JPS584945B2 - Slightly flammable aerosol paint - Google Patents

Description

[Detailed description of the invention] The present invention relates to a slightly flammable aerosol paint.

More specifically, the present invention relates to a slightly flammable aerosol paint obtained by blending a nonflammable organic solvent, a high boiling point solvent, and a propellant in specific proportions.

Conventional aerosol paints use large amounts of highly flammable organic solvents such as toluene, solvent naphtha, ethyl acetate, and methyl ethyl ketone to dissolve resin components, but these organic solvents have low flash points. There is a high risk of ignition and explosion when exposed to fire, and constant care and skill are required when manufacturing aerosol paints on a large scale in factories.Also, when spraying with aerosol products filled in cylinders, there is a high risk of ignition and explosion. There are many difficulties in handling, such as the need for regulation.

Most aerosol paints currently on the market are designated as "hazardous materials 1" under the Fire Service Act, and are classified as "highly flammable" according to the High Pressure Gas Control Law.

In order to eliminate such handling hazards, some aerosol paints use high-boiling organic solvents with relatively high flash points as solvents, but when combined with resin, which is a paint component, the resin's There are problems with solubility and sagging properties when sprayed into a film, and therefore large amounts of highly volatile and low flash point solvents must be used together until a satisfactory solution is achieved. This has not yet been achieved.

The inventors of the present invention have conducted research in order to solve these problems and obtain an aerosol paint that completely eliminates the risk of fire, and have finally obtained a slightly flammable aerosol paint.

Therefore, an object of the present invention is to provide a slightly flammable aerosol paint which is not dangerous to fire and does not cause sagging in the paint film formed by spraying.

As used herein, the term "slightly flammable" means the combustibility classification "slightly flammable" defined by the High Pressure Gas Control Law.

The slightly flammable aerosol paint of the present invention is obtained by blending a resin vehicle and, if necessary, a pigment dissolved and dispersed in a nonflammable organic solvent and a high boiling point solvent, with an aerosol propellant in a specific ratio.

That is, the slightly flammable aerosol paint of the present invention comprises (1) a stock solution consisting of a nonflammable organic solvent, a high-boiling solvent, a resin vehicle, and, if necessary, a pigment, and (2) a propellant consisting of dimethyl ether and dichlorodifluoromethane. (3) Dimethyl ether is 20 to 40% by weight of the entire aerosol paint, and the total of dichlorodifluoromethane and nonflammable organic solvent is 35 to 60% by weight; (4) Nonflammable organic solvent Dimethyl ether is present in an amount of 55% by weight or less based on the total of the three components, dimethyl ether and dichlorodifluoromethane.

The aerosol paint of the present invention obtained in this way is classified as a "slightly flammable" aerosol as defined by the High Pressure Gas Control Act (Ministry of International Trade and Industry Notification No. 557, Article 3, Item 7), and poses little danger to fire. It's not easy.

In the aerosol paint of the present invention, the mixing ratio of the paint paste consisting of a high floating point solvent, a resin vehicle, and a desired pigment, the sum of the three components of the propellants dimethyl ether and dichlorodifluoromethane, and a nonflammable organic solvent is 20 ~30 volume receptacle 70-80 volume% is preferred.

The high boiling point solvent used in the present invention has a flash point higher than the boiling point of the nonflammable organic solvent, such as water, ethyl cellosolve (flash point 44°C or lower), butyl cellosolve (59.5°C), methyl Cellosolve acetate (56℃), ethyl cellosolve acetate (51℃),
Butyl cellosolve acetate (88℃), aromatic high boiling point mixed solvent such as "Solbesoso #100" (38-42
°C), "#-150" (65 °C) (manufactured by Esso): Other commercially available products include "Swazol 1000, 1500" (
Maruzen Oil), “Spasol 1500, 1800” (Mitsubishi Oil), “MSS” (Mitsui Petrochemical), “Hysol 100, 150” (Nippon Oil), Pekazol 10
0,150” (manufactured by Mobil), “I Special Hysol” (
(manufactured by Showa Sekiyu).

Among these solvents, organic solvents such as ethyl cellosolve and butyl cellosolve are used to prevent the whitening phenomenon (whitening and matting of the paint film due to adhesion of moisture in the air) when spraying the paint, and to prevent the paint from coating. It is preferable to use it as a true solvent when blending nitrocellulose added to improve film hardness.

Although aliphatic lower alcohols such as ethanol, n- and 1-propanol, and butanol are not high-boiling solvents, they may be added in small amounts to improve the sprayability and drying properties of the aerosol paint.

