better the deodorizing performance tends to be. However, when the amount exceeds a certain level, it does not change so much. Alternatively, when the amount is too large, the film forming property deteriorates. On the other hand, if the amount is too small, the deodorizing performance cannot be maintained. According to the results of various experiments, the economic effect is also taken into consideration, and the amount of the metal phthalocyanine polycarboxylic acid is suitably 0.1 to 20% by weight. Preferably 0.5
~ 10% by weight.

The deodorant film of the present invention is manufactured by kneading a metal phthalocyanine polycarboxylic acid with the above-described polymer substance and then forming a film by a conventional method.

If necessary, for example, silica, titanium oxide, calcium carbonate, alumina, zeolite, talc, or other powder or granules, or a water absorbent or chitosan is added to these polymer substances as an additive together with a plasticizer. Helps improve activity. Further, the surface area may be increased by foaming the film or forming fine irregularities.

The metal phthalocyanine polycarboxylic acid may be mixed as a single substance, or may be mixed after being once adsorbed on fibers, paper, pulp, ceramics, etc. By doing so, the molecular dispersion state of the metal phthalocyanine polycarboxylic acid is improved and no association occurs, and the catalytic activity can be improved.

[Action]

The metal phthalocyanine polycarboxylic acid, which is the deodorant component of the deodorant film of the present invention, can keep the state in which the metal ion M at the center of catalytic activity is exposed, and can sufficiently exert the catalytic action.

The metal phthalocyanine polycarboxylic acid in 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 oxygen (autooxidation action by oxygen in the air).

In the formula, Sub stands for Substrate.

M-paPc: Metal phthalocyanine polycarboxylic acid (Sub) H: Odorant 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 (which occurs in a chain) with hydrogen peroxide (*) generated above.

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 kneaded into the polymer substance that is a constituent component of the film, and rarely separates due to aging. Moreover, the film itself does not absorb or contain an offensive odor substance, and is not consumed in the deodorant reaction system. Therefore, the deodorizing effect can be maintained semipermanently.

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 tray, garbage bag, house interior material, wallpaper, livestock wall material, shoe insole, bag insole, clothing cover, calendar with deodorant function, deodorant poster, refrigerator, microwave oven It can be used for internal sticking and the 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. 0.25 g of iron phthalocyanine octacarboxylic acid was ground in a ball mill for 24 hours, and then triacetyl cellulose resin 25
g and CH ₂ Cl ₂ 175 g were added, and the mixture was further mixed for 24 hours. The obtained dope was cast on a glass plate with a glass rod and dried with a drier to obtain a deodorant film. The amount of iron phthalocyanine octacarboxylic acid in the deodorant film was 1% by weight.

Example 2 A deodorant film was obtained in the same manner as in Example 1 except that iron phthalocyanine octacarboxylic acid was treated with copper sulfate.

Example 3 A deodorant film was obtained in the same manner as in Example 1 except that cobalt phthalocyanine tetracarboxylic acid treated with calcium chloride was used.

Example 4 0.25 g of chitosan was well pulverized with a ball mill and mixed with 0.25 g of iron phthalocyanine octacarboxylic acid, and otherwise the same as in Example 1 to obtain a deodorant film.

Example 5 100 g of a linear low-density polyethylene resin was mixed with 10 g of iron phthalocyanine octacarboxylic acid, which was well dried, and well mixed by a heating kneader to prepare a masterbatch.
900g of linear low-density polyethylene pellets and 100g of this masterbatch are mixed, and the thickness is 30
A deodorant film of μ was obtained.

<Characteristics evaluation> Catalyst activity test by Warburg pressure gauge. Mercaptan (RSH), which is one of the malodorous gas, 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). 1 ml of H ₂ O in the main chamber 1a of the reaction vessel 1
Put the sample (deodorant film of each example) weighed exactly
Into the side chamber 1b, 1 ml of about 0.5 mol / l 2-mercaptoethanol aqueous solution is put. After keeping the reaction vessel 1 at a constant temperature, the reaction is started, and the amount of O ₂ consumed is read from the scale of the manometer 3 at regular intervals. After pyrolyzing the sample, the metal phthalocyanine polycarboxylic acid is quantified by an atomic absorption photometer.
From this quantification result and the amount of O ₂ consumed, how much RSSR was generated per hour per 1 mol of the metal phthalocyanine polycarboxylic acid in the sample is calculated. The results of the catalytic activity of the deodorant film of each example are shown in FIG.

Deodorization performance test with a gas detector tube This deodorization performance test measures the gas removal rate of malodorous methyl mercaptan. Each sample (150 x 150 mm) of the example is placed in a 2 l quantitative container and filled with methyl mercaptan gas having an initial concentration of 120 PPM. A small amount of this gas is taken out at regular intervals, and the concentration of residual methyl mercaptan is measured by a gas detector tube. Graphs of the measurement results are shown in FIG. 3 (sample of Example 1) and FIG. 4 (sample of Example 5). The test is performed at room temperature of 25 ° C and humidity of 75%.

The amount of iron phthalocyanine octacarboxylic acid mixed in 25 g of the triacetyl cellulose resin of Example 1 was variously adjusted to be 0.02 g to 5 g to adjust the amount of iron phthalocyanine octacarboxylic acid in the deodorant film to 0.08% by weight to 20%. A large number of samples of deodorant films varying between wt% are made. A sensory test is performed 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 appeared when the amount of iron phthalocyanine octacarboxylic acid was about 0.1% by weight or more.

Note that the samples of each example are packed with natural odorous substances such as manure, fish cotton, and sewage sludge, and an official response 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.

Claims (1)

[Claims] 1. A deodorant film, characterized in that a polymeric substance is mixed with 0.1 to 20% by weight of a metal phthalocyanine polycarboxylic acid to form a film.