JPS5856589B2 - Non-flammable paint concentrate composition for aerosol injection - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a paint solution that is non-flammable and highly stable before being sealed in an aerosol container together with a propellant, and the coating film formed by spraying has excellent water resistance. The purpose is to provide something.

Since aerosol spray paints are often used for household purposes, it is particularly desirable that they be non-flammable.

Water-based paints are ideal in terms of non-flammability, and the present applicant disclosed a paint stock solution composition for aerosol spraying in Japanese Patent Publication No. 53-34207, and put the invention into practice and received favorable reviews. It has gained.

However, since this product contains water and uses a water-soluble resin vehicle, the dryness and water resistance of the wall film may be affected.
It is inevitable that it is inferior to flammable paints, and the solvent is limited to relatively expensive glycol ether and ethanol.
In particular, it is necessary to take anti-corrosion measures for containers due to the presence of water.
Price increases are inevitable.

Therefore, the inventor of the present invention has made efforts to develop a non-flammable aerosol paint that overcomes all of the above-mentioned drawbacks, and as a result has achieved remarkable and excellent results that have not been provided in the past.

The present invention will be explained in detail below. That is, the non-flammable paint stock solution composition for aerosol injection according to the present invention comprises a water-insoluble resin paint vehicle, a medium-boiling point or high-boiling point flammable organic solvent,
Trichlorotrifluoroethane is blended in an amount of 10 to 40% by weight based on the total amount of the composition.

The water-insoluble resin paint vehicle is a well-known vehicle for water-insoluble resin paints, which uses water-insoluble resins, such as natural resins, synthetic resins, or resin analogs, as coating film-forming materials as solutes or It contains at least a part of suspended solids, and may further include pigments, metal powder, plasticizers, etc. as required.

Examples of resins that are already used in the vehicle include acrylic, modified acrylic, alkyd, modified alkyd, polyester, vinyl acetate, vinyl chloride, vinyl acetate/vinyl chloride copolymer, organosilicon, Examples include resin analogs that are natural products or processed products thereof, such as butyral, styrene, vinyltoluene, epoxy, and urethane synthetic resins, nitrified cotton, ethyl cellulose, acetyl cellulose, chlorinated rubber, tar, and bitumen.

Of course, all of these known resins can be blended in the present invention, but resins other than those listed above may also be used as long as they are effective for forming a coating film.

However, "insoluble in water" here means that it has very poor affinity for water at room temperature and pressure.

In the present invention, the medium-boiling point or high-boiling point flammable solvent mentioned above includes, for example, toluene, xylene, cyclohexane, methylcyclohexane, ethylcyclohexane, normal heptane, isooctane, isoparaffin, solvent naphtha, mineral spirit, ethanol, normal propyl alcohol, Isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, isoamyl alcohol, benzyl alcohol, methylbenzyl alcohol, 3-methoxyphtanol, cyclohexanol, 2-methyl-1-butanol, methyl Amyl alcohol, methyl isobutyl J'V calpitol, diacetone alcohol, polyhydric alcohol, ethyl amyl ketone, methyl isobutyl ketone, diisopropyl ketone, methyl propyl ketone, diethyl ketone, methyl butyl ketone, methyl amyl ketone, isophorone, cyclohexanone, isopropyl ether, Dioxane, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol acetate,
These include ethylene glycol monoethyl ether acetate, isopropyl acetate, butyl acetate, secondary butyl acetate, n-propyl acetate, amyl acetate, ethyl amyl acetate, isobutyl acetate, methyl propionate, and the like.

Among the above, isopropyl alcohol and ethanol have boiling points of 82.4°C and 78.3°C, respectively, which is different from the usual classification in which low boiling points are 100°C or less, but in the present invention, they have particularly low boiling points. Isopropyl alcohol and ethanol are also treated as medium-boiling solvents to distinguish them from trichlorotrifluoroethane.

Although methyl ethyl ketone belongs to the medium boiling point solvent defined above in the present invention, it must be excluded for the reasons described below.

Now, as mentioned above, the first object of the present invention is to provide a non-flammable coating composition.

By the way, it is well known that it is effective to incorporate a nonflammable solvent in the preparation of a nonflammable composition.

Water, 1,1,1-trichloroethane, perchlorethylene, trichloroethylene, methylene chloride, etc. are well known as nonflammable solvents, but non-water-soluble solvents that are themselves highly water resistant and contribute to improving the quality of the coating film are well-known. The vehicle is
They have poor stability in nonflammable solvents and are highly toxic except in water.

In addition, even though the above-mentioned chlorinated solvents are nonflammable themselves, they contain hydrogen atoms in their molecules, so they have a weak combustion suppression effect. When a solvent is used in combination, no effect can be expected unless it is blended in a large proportion.

On the contrary, trichlorotrifluoroethane (Freon 1
13) is itself nonflammable and has a large combustion suppressing effect, and its blending ratio is 10% of the total amount of the paint composition.
It is possible to make the composition non-flammable even if the degree is low.

An example of this experimental result is shown in the drawing, so please refer to it.

Not only that, but the mixing ratio may be relatively small, so
An advantage is that the porridge composition has good stability within the aerosol container.