There are no restrictions on the resin vehicle used in the present invention, but
Examples include water-soluble acrylic resins, alkyd-modified acrylic resins, amino-modified acrylic resins; alkyd resins, urethane-modified alkyd resins, and amino-modified alkyd resins.

Preferred nonflammable organic solvents include aliphatic halogenated hydrocarbons such as trichloromonofluoromethane, trichlorotrifluoroethane, methylene chloride, and methylchloroform.

These solvents can be selected as appropriate, taking into consideration the toxicity, solubility of the resin, price, etc. For example, when the resin vehicle is water-soluble, it is preferable to use trichlorotrifluoroethane, and when the resin vehicle is water-soluble, it is preferable to use trichlorotrifluoroethane. Preference is given to using methylene chloride.

Products containing 40 to 60% by weight of nonflammable organic solvents based on the original solution are not only "slightly flammable" under the High Pressure Gas Control Law, but also meet the requirements for "non-hazardous materials" under the Fire Service Law. Therefore, an extremely safe aerosol paint can be obtained.

Nonflammable organic solvents include, for example, trichloromonofluoromethane (boiling point 23.7°C, the same applies hereinafter), trichlorotrifluoroethane (47.6°C), methylene chloride (4°C),
0.6°C), methyl chloroform (75°C), methylene chloride (40.6°C), etc., and they can be used in various combinations with the above-mentioned high boiling point solvent, taking into account the flash point and boiling point of both.

If the amount of dimethyl ether in the propellant is less than 20% by weight based on the entire aerosol paint, the resin dissolving power will decrease and a sufficiently good atomization will not be obtained. ” requirements will no longer be met.

Furthermore, if the total amount of cyclodifluoromethane and nonflammable organic solvent is less than 35% by weight based on the total aerosol paint, it will not be possible to obtain a "slightly flammable" aerosol paint.
If it exceeds 0% by weight, good spraying cannot be obtained.

When using a resin vehicle as described above, in order to improve the properties of the coating film, the hardness of the coating film is improved by adding 5 to 20% by weight of nitrocellulose as a modifier based on the solid content of the resin vehicle. be able to.

Examples of preferred combinations of resin vehicle and solvent are shown in the following table.

Table 1 Resin vehicle High boiling point solvent Non-flammable organic solvent Water-soluble acrylate Ethyl cello trichlorotolyl resin Rubbutirse Fluoroethane Rosolve Water-insoluble aqueous Sorbetsoryl resin (Soluble in methylene chloride and beneben ≠ 150 ethyl) Cellosolve Solutso alkyd resin ≠ 150 ethyl Methylene chloride Cellosolve The propellants used in the present invention are dimethyl ether and dichlorocyfluoromethane, and the mixing ratio of these propellants and the nonflammable organic solvent is such that dimethyl ether accounts for 30 to 60% by weight of the total of these three components. Must be present in quantity.

The aerosol paint of the present invention obtained when the mixture included in this mixing ratio is contained in the aerosol paint is classified as a "non-hazardous substance" according to the Fire Service Act, and is classified as a "non-dangerous substance" according to the High Pressure Gas Control Law against fire. Indicates safety of "slightly flammable" or better.

Note that ordinary propellants other than the above-mentioned dimethyl ether and dichlorofluoromethane, such as monochlorodifluoromethane, liquefied petroleum gas such as propane gas, n- and i-butane gas, etc., can also be used in appropriate amounts as necessary.

The slightly flammable aerosol paint according to the present invention is "slightly flammable" as defined in the High Pressure Gas Control Law, and is highly safe in handling, especially in storage, transportation, and commercialization, and is extremely advantageous in manufacturing and use.

In addition, this aerosol paint is classified as "slightly flammable" under the flammability classification of the High Pressure Gas Control Law, and its explosive limit concentration is much higher than that of conventional highly flammable aerosol paints, making it safer. Become.

Furthermore, the amount of flammable gas generated when sprayed can be reduced to approximately half that of conventional aerosol paints, making it extremely safe.

The present invention will be specifically explained by the following examples.

Examples Slightly flammable aerosol paints of the present invention were prepared according to the following formulations.

