JPH05140479A - Deodorizing coating material - Google Patents

Abstract

PURPOSE:To obtain a deodorizing coating material excellent in deodorizing effect, deodorizing rate, persistence, water resistance, etc., by incorporating an aluminosilicate and an oxidizing agent into a coating material so that the volume concentration of pigment in a coating film is controlled to be within a specified range. CONSTITUTION:An aluminosilicate and an oxidizing agent (e.g. hydrogen peroxide) are incorporated into a coating material so that the volume concentration of pigment in a coating film including the aluminosilicate and the oxidizing agent is 20-45%, thus producing a deodorizing coating material. As the aluminosilicate, those having a composition consisting of three constituents in terms of oxides, i.e., 5-80mol% SiO2, 5-65mol% MOn/2, (wherein M is Zn, Cu, Ag, Co, Ni, Fe, Ti, Ba, Sn or Zr; (n)is the valence of M), and 1-60mol% Al2O3 are preferably used. The obtained deodorizing coating material is suitably used for coating, e.g. wood for the walls, bathroom and toilet in a house, a hospital, etc.

Description

Detailed Description of the Invention

[0001]

The present invention has an excellent deodorizing power,
The present invention relates to a deodorant paint that can be widely used for household odors generated from home and industrial odors generated from factories.

[0002]

2. Description of the Related Art With the urbanization and diversification of living environments, interest in the odors around us has been increasing, and the criticism of bad odors has become particularly severe. Hitherto, what has been proposed as a deodorizing paint is a deodorizing hygroscopic paint obtained by mixing a fine powder of zeolite with an emulsion paint (Japanese Patent Laid-Open No. 50-322).
33), an organic polycarboxylic acid and a binder resin, or a deodorizing paint obtained by adding a ferrous salt to these (Japanese Patent Application Laid-Open No. 61-151273) and the like.

Of these, physical adsorption by means of zeolite or the like generally has a drawback that the adsorption capacity is limited and the adsorption force is lowered relatively early. Further, the method of using a carboxylic acid or the like is effective for ammonia and amines, but is insufficient for a sulfur type such as mercaptan.

In order to improve this point, a deodorant paint for construction (Japanese Patent Laid-Open No. 1-217083) containing an enzyme deodorant and a deodorant containing phytoncide as an active ingredient, titanium, aluminum, magnesium, calcium and silicon. A deodorant coating composition composed of oxide agglomerated particles containing zinc as a main component and one or more elements selected from the group consisting of:
No. 2967), phosphoric acid, phosphorous acid, hypophosphorous acid, chloric acid, chlorous acid, hypochlorous acid, or a deodorizing paint containing at least one selected from salts thereof (Japanese Patent Laid-Open No. 2-33).
No. 05867), a coating composition in which at least one acid selected from ascorbic acid and oxypolybasic acid or a salt thereof is bonded to manganese (II) ion (JP-A-3-12463). Has been done.

Although the above deodorant paints have both improved deodorant capacity and selectivity of deodorant effect, they are still sufficient in that they rapidly deodorize various malodorous components to below a human threshold. Not a thing.

[0006]

DISCLOSURE OF THE INVENTION The present invention has an excellent deodorizing effect against various malodors, and has a high deodorizing rate.
It is intended to provide a deodorant paint having excellent durability.

[0007]

As a result of various studies, the present inventors have blended (a) an aluminosilicate and (b) an oxidizer into a coating material, and have added the aluminosilicate and the oxidizer to the paint. The inventors have found that a paint having an excellent deodorizing effect against various malodors can be obtained by setting the volume concentration of pigment in the coating film including 20% to 45%, and completed the present invention.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the component (a) in the present invention, it is preferable that the three-component composition ratio expressed as an oxide has the following chemical formula 2.

[0009]

[Chemical 2] (M represents at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin and zirconium, and n represents the valence of the metal).

The aluminosilicate as the component (a) is obtained as a white or light colored powder, and the amount of the water-soluble silicate, the water-soluble metal salt and the water-soluble aluminum salt and / or the water-soluble metal salt corresponding to the above composition ratio is obtained. It is prepared by reacting a water-soluble aluminate in the presence of water and heating the resulting precipitate in the presence of water.

As the oxidant of the component (b), percarbonate,
Persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate and potassium monopersulfate, organic peracids such as hydrogen peroxide, diperoxide decanedioic acid and magnesium perphthalate, and salts thereof are preferred.

