JPH0224870B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to surface coating compositions containing an oxidizable organic film-forming resinous vehicle and a dryer system. Metal salts of organic acids are useful for surface coating compositions containing drying oils and other oxidizable organic vehicles to accelerate the drying process and promote polymerization of unsaturated oils into mechanically resistant dry coatings. It has been used for a long time. Commonly used dryer systems include a primary or active dryer and a secondary or auxiliary dryer. Activated dryers speed up the surface drying of the film, but do not allow internal drying (throughdry).
It is a strong oxidizing agent with little or no effect on Auxiliary dryers do not promote drying by themselves, but when used in conjunction with active dryers they promote overall drying of the film and affect the hardness or flexibility of the dried film. Until recently, lead has been most widely used as an auxiliary dryer for surface coating compositions. Moreover, due to current government regulations that surface coating compositions that can be used as residential paints may contain no more than 0.06% lead, they may not be as effective as lead-containing ones. It has become necessary to develop dryer systems that do not contain or contain other highly toxic substances. Dryer systems developed as replacements for leaded systems include those that use zirconium and/or calcium as supplemental dryers. Such systems are described in U.S. Pat. No. 2,739,902 to Mack et al.
U.S. Pat. No. 3,901,837 to Gottesman et al.;
Burger, “Treatise on Coatings”, Volume 4,
“Formulations”, (Marcel Dekker, Inc., New
York, 1975), pp. 557-568. These alternative dryer systems generally provide good results for interior or exterior coating compositions under moderate atmospheric conditions. However, they contain oxidizable resinous binders, such as linseed oil, and under unfavorable atmospheric conditions, e.g.
Unsatisfactory as a replacement for leaded drying systems in household paints applicable at temperatures not higher than (10°C) and relative humidity higher than 50%. Such celestial conditions are found, for example, in autumn in the northern United States. Under these conditions, surface coating compositions containing cobalt and zirconium and/or calcium as dryers do not air dry within 24 hours. According to the present invention, a surface coating composition containing a dryer system in which the auxiliary dryer comprises bismuth is characterized in that the auxiliary dryer was found to be comparable to corresponding compositions containing lead conventional dryer systems. However, the surface coating composition of the present invention does not contain ingredients known to be highly toxic. Bismuth salts of organic acids and their use as dryers for surface coating compositions are known in the art. For example, bismuth salts of alkylated salicylic acids have been found to be particularly useful as dryers in marine coatings, which also serve as repellents for marine organisms.
Disclosed in Bruson, US Pat. No. 1,933,520. No. 2,251,798 to Meidert et al. discloses a number of polyvalent metal salts of branched-chain carboxylic acids obtained by alkaline oxidation of primary alcohols at high temperatures and pressures, and that these salts are useful as varnish and lacquer driers. It is reported that It has also been reported that bismuth salts are less suitable than cobalt, lead and zinc salts, for example because of their high cost. A method for preparing bismuth salts of various organic acids is described in U.S. Pat. No. 2,044,968 to Bruson, Considine.
No. 3,211,768 to Cukor et al. and US Pat. No. 3,962,298 to Cukor et al. The surface coating composition of the present invention comprises an oxidizable organic film-forming resinous vehicle and 0.02 to 0.1%, based on the solid weight of the vehicle, of cobalt, manganese, iron, cerium and other lanthanides, and mixtures thereof. active dryer metals such as, and 10-100% by weight of bismuth and calcium,
0.05-0.50%, based on the solid weight of the vehicle, of an auxiliary dryer metal containing 0-90% by weight of barium, zinc, zirconium, lead or a mixture of these metals, in proportions such that the total amount is 100% by weight. . If the auxiliary dryer metal is a mixture of bismuth and lead, the amount of lead in the surface coating composition should be at least 0.06% of the maximum of government regulations (i.e., 0.06 based on the solid weight of the surface coating composition).
