JPH06107971A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating compound composition for forming a deodorizing and antimicrobial coated face. CONSTITUTION:0.1-5.0% solution of chlorine dioxide adjusted to pH 8.0-12.0 is adsorbed and supported on an adsorption carrier having at least 50wt.% or higher water absorption capacity and a particle size distribution from powder to granule and dispersed into a resin solution which has film forming ability and whose aqueous solution or 5% suspension shows 7.0 or higher pH to give a composition, which is used as a main component to give a coating compound composition for evolving chloride dioxide. The composition prevents algae and slime of a water tank, etc., has antifungal and antimicrobial effects on a wall, etc., and is applied to a plastic container for storing fishes and shellfishes to maintain freshness retaining effect.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorine dioxide-generating coating composition, and more particularly to a coating composition suitable for application to an object to gradually generate chlorine dioxide.

[0002]

2. Description of the Related Art Chlorine dioxide is a well-known deodorant and bleaching bactericide, but since it is gaseous at room temperature and atmospheric pressure,
For bleaching flour and pulp, its use was limited, such as by generating gas at the site of use.

In addition, chlorine dioxide is absorbed into a peroxide such as sodium percarbonate to form a complex salt, which is stably dissolved and held in water, and a stabilized chlorine dioxide solution, and this solution is adsorbed on an adsorption carrier. It has been proposed and publicly known to use a large amount of chlorine dioxide, or to mix a chlorite with a gas generation promoter for use as a deodorant germicide.

For example, Japanese Patent Publication No. 48-32079 discloses an example in which a stabilized chlorine dioxide solution is adsorbed on a basic water-absorbing powder and mixed with an acidic solid powder to generate chlorine dioxide gas at the time of use. Further, an example of mixing a chlorite with a protic acid such as citric acid or an acidic inorganic compound such as titanium oxide to generate a gas (JP-A-60-103003, JP-A-1-349).
No. 04, Japanese Patent Application Laid-Open No. 2-104509, etc.). All of these had a drawback that chlorine dioxide gas was rapidly generated and was not suitable for the purpose of continuously generating and using the gas.

On the other hand, as an attempt to gradually release the gas generation, for example, as disclosed in Japanese Patent Laid-Open No. 3-285801, sulfurous oxygen-containing acid such as potassium peroxodisulfate is added to chlorite. Example of mixing an aqueous solution, an attempt to add trichloroisocyanuric acid as a generator and calcium silicate as a diluent to chlorite (JP-A-63-
No. 246304), a composition comprising silica zeolite and chlorite (JP-A-1-71804), and a mixed composition of an aluminosilicate and an oxidizing agent (JP-A-2-2).
77455), or an attempt to generate a gas by using a transition metal such as platinum or boric acid (JP-A-3-164).
No. 402).

[0006]

However, although the above-mentioned compositions for the purpose of sustained release have some effect of delaying the gas generation, as long as they are mixed with a gas generating agent, they can be stored during storage. Since it is impossible to suppress the generation of gas, it is not suitable for long-term storage, and furthermore, it is impossible to continue the gas generation for a long period of time such as 1-2 months from the start of use. .

The present inventor has studied compositions and methods for controlling the generation of chlorine dioxide gas for many years and found that the iron content in the carrier is involved in the rate of gas volatilization. As a result, a composition in which a small amount of gas is generated without adding a gas generating agent separately has been found (Japanese Patent Publication No. 63-59738 and Japanese Patent Publication No. 1-38).
151 publication). However, even these were not sufficient to exert their effects over a long period of time such as 6 months or longer.

The chlorine dioxide gas generating composition is roughly classified into paste form or agar form using an aqueous solution such as a stabilized chlorine dioxide solution, a superabsorbent resin or a gelling agent such as carrageenan. It is divided into a gel material, or a powder or granular solid material.

