Stabilization of high solids coatings with liquid compositions of triazine UV absorbers

Polymers are stabilized against degradation by the addition of a liquid composition comprising an organic solvent and at least 40% by weight of a triaryl triazine of the formula (I): ##STR1## wherein X, Y, and Z are each the same or different aromatic carbocyclic radicals, and at least one of X, Y, and Z is substituted by a hydroxy group ortho to the point of attachment to the triazine ring, and at least one of R1 to R9 is an alkoxy radical of the formula, --O-(mixed alkyl) substituted at a point para to the point of attachment to the triazine ring, and the remainder of R1 to R9 are selected from the group consisting of hydrogen, hydroxy, alkyl, alkoxy, sulfonic, carboxy, halo, haloalkyl, and acylamino; with the proviso that --O-(mixed alkyl) is an alkoxy radical formed from an mixture of isomeric C.sub.6 to C.sub.12 alkyl halides containing at least 10% each of at least three different isomers.

FIELD OF THE INVENTION 
This invention relates to stabilization of polymers with liquid 
compositions containing highly soluble triazine ultraviolet absorbers 
(UVA). 
BACKGROUND OF THE INVENTION 
The use of triazine-type UVAs by themselves or in combination with HALS to 
stabilize plastics and coatings against light-induced degradation is well 
known. 
U.S. Pat. Nos. 3,118,887 and 3,268,474 disclose the stabilization of 
plastic and resinous compositions against the effects of ultraviolet light 
by incorporating therein one or more triaryl triazines. It is further 
taught that at least one of the aryl groups is substituted by a hydroxyl 
group ortho to the point of attachment of the aryl group to the triazine 
nucleus. 
U.S. Pat. Nos. 4,619,956 and 4,740,542 disclose a method of stabilizing a 
polymer film, coating, or a molded article against the action of light, 
moisture, or oxygen. This method incorporates in a polymer a stabilizingly 
effective amount of a 2,2,6,6-tetraalkylpiperidine compound hindered amine 
light stabilizer (HALS) or salts or complexes thereof, together with a 
tris-aryl-s-triazine compound (UVA). Triazines taught to be particularly 
effective are those in which at least one aryl group was substituted with 
(i) a hydroxyl group ortho to the point of attachment of the aryl group to 
the triazine nucleus, and (ii) an alkoxy group --(OR) which is para to the 
point of attachment of the aryl group to the triazine nucleus. 
Despite good performance of UVAs or UVA/HALS combinations there are limits 
to the usefulness of these stabilizer ingredients due to physical 
properties such as UVA solubility. For example, 2,4,6-tris-s-triazines 
having octyl and hydroxyl substituents are relatively high melting solids 
with low solubilities in organic solvents such as xylene and butyl 
acetate. Consequently, the manner in which such triazines can be employed 
in the coatings industry is restricted to (i) direct addition of solid UVA 
to a polymer, or, (ii) addition as a relatively dilute (less than 30 
weight percent concentration) of UVA in an organic solvent. 
The direct addition of a solid stabilizer to a polymer is often not 
practical on an industrial scale. For example, caking may become a serious 
problem, the mixture may require additional heating and stirring to become 
homogeneous, dissolving the solid may require long periods of time, or 
dissolution may be incomplete. Moreover, problems of incompatibility 
between polymer and stabilizer can appear as "blooming" or exudation of 
stabilizer in the finished polymer product. All of these factors affect 
the overall quality of the stabilized polymer product. 
A second method of stabilizer addition to polymers is to add the stabilizer 
as a solution. Typically, the stabilizer is added as a solute dissolved in 
a suitable organic solvent. The disadvantage of this method in the case of 
low solubility triazine UVAs is that it permits addition of only 
relatively small amounts of stabilizer, together with excess solvent. 
Excessive solvent volumes become a problem in coatings and plastics 
manufacturing and result in a buildup of unwanted volatile organic 
components ("VOC") in the polymer product. 