%) must be lower. The surface coating composition preferably contains active dryer metal 0.04~
0.08% and one of the aforementioned auxiliary dryer metals 0.05
Contains ~0.20%. A particularly useful result is that the surface coating composition contains 0.04-0.08% cobalt and 0.05-0.15% cobalt based on the weight of the resinous vehicle solids.
% bismuth or 0.05~0.10% bismuth and
Obtained when containing a mixture of 0.02-0.10% calcium. Active and auxiliary dryer metals have 6 to 22 carbon atoms.
It is mixed into the dryer system as an oil-soluble metal salt of a branched or straight chain aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid having 6 to 10 carbon atoms, or a mixture of these acids. Examples of these acids are 2-ethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, 2-ethyl-4-methylpentanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, neononanoic acid. , isodecanoic acid, neodecanoic acid, 2-ethyldecanoic acid, isotridecanoic acid, isotetradecanoic acid, n-octanoic acid, n-
These include todecanoic acid, cyclopentanoic acid, methylcyclopentanoic acid, cyclohexanoic acid, methylcyclohexanoic acid, 1,2-dimethylcyclohexanoic acid, and cycloheptanoic acid. Acids suitable for use in the preparation of metal salts include branched aliphatic monocarboxylic acids having 8 to 18 carbon atoms, such as 2-ethylhexanoic acid,
isooctanoic acid, 2,2-diethylhexanoic acid,
2-Methyl-ethylheptanoic acid, 2,2-dimethyloctanoic acid, 2-propylheptanoic acid, 3,
5,5-trimethylhexanoic acid, 3-ethyloctanoic acid, isononanoic acid, isodecanoic acid, isododecanoic acid, 2-ethyldodecanoic acid, and tall oil fatty acids; naphthenic acids, such as cyclopentanoic acid, cyclohexanoic acid, cycloheptanoic acid, and methylcyclohexanoic acid; and mixtures of these acids. Particularly suitable acids include 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, and mixtures thereof. The surface coating composition of the present invention can be prepared by incorporating into the composition a suitable amount of a metal salt, a mixture of metal salts, or a solution containing one or more metal salts. They are prepared by incorporating into the surface coating composition a dryer system of metal salt solutions containing the required amount of active dryer metal and auxiliary dryer metal, preferably from 0.02 to 5% based on the weight of the vehicle. . These dryer solutions generally contain 1-16% by weight of active dryer metals, which are cobalt, manganese, iron, cerium and other lanthanides, and mixtures thereof.
and 6-36% by weight of auxiliary dryer metals containing 10-100% by weight of bismuth and 0-90% by weight of calcium, barium, zinc, zirconium, lead and mixtures thereof, in proportions such that the total amount is 100% by weight. . The dryer system preferably contains 5-7% cobalt or other active dryer metal and 50-100% bismuth and 0-50% calcium.
Auxiliary dryer metal containing 18-30% by weight. The dryer system is a solution of the metal salt in an inert, non-polar organic solvent, preferably a hydrocarbon or halogenated hydrocarbon. Suitable solvents are aliphatic and cycloaliphatic hydrocarbons such as hexane, heptane, octane, isooctane, cyclohexane and cycloheptane; petroleum distillates such as mineral spirits, gasoline, diesel fuel, and fuel oil; aromatics Group hydrocarbons such as benzene, toluene, xylene and ethylbenzene; and chlorinated compounds such as chlorobenzene, carbon tetrachloride and ethylene dichloride. A particularly suitable solvent for dryer systems is County of Los
Angeles Air Pollution Control District Rules
Mineral spirits as defined in Category 66 (K) that are photochemically non-reactive and have a distillation range of about 150-200°C. The dryer system may contain additives that reduce its viscosity. Such additives are described in U.S. Pat.