[0009] Therefore, the mode of use is to generate gas by spraying or spraying an aqueous solution, and by containing a gel or powder or a granular material in a container or bag.
In these usage modes, for example, in order to exert an effect on deodorization such as a bathroom with a high humidity or a closet, and fungicides, the effect cannot be expected unless the entire space has a constant gas concentration, It was not suitable for local use for purposes such as mold prevention on walls.

In order to solve the above problems, it is possible to use a sheet-like material or apply it to an object.
As for the sheet, an attempt was made to adsorb a stabilized chlorine dioxide solution on an inorganic adsorption carrier and form it on a nonwoven fabric using an aqueous synthetic resin as a binder (Japanese Utility Model Publication No. 1-17311), and chlorine dioxide gas was converted to zinc aluminosilicate. A deodorant sheet (JP-A-2-277455) in which a non-woven fabric made of nylon is impregnated with the impregnated impregnated product using an ethylene-vinyl acetate copolymer as a binder has been proposed. It has been revealed that since the non-woven fabric is used as the base material, the effect period is relatively short, 30 to 60 days, and there is a problem that a strange odor is generated during closed storage.

Further, no composition has been proposed so far which is applied to a gas-impermeable substrate such as plastic, metal or concrete to continuously generate chlorine dioxide. This is because when a conventional chlorine dioxide generating composition is coated with a synthetic resin as a binder, the person skilled in the art has the concern / preconception that the composition is buried in the binder and is covered so that the generation of gas is inhibited. It is presumed that the chlorine dioxide-generating composition of the product was not attempted in general because it has the problems of lacking storage stability and sustained release.

The present invention has been made in view of the above-mentioned situation, and cannot be achieved by the conventional use mode of the chlorine dioxide-generating composition, for example, local deodorization and prevention of fungi on the walls of bathrooms. It is an object of the present invention to provide a chlorine dioxide-generating coating composition suitable for being applied to an object such that it is suitable for fungi.

[0013]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention exerted an effect by applying it to an object based on the findings obtained from the research results of a chlorine dioxide generating composition over many years. As a result of intensive studies on the composition, it is essential for storage stability to correct the decrease in pH due to dilution of the stabilized chlorine dioxide solution when used, and the adsorption carrier depends on the film thickness to be formed. A composition having a particle size distribution from powder to fine granules is effective for smoothly generating chlorine dioxide gas from the film regardless of the presence of a binder, and as an adsorption carrier,
The present invention has been completed by finding that the use of a carrier having fine pores (10 ² to 10 ⁴ Å) structurally has an effect on the sustained release of gas.

That is, the present invention has a pH of 8.0-12.
0.1 to 5.0% of stabilized chlorine dioxide solution prepared to 0 is adsorbed and supported on an adsorption carrier having a water absorption capacity of at least 50% by weight or more and having a particle size distribution from powder to fine granules, Chlorine dioxide generation characterized by having as a main component a composition having a film-forming ability and being dispersed in a resin liquid having an aqueous solution or a 5% aqueous suspension thereof having a pH of 7.0 or more. The main point is a coating composition.

[0015]

The structure and operation of the present invention will be described. The stabilized chlorine dioxide solution used in the present invention is different from chlorine dioxide water in which chlorine dioxide gas is simply dissolved in water, for example, a peroxide such as sodium percarbonate absorbs chlorine dioxide gas to form a complex salt. Is stably retained and dissolved in water, and an example of its production method is disclosed in US Pat. No. 3,123,521.

In the present invention, not only the liquid stabilized by the method described in the above specification, but also a chlorine dioxide liquid stabilized by another method can be used. A commercially available 5% stabilized chlorine dioxide solution has a pH in the range of about 7.5 to 10 (for example, the pH of product A is 7.5 to 9.5, the pH of product B is 8.5 to 8.5, depending on the manufacturing method and the like). 9.5, pH of C company product 9.4 to 9.
9) and when diluted with water before use, pH
There is a decrease in
A 1.0% aqueous solution has a pH of 6.8 to 9.0.