The deodorant coating composition of the present invention contains the above-mentioned components (a) and (b) as essential components. If necessary, both components may be mixed in the form of powder or granules, or ( The component (b) is affixed to the component (a), and the amphoteric components (a) and (b) are kneaded and granulated under the condition of holding the solvent.

In order to make full use of the ability of these deodorants, it is necessary for the binder to exhibit its function without being hidden by the binder when formed into a coating film.
For this purpose, it is necessary that the deodorant is kept in contact with the outside air in a porous coating film state, and the pigment volume concentration in the coating film is 20%.
% To 45%, and more preferably 3
5 to 42%. The pigment volume concentration is ((a),
(Volume of pigment component in coating film including aluminosilicate of component (b)) / (total coating film volume).

That is, when the volume concentration of the pigment is less than 20%, the deodorant is hidden by the binder as described above and the effect is weakened. On the other hand, when it exceeds 45%, the brittleness of the coating film which cannot be practically used. It is not preferable because

The weight ratio of (a) aluminosilicate to (b) oxidizing agent is (a) / (b) = 1/99 to 99.9 /.
0.1, more preferably 50/50 to 99.5 / 0.5
It is preferable to coexist within the range of.

As the binder resin, urethane type resin, acrylic type resin, vinyl acetate type resin and the like are suitable, but any of the resins used in various other paints may be used alone or in combination.

As the solvent or dispersion medium, alcohol,
Ketones, esters, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, other organic solvents, or mixed solvents thereof can be used, but are not particularly limited.

The method of compounding may be at the time of preparation of each coating agent or after preparation, for example, ball mill,
It is preferable to disperse the ingredients sufficiently uniformly by a mixing means such as a roll, a sand mill, an attritor, or a kneader.

Further, in making the paint, it is desirable to carry out a molecular sieve method or the like so that the deodorant is uniformly distributed in the formed coating film. Further, it is optional to add an organic or inorganic coloring pigment, an extender pigment, a thickener, a film-holding colloid agent, a film-forming aid, a defoaming agent, a dispersant, and other additives which are usually used in paints.

However, in the case of the auxiliary pigment of the present invention which has the function of remarkably improving the deodorizing effect, scaly flakes such as talc relieve the shrinkage stress of the coating film and improve the water resistance. A large oil absorption is desirable.

[0021]

The mechanism of deodorization in the deodorant paint of the present invention is not clear, but it is considered that physical adsorption proceeds at a very fast rate until equilibrium adsorption, followed by chemical reaction. That is, by combining the aluminosilicate of the component (a) and the oxidizing agent of the component (b), the speed of adsorption of the malodor on the aluminosilicate having a large specific surface area and the chemical reaction by the adsorbed malodorous oxidizing agent are achieved. It is believed that they act synergistically and more effectively deodorize.

Furthermore, by controlling the pigment volume concentration in the coating film within an appropriate range, the deodorant base is effectively hidden without being hidden by the binder resin in the coating film.

Further, the bad odor captured by the adsorption and the chemical reaction is no longer released as an odor, and the deodorization which is a drawback of the deodorization due to physical adsorption is suppressed and the deodorizing effect is improved. It is considered that sustainability has improved.

[0024]

According to the deodorant paint of the present invention, the aluminosilicate as the component (a) and the oxidizing agent as the component (b) are used in combination,
By controlling the pigment volume concentration in the coating film within an appropriate range, it exerts an excellent deodorizing effect, promptly exhibits the deodorizing effect, and is excellent in the sustainability of the effect.

Therefore, although various malodorous components are mixed in the malodor generated in the human body, indoors, living environment, industrial facilities, etc., the deodorant paint of the present invention quickly eliminates these malodors.
Moreover, since the deodorizing effect is maintained for a long period of time, it can be widely used.

The deodorant paint of the present invention can be applied to walls such as residences, public facilities, hospitals, toilets, bathrooms, kitchen areas, woods, ceramics, gypsum boards, metal materials, plastics, etc. in vehicle interiors.

Further, since the deodorant used in the present invention is a white powder, it can be freely color-matched to the color tone desired for decoration, and is suitable for cosmetics.
Further, since it is excellent in water resistance, adhesion to various materials, oil resistance, crack resistance, aging resistance, etc., it can be expanded to various applications. Hereinafter, examples of deodorant paints and evaluation results thereof will be sequentially described, but the present invention is not limited to these examples.