Stabilizer systems disclosed in prior art have attempted to address some of 
the unsatisfactory aspects mentioned above, however, the prior art 
approaches to these problems have not been entirely satisfactory. For 
example, U.S. Pat. Nos. 3,658,910 and 3,729,442 disclose an improved 
benzophenone-type ultraviolet absorber, 4-alkoxy-2-hydroxybenzophenone. 
Improvement is obtained by modifying the alkyl group from normal octyl, 
which gives a solid benzophenone-type stabilizer as disclosed in U.S. Pat. 
No. 2,861,105 and German offenlegungschrift 1,806,870, to an isomeric 
mixture of octyl referred to as "Oxo" octyl which gives a liquid 
benzophenone-type stabilizer as disclosed in U.S. Pat. Nos. 3,658,910 and 
3,729,442. Although the liquid form benzophenone has superior performance 
when compared to its solid form, the entire class of benzophenone-type 
stabilizers are inferior in performance to other classes of UV-absorbers 
such as triazines. Benzophenone-type stabilizers further suffer from high 
volatility which makes them unsuited for high temperature bake coatings 
applications, in particular, automotive coatings applications. 
The UVA deficiencies of the benzophenone-type absorbers in areas such as 
volatility and performance, and the deficiency of the triazine-type 
absorbers in the area of solubility could be overcome if an improved 
triazine-type ultraviolet absorber of higher solubility is found. In 
particular, it would be a welcome contribution to the art of polymer 
stabilization if triaryl triazines UVAs of high solubility in common 
solvents were made available. 
SUMMARY OF THE INVENTION 
This invention is a method of making highly organic solvent soluble triaryl 
triazine UVAs useful for the stabilization of plastics. These highly 
soluble triaryl triazine UVAs are prepared by alkylating polyhydroxy 
triaryl triazines with an isomeric mixture of an alkyl halide. 
This invention is also a highly organic solvent soluble triaryl triazine 
produced by the novel process of the invention. 
This invention is also a polymer stabilizing composition comprising the 
novel triaryl triazines dissolved at high concentration in an organic 
solvent. 
This invention is also a method of stabilizing polymers by incorporating 
into said polymers the highly organic solvent soluble triaryl triazine UVA 
of this invention. 
This invention is also a stabilized film, or coating, or article formed by 
coating a substrate with stabilized polymers produced by the stabilizing 
method of this invention.

DETAILED DESCRIPTION OF THE INVENTION 
The novel triaryl triazine compounds of this invention are represented by 
the formula (I) below: 
##STR2## 
wherein X, Y, and Z are each the same or different aromatic carbocyclic 
radicals, and at least one of X, Y, and Z is substituted by a hydroxy 
group ortho to the point of attachment to the triazine ring, and at least 
one of R1 to R9 is an alkoxy radical of the formula, --O-(mixed alkyl) 
substituted at a point para to the point of attachment to the triazine 
ring, and the remainder of R1 to R9 are selected from the group consisting 
of hydrogen, hydroxy, alkyl, alkoxy, sulfonic, carboxy, halo, haloalkyl, 
and acylamino. 
The symbol, "--O-(mixed alkyl)" as used herein is an alkoxy radical formed 
from a mixture of isomeric C6 to C12 alkyl halides containing at least 10 
weight percent of at least three different isomers. Preferably, the 
"--O-(mixed alkyl)" group is predominantly a mixture of alkyl isomers 
having the same number of carbon atoms. For example, the --O-(mixed alkyl) 
group may be a mixture of eight carbon atom alkyl isomers wherein at least 
three different octyl isomers are present. 
Preferred triaryl triazine compounds of this invention are represented by 
the formula (I), wherein X, Y, and Z are each phenyl radicals and only one 
of X, Y, or Z is substituted by a hydroxyl group in the ortho position, an 
alkoxy group of the formula --O-(mixed alkyl) is substituted on the same 
phenyl radical as the hydroxyl group at a point para to the point of 
attachment of the phenyl radical to the triazine ring, and the remainder 
of R1 to R9 are selected from the group consisting of hydrogen, one to 
twelve carbon atom alkyl, and --O-(mixed alkyl) groups. 