Therefore, in the present invention, when the stabilized chlorine dioxide solution is adsorbed on the adsorption carrier and diluted with water, the pH of the alkaline compound is 8.0 to 12.0, preferably 9.
It is necessary to adjust it to 0-10.0. As the alkaline compound used for this purpose, sodium percarbonate and sodium bicarbonate are preferably used, but the alkaline compound is not limited thereto.

When the pH is 8.0 or less, the storage stability of the composition of the present invention is impaired, and the pH is 12.0.
It has been found from many experimental results that generation of chlorine dioxide gas in the case of forming a film is suppressed as described above, so it is preferable to avoid it.

The stabilized chlorine dioxide solution used in the present invention is
A liquid of 0.1 to 5% is used according to the intended use, but the concentration can be selected mainly depending on the required strength of chlorine dioxide gas (concentration of generation) and the duration of gas generation when applied. Good. If the concentration is less than 0.1%, the deodorant / antibacterial effect is inferior, and if the concentration is more than 5%, the storage stability until the use of this composition is insufficient. Is preferred.

Next, as a carrier for adsorbing and carrying the stabilized chlorine dioxide liquid used in the present invention, if the adsorption capacity is 50% by weight or more and the powder or granules can stably hold the liquid, its composition and There is no limitation on the type, but preferably white carbon, synthetic zeolite, diatomaceous earth, activated alumina, which has a pH of a 5% aqueous suspension of 7.0 or more,
Examples include activated alumina / silica, calcium silicate, and clay minerals.

An adsorbent carrier having a pH of a 5% aqueous suspension of 7.0 or less is not used because it tends to generate chlorine dioxide during storage depending on the pH of the stabilized chlorine dioxide solution used. It is preferable to avoid it.

Among the above carriers, structurally 10 ² to 1
Carriers with excellent liquid adsorption capacity because they have 0 ⁴ Å micropores, such as synthetic zeolite and activated alumina, are more preferable because they have a better gas sustained release property than carriers without micropores. Used for. Further, these carriers may be used in combination of two or more kinds.

One of the features of the present invention is the use of an adsorption carrier having a particle size distribution ranging from powder to fine granules, and the action and effect are as follows. That is, since the composition of the present invention is one in which a carrier having a stabilized chlorine dioxide solution adsorbed therein is dispersed in a resin solution and is applied to an object, the relative magnitude of the particle size of the carrier powder and the formed film thickness. Depending on the relationship, a phenomenon was observed in which the adsorption carrier was thickly covered by the coexisting resin layer and gas generation was suppressed.

In order to solve this problem, the present invention adjusts the particle size of the carrier according to a desired film thickness to be formed, so that gas can be smoothly generated. Specifically, for example, the coating object is a water tank or the like and the film thickness is 270 to 300 μm.
In the case of forming into a powder, the particle size distribution of the carrier is 200-250.
Approximately 60% of particles with a size of 200 μm
%, And so on.

In order to prepare an adsorption carrier from powder to fine granules, it can be obtained by mixing components of each particle size, but it is preferable to grind a granular molded product having a size of 1 to 10 mm and to use the ground product as it is. It is advantageous to use it in terms of preparation.

The resin liquid having a film-forming ability used in the present invention is an aqueous solution thereof if it is an aqueous system (including an emulsion system) and a pH of a 5% aqueous suspension is 7.0 or more if it is a non-aqueous system, preferably. Is a resin liquid having a value of 8.0 or more.

When a resin liquid having a pH of 7.0 or less is used as a coating composition by dispersing an adsorbent carrier, there are some cases in which the resin liquid is deteriorated during storage for a long time and an offensive odor is generated. . In addition, it is preferable to avoid the use of an epoxy-amine-based resin containing amines having a strong reactivity with chlorine dioxide in the resin component.