A further great advantage of trichlorotrifluoroethane as a solvent is its reasonably low boiling point.

Therefore, in the coating composition of the present invention, most important solvents can be used, including relatively inexpensive solvents, with the exception of -12.

In other words, when a solvent with a boiling point higher than that of trichlorotrifluoroethane is used together with trichlorotrifluoroethane, even if the proportion of the latter is small, it accounts for a large proportion of the composition of the mixed vapor generated due to the combined use. , the combustion suppressing effect becomes large, and therefore the blending ratio of trichlorotrifluoroethane may be relatively small.

The boiling points and flash points of the main solvents in common coating compositions are shown in the table below.

Generally speaking, the higher the boiling point, the higher the flash point, and the lower the boiling point, the lower the flash point.
The degree of boiling point and the degree of flash point are not the same.

Therefore, in order to make the coating composition non-flammable, the tricks of the present invention are necessary.

. In order to determine the possible blending ratio of a combustion inhibiting factor such as trifluoroethane, it is necessary to specify the flammable solvent to be used together and to determine it through experiments.

On the other hand, as is well known, in paint compositions,
It is not possible to use a single type of solvent, or even if multiple types of solvents are used, only those having the same boiling point can be blended.

In other words, if only low-boiling point substances are mixed, when the paint is sprayed, the painted surface will rapidly cool down due to rapid evaporation, causing whitening due to moisture in the atmosphere, while whitening due to poor fluidity (pinholes) will occur. This may cause foaming.

If only a high boiling point is used, the drying properties will be poor and the coating will sag.

Therefore, in order to obtain a good coating film, it is necessary to mix a low boiling point solvent and a high boiling point solvent in an appropriate ratio.

However, the boiling point of trichlorotrifluoroethane is 47
°C, and belongs to those with a particularly low boiling point among those normally classified as low-boiling point solvents.

Therefore, from the viewpoint of coating film formation, it is very advantageous to blend trichlorotrifluoroethane, and by blending it with a medium to high boiling point solvent, suitable fluidity that does not cause sagging can be achieved. A beautiful coating film can be formed.

According to the inventor's experimental research, when using the above-mentioned medium- to high-boiling point solvents, it is necessary to include the vehicle in order to maintain good coating film formation and vehicle stability. It was found that the upper limit of the proportion of trichlorotrifluoroethane that can be incorporated into the entire composition is 40%.

However, when targeting medium to high boiling points that are easily available, 15
Approximately 25% is optimal.

That is, in the present invention, the proportion of trichlorotrifluoroethane in the total composition needs to be 10% or more from the viewpoint of ensuring non-flammability as described above, and it is necessary to prevent coating film formation and composition. From the viewpoint of stability, it is necessary that it be 40% or less.

Incidentally, the high boiling point solvents that are allowed to be incorporated into the composition of the present invention include ethanol and isopropyl alcohol, but these have boiling points of 78.3°C and 82.4°C, respectively, and are not commonly used. is classified as a low boiling point solvent.

However, as mentioned above, trichlorotrifluoroethane has a particularly low boiling point of 47° C., so it can be used like other solvents that are normally classified as medium-boiling solvents.

Furthermore, even if the solvent has a boiling point similar to that of isopropyl alcohol, methyl ethyl ketone (boiling point 79.6°C)
Although its boiling point alone is clearly higher than trichlorotrifluoroethane, its flash point (-5.6°C) is low and cannot be used from the standpoint of ensuring non-flammability of the composition.

Thus, according to the present invention, all the drawbacks of water-based paints for aerosol injection have been eliminated, and despite being non-flammable, it is possible to form a highly water-resistant and beautiful paint film, and the aerosol is low in toxicity and inexpensive. Spray paint is provided.

Example 1 Properties: (Measurement method and conditions are the same as Example 1) Flash point Nil viscosity ■ 8 seconds The paint stock solution composition according to the present invention is placed in an aerosol container together with a propellant such as dichlorodifluoromethane, methyl ether, or LPG. It is packaged and sold commercially.

A suitable ratio for this inclusion is 30 to 70 volume % of the propellant to 70 to 30 volume % of the paint stock solution.

When dichlorodifluoromethane, a non-flammable propellant, is used as a propellant, the combustibility classification of the propellant according to the High Pressure Gas Control Law falls under the slightly flammable to mildly flammable category, and even when methyl ether, a flammable propellant, is used, A thermally classified and safe aerosol paint is provided.

[Brief explanation of the drawing]

The drawing shows trichlorotrifluoroethane (A), flammable solvent (B) (methyl isobutyl ketone, butyl acetate, butyl cellosolve), and a vehicle obtained by removing (A) and (B) from the entire paint stock solution composition corresponding to Example 1. (This is a diagram showing the measurement results of the flammability range depending on the blending ratio of a three-component system of q.

Claims (1)

[Claims] 1 A mixture of a water-insoluble resin paint vehicle, a medium or high boiling point flammable organic solvent excluding methyl ethyl ketone and including ethanol and isopropyl alcohol, and trichlorotrifluoroethane in an amount of 10 to 40% by weight of the total amount. Non-flammable paint concentrate composition for aerosol injection.