An illustrative triaryl triazine is 
2,4-di-(2,4-di-methylphenyl)-6-(2-hydroxy-4-O-(mixed 
alkyl))phenyl)-1,3,5-triazine. 
I. A PROCESS FOR PREING NOVEL TRIARYL TRIAZINES 
General methods for preparing triaryl triazines have been disclosed in U.S. 
Pat. Nos. 3,118,887 and 3,268,474, the disclosures of which are 
incorporated herein by reference. However, the prior art does not teach 
alkylation products of hydroxyaryl triazines with mixed isomer alkyl 
halides to produce the novel highly soluble triaryl triazines of this 
invention. 
The process for preparing the novel highly soluble triazines is by 
alkylating with mixed isomeric alkyl halides a polyhydroxy triaryl 
triazine represented by the formula (II) below: 
##STR3## 
wherein X, Y, and Z are each the same or different aromatic carbocyclic 
radicals, and at least one of X, Y, and Z has two hydroxy groups having 
positions, respectively, ortho and para to the point of attachment to the 
triazine ring, and the remainder of R10 to R18 are selected from hydrogen, 
hydroxy, alkyl, alkoxy, sulfonic, carboxy, halo, haloalkyl, and acylamino. 
Preferred triaryl triazine reactants suitable for alkylation with mixed 
isomeric alkyl halides are represented by the formula (III) below: 
##STR4## 
wherein R19, R20, R21, R22, R23, R24, and R25 are selected from the group 
consisting of hydrogen and one to twelve carbon atom alkyl groups. 
A preferred process of the invention is to monoalkylate the triazine of 
formula (III) with an isomeric mixed alkyl halide. It is particularly 
preferred to use an isomeric mixture of eight carbon alkyl halides as the 
alkylating agent. 
The triaryl triazine UVAs of the invention may also be substituted by 
ortho-hydroxy groups on 2 or 3 of the aromatic carbocyclic rings attached 
to the triazine nucleus. However, these poly-ortho-hydroxy type triazines, 
although effective as ultraviolet absorbers, are generally more highly 
colored than mono-ortho-hydroxy type triazines. Consequently, the 
mono-ortho-hydroxy triazines prepared from triaryl triazines of formula 
(III) are generally preferred for stabilization of coatings. 
An illustration of a specific triaryl triazine reactant useful for 
practicing the method of this invention is 
2-(2,4-dihydroxyphenyl)4,6-bis-(2,4-dimethylphenyl)-1,3-5-triazine. 
The mixed isomeric alkyl halides suitable for practicing the method of the 
invention are generally chlorides, bromides, or iodides, with chlorides 
being preferred because of cost and availability. 
The alkyl radicals of the mixed isomeric alkyl halide reactant may contain 
a wide variety of isomers having a range of from six to twelve carbon 
atoms. It is a preferred practice of this invention that the alkyl 
radicals of the alkyl halide be predominantly (over 90 weight percent) a 
mixture of isomers of one given carbon atom chain length, for example, a 
mixture of eight carbon atom isomers. It is also within the preferred 
practice of this invention to combine isomer mixtures, that is, to use an 
alkyl halide ingredient wherein, for example, one-third of the alkyl 
groups are derived from six carbon atom mixed isomers, one-third of the 
alkyl groups are derived from eight carbon atom mixed isomers, and 
one-third of the alkyl groups are derived from ten carbon atom mixed 
isomers. 
The alkyl halide reactant predominantly reacts with the hydroxyl group in 
the para positions in formulae (II) and (III). The para hydroxyl group is 
more reactive than the ortho position hydroxyl and its predominant 
reaction is accomplished by using no more than about a 10% stoichiometric 
excess of mixed isomer alkyl halide reactant per mole of para hydroxyl 
group on the triazine reactant. Other reaction conditions which favor 
predominant reaction of the para hydroxyl group are (i) use of a catalyst, 
and (ii) use of reaction temperatures below 200.degree. C. 