Since the carrier carrying the stabilized chlorine dioxide solution adsorbed and supported in the present invention is heated at 80 ° C. or higher, the retention stability is impaired and chlorine dioxide gas is easily generated.
It is necessary to avoid a thermosetting resin as the above resin liquid, and to select a resin liquid such as a normally dry type or a moisture curing type that can form a film by heating at 80 ° C. or lower.

The types of resins that can be used are acrylic,
Acrylic-vinyl acetate copolymers, vinyl acetate, vinyl chloride, vinyl chloride-vinyl acetate copolymers, vinylidene chloride, alkyd resins, styrene alkyds, acrylic silicones, cellulose compounds, and the like. Resin, vinyl chloride-vinyl acetate copolymer resin, and vinylidene chloride resin are preferably used.

Which of these resin liquids is used,
In addition, whether to use an aqueous system or a solvent type is selected according to the type of target material such as whether the target object to be applied is plastic or concrete, the required deodorizing ability and the degree of antibacterial effect. You can do it.

Next, the method for preparing the composition of the present invention and the mutual quantitative ratio of each component will be described. First, for the operation of adsorbing the stabilized chlorine dioxide liquid onto the adsorption carrier, a conventional method of spraying the liquid on the carrier powder or granules while stirring can be adopted. The adsorption amount of the liquid is more uniform when it is adsorbed to near the adsorption capacity of the carrier. The obtained adsorbate must be sealed in a gas barrier bag or the like until it is dispersed to avoid gas volatilization.

In order to disperse the thus obtained adsorbate of the stabilized chlorine dioxide solution in the resin solution, it can be prepared by a conventional method using a general disperser used in the production of paint. The ratio of the amount of adsorbate to the resin liquid is usually 10 with respect to the resin content.
~ 50 wt% is used. In this dispersion operation, in order to improve coatability, addition of additives such as anti-sagging agent and defoaming agent and coloring with dyes and pigments may be optionally performed. The coating composition of the present invention has a characteristic of withstanding storage because, when the chlorine dioxide gas is saturated, no further gas generation is observed during closed storage.

[0033]

EXAMPLES The present invention will be specifically described with reference to Examples.
The present invention is not limited thereby. In addition,
Parts and% are parts by weight and% by weight, unless otherwise specified. Example 1 Activated alumina powder (Sumitomo Chemical Co., Ltd., particle size 10 to 15 μm)
m, pH 8.4) 50 parts and calcium silicate powder 3
After uniformly mixing 0 parts (particle size 20 to 30 μm, pH 8.6), 5% stabilized chlorine dioxide solution (manufactured by Daiso, pH
8.6) 100 parts of the mixture was added and mixed to prepare an adsorbate (A). As a comparative product, the above powder mixture (B) which does not adsorb the stabilized chlorine dioxide solution is prepared.

Commercially available vinyl chloride resin (Kanebuchi Chemical Co., Kanevirak, resin content 38.4%, pH 7.0) 100 parts, calcium carbonate 30 parts, the above adsorbate (A) 20 parts using toluene and ethyl acetate as solvents. The coating composition of the present invention having a nonvolatile content of 50% was dispersed and mixed (the ratio of the adsorption carrier to the nonvolatile content was 23%). A coating composition was obtained in the same manner except that (B) was used instead of (A) as a comparative product.

An ABS plate of 70 mm × 150 mm × 1 mm is prepared, and one surface of the ABS plate is brushed with one of the above two compositions.
It was formed to a film thickness of 00 μm (one-time coating) and 300 μm (three-time coating). The test piece thus obtained was exposed to a sunshine weatherometer (abbreviated as SSWOM) for a certain period of time to test the durability of its antifungal function.
Excellent results were shown as shown in.