No. 2,456,824 and the polyoxyalkylene glycols described in US Pat. No. 2,807,553. Dryer systems can be used to accelerate the drying rate of a wide variety of surface coating systems, including paints, varnishes, enamels, printing inks, etc. that contain oxidizable organic film-forming resinous vehicles. The vehicle may be a drying or semi-drying oil, such as linseed oil in crude, brown or heat-bodied form, soybean oil, tung oil, or dehydrated castor oil. Others may be alkyd resins or oleoresinous varnishes. Surface coating compositions contain pigments, dyes, extenders, solvents, plasticizers, antiskinning agents, fungicides, and other additives in addition to oxidizable organic film-forming resinous vehicles and dryer systems. It may be contained in an amount commonly used in compositions. Examples of pigments used in surface coating compositions include:
Titanium dioxide, iron oxide, zinc oxide, antimony oxide, kaolin, china clay, calcium carbonate, silica, talc, zinc chromate, carbon black, and mixtures thereof. Useful solvents include benzene, toluene, xylene, naphtha, mineral spirits, hexane, isooctane and petroleum ether and water for water-based surface coating compositions. The following examples further illustrate the invention. Examples 1 and 2 Household paints were prepared by grinding the following raw materials in a pebble mill: Parts by weight Titanium dioxide (type) 6.90 Brown iron oxide (class) 6.90 Iron oxide (class) 0.40 Calcium carbonate 6.90 Silica and Silicates 3.90 Soybean alkyd resin 17.55 Q-type linseed oil 5.25 Neutral linseed oil 10.50 Bodied linseed oil 2.25 Ester rubber 4.74 Bactericide (FUNGITROL11) 0.51 Mineral spirits 34.20 The dryer system of the present invention and the comparative A dryer system was added. Dry times for household paints can be measured using an Improved Gardner Circular Dry Time Recorder on a 2 mil wet film.
Recorder) at 70〓 (21℃), relative humidity 50%
and 50〓 (10°C) and 60% relative humidity. The dryer system used and the results obtained are given in the table below.

[Table] From the data in the table, all dryer systems were found to be effective when the paint was air dried under moderate conditions (70°/50% relative humidity). When the paint was dried under severe conditions (50〓/60% relative humidity), the dryer system of the present invention (Examples 1 and 2)
was almost as effective as the leaded dryer system (Comparative Example A), while the cobalt/zirconium/
The paint containing the calcium dryer system (Comparative Example B) showed unsatisfactory performance in not air drying in 24 hours under the above-mentioned industrially required conditions.

Claims (1)

[Scope of Claims] 1. An oxidizable organic film-forming resinous vehicle and 0.02 to 0.1 based on the solid weight of the vehicle.
% of an active dryer metal selected from the group consisting of cobalt, manganese, iron, cerium and other lanthanides, and mixtures thereof, and 0.05-0.50% bismuth based on the solid weight of the vehicle.
10-100% by weight and calcium, barium, zinc,
comprising an auxiliary dryer metal containing 0 to 90% by weight of a metal selected from zirconium, lead and mixtures thereof in such a proportion that the total amount is 100% by weight, provided that lead is included as the auxiliary dryer metal; is in an amount of 0.06% or less based on the solid weight of the surface coating composition, and the active dryer metal and auxiliary dryer metal are in an amount of 6 to 22
aliphatic monocarboxylic acid having 6 carbon atoms
A surface coating composition characterized in that it is present as a salt of an acid selected from the group consisting of cycloaliphatic monocarboxylic acids having ~10 carbon atoms and mixtures thereof. 2.0.04 to 0.08% of the active dryer metal, expressed as a percentage based on the weight of the resinous vehicle solids.
and 0.05 to 0.20% of said auxiliary dryer metal. 3.0.04-0.08% cobalt and bismuth, expressed as percentages based on the weight of the resinous vehicle solids.
A surface coating composition according to claim 1 containing 0.05-0.15%. 4 Cobalt 0.04-0.08%, bismuth, expressed as percentages based on weight of resinous vehicle solids
A surface coating composition according to claim 1 containing 0.05-0.10% and 0.02-0.10% calcium.