[0028]

【Example】

Example 1 As a liquid A, the three-component composition ratio is SiO ₂ : 31 mol%, Z
Compounding ratio 95/5 of aluminosilicate and potassium persulfate corresponding to nO: 54 mol% and Al ₂ O ₃ : 15 mol%
25 parts of deodorant mixed by weight (weight basis, the same applies hereinafter), 7.5 parts of molecular sieve powder (Showa Denko KK),
1.5 parts of the nip seal 220A (Nippon Silica Co., Ltd.) is mixed and gently stirred. After standing for about 10 minutes, 18.1 parts of a hydroxyl group-containing acrylic polyol (Dainippon Ink and Chemicals, Inc.) and 15 parts of butyl acetate are added and thoroughly mixed with a high-disper device.

Next, 2 parts of Microgel (Mitsui Toatsu Chemicals, Inc.) was added and mixed, and Cellosolve acetate 15 was added.
The part with parts added is the mill base. This mill base was dispersed by a motor mill for 2 passes, and after taking out the mill base, the inside of the mill was washed with 9 parts of ethyl acetate and 5.7 parts of toluene, and then, butyric acid acetate fibrin (20% liquid) 0.6
Parts, 0.5 parts of a silane coupling agent, and 0.1 parts of zinc octate are added and mixed with a high disper to form a coating.
It is filtered through a 150 mesh screen and stored.

As the solution B, 7 parts of a buret type polyisocyanate solution (Asahi Kasei Kogyo Co., Ltd.) and 3 parts of toluene are sufficiently stirred, and nitrogen gas is sealed and stored. These A liquids,
Mixing weight ratio of liquid B, liquid A: liquid B: thinner = 100: 1
The mixture was thoroughly mixed at 0:40, spray-coated on the ABS resin, and then dried at 25 ° C. for 8 hours.

The pigment volume concentration in this coating film was 41.7%, and the temperature dispersion in the viscoelastic properties of the coating film was such that the glass transition temperature was 70 to 80 ° C. and Tan δ was 0.7 to 0.8. It was an ideal area showing the range. Besides this,
General coating film properties are shown in Table 1 below.

Example 2 The three-component composition ratio of aluminosilicate was SiO ₂ : 41 mol%, ZnO: 38 mol%, Al ₂ O ₃ : 21 mol%, and hydrogen peroxide was used as the oxidizer. 90/10
A deodorant paint was obtained in the same manner as in Example 1 except that the deodorant mixed in step 1 was used.

Example 3 The three-component composition ratio of aluminosilicate was SiO ₂ : 55 mol%, CoO: 28 mol%, Al ₂ O ₃ : 17 mol%, and the oxidizing agent was potassium permanganate. A deodorant paint was obtained in the same manner as in Example 1 except that the deodorant mixed in the ratio 80/20 was used.

Example 4 The composition ratio of the three components of aluminosilicate was SiO ₂ : 55 mol%, NiO: 28 mol%, Al ₂ O ₃ : 17 mol%, and the oxidizing agent was diperoxide decanedioic acid. A deodorant paint was obtained in the same manner as in Example 1 except that the deodorant mixed in a weight ratio of 55/45 was used.

Examples 5 to 8 Deodorizing paints were obtained in the same manner as in Example 1 except that the raw materials shown in Tables 2 and 3 were used. The same molecular sieve powder, hydroxyl group-containing acrylic polyol, and burette type polyisocyanate solution as in Example 1 were used.

Comparative Example 1 A deodorant paint was obtained in the same manner as in Example 1 except that activated carbon was used as the deodorant.

Comparative Example 2 A deodorant paint was obtained in the same manner as in Example 1 except that the raw materials shown in Tables 2 and 3 were used. These deodorant performances were evaluated according to the following evaluation methods, and the evaluation results are shown in Table 4 together with Comparative Examples.

<Evaluation method of deodorizing effect> Meat, vegetables, fish and the like were put in a 6-liter desiccator and left for 2 weeks to create artificial garbage odor. The deodorant paint piece applied on the ABS resin was cut into 5 × 10 cm and put in a 1.8 liter wide-mouth bottle to prepare a sample. Into this wide-mouthed bottle, add 10 ml of headspace gas with an artificial garbage odor from the 6 l desiccator,
The odor intensity over time was sensory evaluated according to the following criteria.