[0036]

[Table 1]

For the medium, test bacteria, mixed spore suspension, etc., J
It became IS Z2911. In the mold resistance test, each sample was placed on a Sabouraud agar medium, 1 mL of a mixed spore suspension of mold was sprinkled on the sample, and the mixture was cultured at 28 ° C. for 28 days. Further, in the residual chlorine concentration measurement orthotrizine method, the residual chlorine dioxide concentration was calculated by dropping an orthotrizine solution on each sample and checking the yellowness after 2 hours.

[0038]

Example 2 A commercially available stabilized chlorine dioxide solution was diluted with water and p
Prepare a 0.1% aqueous solution of H8. pH is 8.2 (5%
320 parts of the above 0.1% solution was sprayed and adsorbed onto 100 parts of calcium silicate powder (6 to 25 μm particle size) of a water suspension).

To 100 parts of a 38% solution of vinyl chloride resin (Kanebuchi Chemical Co., trade name Kanevirak), 19 parts of the above adsorption carrier (solid content ratio of 50%) was added and uniformly dispersed using a homomixer. It was a composition. The above composition was applied to the inner surface of a tray (13 cm × 24 cm × 4 cm) made of polyvinyl chloride so as to have a thickness of about 40 μm. Twelve strawberries were placed in each of this tray and an untreated tray and allowed to stand in a room to compare their freshness-retaining effects. The results shown in Table 2 were obtained and the effects were recognized.

[0040]

[Table 2]

[0041]

Example 3 A commercially available 5% stabilized chlorine dioxide solution (manufactured by Sukegawa Chemical Co., Ltd., pH 7.6) was diluted to 3% with tap water, and the pH was 7.2. Adjust the pH to 1 using sodium bicarbonate
100 parts of this aqueous solution adjusted to 2.0
Pulverized product (100-200 μm 6) of activated alumina molded product (Sumitomo Chemical Co., Ltd., 2-4 mmφ) having 0Å fine pores
It was adsorbed on 200 parts of a composition of 0% and composition of 40 μm or less of 150 μm) to obtain a stabilized chlorine dioxide liquid adsorption carrier.

50% of vinyl chloride-vinyl acetate copolymer
The chlorine dioxide-generating coating composition of the present invention was obtained by uniformly dispersing and mixing 5 parts of the adsorbate (10% solid content ratio) in 100 parts of a solvent solution (pH 7.0 of 5% aqueous suspension).

This composition was applied to the inner surface of a polyvinyl chloride-containing trash box having a capacity of 18 L so as to have a film thickness of 250 to 300 μm. The thus-obtained trash box has a deodorant effect that lasts for almost a year, and is also effective in preventing the occurrence of "lubrication" that tends to occur on the inner surface.

[0044]

As is clear from the examples, the coating composition of the present invention volatilizes a small amount of chlorine dioxide gas from the coated surface over a long period of time, and the antibacterial and antibacterial effects on the coated surface, or It can exert the deodorizing effect of the space in contact with the coated surface and the freshness maintaining effect of fruits and vegetables, which cannot be achieved by conventional products of this kind.

Therefore, the coating composition of the present invention is used, for example, in a water tank, a water tank of an air conditioner, a sink, etc. to prevent algae and slimy water, to prevent slimy areas around pools and dives, bathrooms,
It can be widely used for various purposes such as anti-fungal and anti-bacterial walls such as push-in, and can be applied to plastic containers that store seafood and fruits and vegetables for various purposes such as keeping freshness, which is extremely useful in industry.

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[Procedure amendment]

[Submission date] January 26, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

Among the above carriers, structurally 10 ² to 1
Carriers with excellent liquid adsorption capacity due to having 0 ⁴ Å micropores, such as synthetic zeolite and activated alumina, are more preferable because they have a better gas sustained release property than carriers without micropores. Used for. Further, these carriers may be used in combination of two or more kinds. Further, the adsorption used in the present invention
Use in combination with a carrier to provide release control of gas emission
As a material to improve, keep the stabilized chlorine dioxide liquid inside.
Inorganic microcapsules that have been held. In paint
It is known to mix microencapsulated drugs into
However, as the type of microcapsules used in the present invention,
Is a stabilized dioxide that is retained inside the microcapsules
The elementary aqueous solution must be liquid and reactive with organic matter.
From the above, the pH of a 5% aqueous suspension of microcapsules was 7.
Silica or calcium silicate micro that shows 0 or more
Capsules are preferred. Organic microcapsules are stable
Avoid using chlorine dioxide because it has poor retention stability
Better.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