Comparative formulation 1. Transparent aerosol paint (wt%) Room temperature drying turben-soluble acrylic resin (resin solid content 50 wt%; solvent: Solbetsuso≠150, ethyl cellosolve) 19 Butyl cellosolve (high boiling point organic solvent) 6 Methylene chloride (nonflammable) Organic solvent) 12 Dichlorodifluoromethane (propellant) 14 Dimethyl ether (propellant) 49 Total 100 Prescription 1 Transparent aerosol paint (wt%) Room temperature drying water-soluble acrylic resin (resin solid content 50 wt%; Solvent: ethyl cellosolve, Water) 18 Butyl cellosolve (high boiling point organic solvent) 5 Methylene chloride (non-flammable organic solvent) 20 Dichlorodifluoromethane (propellant) 17 Dimethyl ether (propellant) 40 total 100 Prescription 2 White aerosol paint (wt%) Room temperature drying water soluble Acrylic resin (resin solid content 50% by weight: Solvent: ethyl cellosolve, water) 11 Titanium white 7 Butyl cellosolve (high boiling point organic solvent) 4 Trichlorotrifluoroethane (non-flammable organic solvent) 25 Dichlorodifluoromethane (propellant) 21 Dimethyl ether (propellant) 32 Total 100 Prescription 3 Black aerosol coating rate (wt%) Room temperature drying alkyd resin (medium oil alkyd resin solid content 50 wt%; Usai L Solbetsuso 8150) 15 Carbon black 1 Butyl cellosolve (high boiling point organic Solvent) 4 Methylene chloride (nonflammable organic solvent) 30 Dichlorodifluoromethane (propellant) 25 Dimethyl ether (propellant) 25 Total 100 Comparative formulation 2. Black aerosol paint (wt%) Room temperature drying alkyd resin (urethane modified alkyd resin solid content 50 wt%; solvent: Solbetsuso≠150) 14 Carbon black 1 Butyl cellosolve (high boiling point organic solvent) 4 Methylene chloride (nonflammable organic solvent) 34 Dichlorodifluoromethane (propellant): 34 Dimethyl ether (propellant): 13 Total: 100 Table 2 shows the results of testing the flammability of the slightly flammable aerosol paint of the present invention obtained using each of the above formulations.

In the same table, A is the weight percent of the nonflammable organic solvent in the stock solution (before adding propellant), B is the weight percent of dimethyl ether in the aerosol paint, and C is the weight percent of the nonflammable organic solvent in the aerosol paint. Weight% of dichlorodifluoromethane
where D is the value (g/l) determined by the explosive test based on the Ministry of International Trade and Industry Notification No. 557, and E is the value (cm) determined by the flame length test based on the Ministry of International Trade and Industry Notification No. 557, and the former indicates that the larger the value, the more The latter means that the smaller the value, the more difficult it is to burn, and F is the value (°C) determined by a flash point test based on JIS K-2539 tag closed cup method 5°C → 80°C, and no flash point is found. This means that they do not qualify as "hazardous materials" as defined in the Fire Service Act.

Furthermore, G indicates the type of aerosol based on Ministry of International Trade and Industry Notification No. 557.

The proportions of dimethyl ether, dichlorodifluoromethane and nonflammable organic solvent in these formulations are shown in Table 3.

Table 3: Dimethylethane, dichlorodifluoromethane, dichlorodifluoromethane, dichlorodifluoromethane, nonflammable organic solvent (wt%)
) (% by weight) Comparative formulation 1 65 16+191
51 22+27 2 41 27+323 3
1 31+38 comparative prescription 2 16
42+42 As is clear from Tables 2 and 3, those in which the proportion of dimethyl ether exceeds 60% by weight based on the total of the three components (comparative formulation 1) are not "slightly flammable" and are It can be seen that the one containing 30% by weight or less (comparative formulation 2.) has a D value of 3.4 or more (cannot be atomized) and cannot be used as an aerosol paint.

It was also found that the slightly flammable aerosol paints (formulations 1 to 3) of the present invention completely meet the requirements for "slightly flammable".
Furthermore, the coating films formed with these coatings all exhibited sufficiently satisfactory sagging resistance.

Claims (1)

[Claims] 1 A propellant consisting of dimethyl ether and dichlorodifluoromethane is blended into a stock solution consisting of a non-flammable organic solvent, a high boiling point solvent, a resin vehicle and, if necessary, a pigment, and the amount of dimethyl ether is 20 to 40% by weight of the entire aerosol paint. %, the total of dichlorodifluoromethane and the nonthermal organic solvent is 35 to 60% by weight, and the amount of dimethyl ether is 3C to
A recirculating aerosol paint characterized in that it is present in an amount of 60% by weight.