[0039] Evaluation is carried out by a panel of 5 people, and the upper and lower 2 people are cut and 3
The average of names was rounded off.

[0040]

[Table 1] Test items result Test condition Painted appearance White Matte Visual judgment  Adhesiveness 100/100 100 squares of 1mm square that reach the base are made and the adhesive tape is adhered and peeled off. Find out the number of Passed impact resistance Passes a load on the coated surface with a DuPont impact tester. give. Weight 500g, drop 50cm Thermal non-adhesiveness 5 pieces of 50mm square gauze are piled up and 500g weight is applied. Place it on and leave it at 50 ℃ for 24 hours. Passed warm water resistance Soak in warm water at 40 ℃ for 240 hours and pull up at 24:00 After 100/100, carry out the adhesion test. Moisture resistance Pass After leaving at 50 ℃ -95% for 240 hours, leave it at room temperature for 24 hours. After 100/100 hours of storage, conduct an adhesion test. Heat cycle resistance Passed 50 ℃ ± 30 ℃ × 1 hour as 1 cycle, 30 No cracks Observe changes after cycling. Weather resistance No crack QU.V. After 500 hours, change in appearance of coating film and 100/100 Observe adhesion. Aging resistance No abnormal appearance Appearance change and coating after 70 ° C x 240 hours Observe 100/100 adhesion.

[0041]

[Table 2]  Comparative example Example  2 5 6 Remarks Pigment volume concentration 15% 20% 25% Liquid A: Raw material name: Molecular sieve powder 3.7 4.6 5.4 Aluminosilicate + 12.0 15.2 18.0 Example 1 used oxide Nipseal 220A 1.2 1.5 1.8 Hydroxyl group-containing 37.0 31.7 27.8 Binder Acrylic polyol Butyl acetate 15.0 15.0 15.0 Ethyl acetate 9.0 9.0 9.0 Cellosolve Acetate 15.0 15.0 15.0 Butyric acid fibrin 20% liquid 0.6 0.6 0.6 Silane coupling agent 0.5 0.5 0.5 Zinc octate 0.1 0.1 0.1 Microgel 2.0 2.0 2.0Toluene 3.9 4.8 4.8  Total 100.0 100.0 100.0 Liquid B: Raw material name; burette type 16.3 13.9 9.2 75% liquid Polyisocyanate liquidToluene 3.7 6.1 10.8  Total 20.0 20.0 20.0  Mixing weight ratio B liquid / A liquid 20/100 20/100 20/100

[0042]

[Table 3]  Example 7 8 Remarks Pigment volume concentration 35% 45%  Liquid A: Raw material name; Molecular sieve powder 6.5 8.0 Aluminosilicate + 21.8 26.7 Example 1 used product Oxide nip seal 220A 2.2 1.6 Hydroxyl group-containing 22.5 16.7 Binder acrylic polyol Butyl acetate 15.0 15.0 Ethyl acetate 9.0 9.0 Cellosolve acetate 15.0 15.0 Butylacetic acid fiber 20% solution 0.6 0.6 Silane coupling agent 0.5 0.5 Zinc octate 0.1 0.1 Microgel 2.0 2.0Toluene 4.8 4.8 Total 100.0 100.0 Solution B: Raw material name; burette type 7.4 7.3 75% solution Polyisocyanate solutionToluene 2.6 2.7 Total 10.0 10.0 Mixing weight ratio B liquid / A liquid 10/100 10/100

[0043]

[Table 4]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 16, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Chemical 1] (M represents at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin and zirconium, and n represents the valence of the metal). The deodorant paint according to claim 1.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

[Chemical 2] (M represents at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin and zirconium, and n represents the valence of the metal).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Minoru Kishi 7-13-12 Hirai, Edogawa-ku, Tokyo Inside Rion Co., Ltd.

Claims (3)

[Claims] 1. A method comprising: (a) an aluminosilicate and (b) an oxidant, wherein the pigment volume concentration (including the aluminosilicate and the oxidant) in the coating film is 20% to 45%. Characteristic deodorant paint. 2. The aluminosilicate of the component (a),
The three-component composition ratio expressed as an oxide is shown below. (M represents at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin and zirconium, and n represents the valence of the metal). The deodorant paint according to claim 1. 3. The oxidizing agent as the component (b) is an organic peracid or a salt thereof, a percarbonate or a persulfate.
Or the deodorant paint according to 2.