In order to disperse the thus obtained adsorbate of the stabilized chlorine dioxide solution in the resin solution, it can be prepared by a conventional method using a general disperser used in the production of paint. The ratio of the amount of adsorbate to the resin liquid is usually 10 with respect to the resin content.
~ 50 wt% is used. In this dispersion operation, in order to improve coatability, addition of additives such as anti-sagging agent and defoaming agent and coloring with dyes and pigments may be optionally performed. The coating composition of the present invention has a characteristic of withstanding storage because, when the chlorine dioxide gas is saturated, no further gas generation is observed during closed storage. Apply the coating composition of the present invention to an object
For cloth, commonly used roll coating, dipping method,
Conventional methods such as the play method can be applied, and the screen is further thickened.
The printing method can also be adopted. When painting, improve the adhesiveness with the base
Good or a primer to avoid the effects of chlorine dioxide
-Painting may be done arbitrarily. The present invention coating
The composition may be applied in various modes depending on the type of object to be applied.
There are advantages available. For example, film, non-woven fabric, cloth
Apply to a sheet-like material such as the ground, and apply these with a release paper
Combine it with the wearing sheet and attach it to the refrigerator, storage, etc.
Anti-fungal antibacterial sheet, which is convenient for
Place them in a sandwich between mesh sheets such as orchids
Use as a shoe insole, combined with a water-absorbent sheet to prevent mildew,
Used for antibacterial water absorption, laminated with a film with fine holes
For more control of gas emission,
A partially perforated shield that does not impair the air or water permeability.
Coated on the board, or coated in a grid or dots
Sheeted material that has been used for a long time, and has an immediate effect when used in contact with water
The coating composition of the present invention is applied so that it is suitable when properties are required.
Part of the cloth not covered with, for example, organic acid powder
Discolored indicator on a part of the seat
Seats with parts to clearly indicate the replacement time,
Anti-fouling coated on a plastic plate with an adhesive with paper pattern
And anti-bacterial plates, and mold-proof packaging materials that have been impregnated and dried on cloth
There are various fields in which can be applied.

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Claims (5)

[Claims] 1. A stabilized chlorine dioxide solution having a pH value of 8.0 to 12.0 and having a water absorption capacity of at least 50% by weight and containing 0.1 to 5.0% of stabilized chlorine dioxide liquid, and formed into fine granules from powder. A composition obtained by adsorbing and supporting on an adsorption carrier having a particle size distribution, which has a film-forming ability and is dispersed in a resin liquid having an aqueous solution or a 5% aqueous suspension having a pH of 7.0 or more. A chlorine dioxide-generating coating composition comprising as a main component. 2. The chlorine dioxide-generating coating composition according to claim 1, wherein the adsorbent carrier is a carrier having structurally fine pores of 10 ² to 10 ⁴ Å and excellent in retaining liquid absorption. 3. The adsorption carrier has a pH of a 5% aqueous suspension of 7.
A carrier comprising a mixture of powder and fine granules obtained by pulverizing a granular molded body having a size of 0 or more.
The chlorine dioxide-generating coating composition described. 4. The chlorine dioxide-generating coating composition according to claim 1, 2 or 3, wherein the resin liquid is a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer or a vinylidene chloride resin in an organic solvent or an aqueous dispersion. . 5. The chlorine dioxide-generating coating composition according to claim 1, 2 or 3, wherein the resin liquid is an alkyd resin, an acrylic resin or an acrylic silicone resin liquid.