A particularly preferred source of mixed isomer C.sub.6 to C.sub.12 alkyl 
groups for the mixed isomer alkyl chloride reactant are "Oxo" process 
alcohols. The "Oxo" process and products are well known and are described 
in detail in the Kirk-Othmer "Encyclopedia of Chemical Technology", 2nd 
Edition, Volume 14, page 373 to page 390. 
The products derived from the `Oxo Process` are further described in U.S. 
Pat. No. 3,658,910 (column 1, line 54 to column 2, line 27) as follows: 
R is a mixture of random branched alkyl groups having 6 to 10 carbon atoms 
and are of the `Oxo` type . . . A typical commercially available 
isooctanol has the analysis 3,4-dimethyl-1-hexanol 20%, 
3,5-dimethyl-1-hexanol 30%, 4,5-dimethyl-1-hexanol 30%, 
3-methyl-1-heptanol and 5-methyl-1-heptanol together 15% and unidentified 
alcohol 5%. A typical commercially available isodecanol is a mixture of a 
plurality of primary saturated alcohols having ten carbon atoms. There is 
a major proportion of a mixture of trimethyl heptanols and small amounts 
of other isomeric primary saturated decanols. . . . In general such 
mixtures contain at least 10% of at least three different branched chain 
isomers. 
Solubility Properties of the Tris-Aryl Triazines: 
It is the discovery of this invention that the triaryl triazines of Formula 
(I) although solids have unexpectedly superior solubility properties not 
found or suggested in the prior art. For example, U.S. Pat. Nos. 3,729,442 
and 3,658,910 teach that when the normal octyl group in benzophenone-type 
UV absorbers is replaced with an isomeric mixture of C.sub.6 to C.sub.12 
alkyl group, the solid benzophenone derivative is converted to a liquid 
derivative. It is a discovery of this invention that when a 
non-benzophenone-type UVA, specifically a triaryl triazine, is reacted 
with an isomeric mixed alkyl halide derived from an isomeric alcohol that 
a solid results, and that this solid unexpectedly has significantly 
improved solubility in compositions useful for polymer stabilization. 
The increased solubility of the triazines of this invention gives rise to 
two important advantages not present in the methods of stabilization in 
prior art, namely; 
a. Low Volatile Organic Components (VOC), which is the direct result of the 
increased solubility of the triazines of this invention, and 
b. Increased compatibility with coatings and plastics to which the 
triazines of this invention are added. 
Without being bound by any theory of operation it is believed that the 
triaryl triazines produced by alkylating the triaryl triazines of formulae 
(II) and (III) gives an isomeric mixture having unexpectedly enhanced 
solubility properties. This enhanced solubility is conceivably related to 
enhanced compatibility of the triaryl triazines of this invention in 
polymer systems, and includes such possible advantages as resistance to 
"blooming", stabilizer exudation, and etc. 
II. A POLYMER STABILIZING COMPOSITION 
The triaryl triazine UV absorbers of this invention are characterized as 
being highly soluble in organic solvents. For the purpose of this 
invention high organic solvent solubility is defined as the triaryl 
triazines of formula (I) having a solubility of at least 40 weight percent 
in xylene at 25 degrees C. (based on the total weight of solution). The 
triazines of the invention are typically dissolved in a solvent with 
agitation with or without the aid of heat. It is preferred to prepare 
solutions of novel triazines having a concentration of from 40 weight 
percent up to the solubility limit of the triazines. Typically, triazine 
concentrations of from 50 to 80 weight percent are preferred for 
commercial applications. 
The polymer stabilizing composition comprises as its essential component 
ingredients the following: 
A. an organic solvent, 
B. a triaryl triazine compound represented by formula (I), supra. 
Preferably the --O-(mixed alkyl) group(s) in the triaryl triazine is 
derived from a mixture of isomers containing at least 10% of at least 
three different branched C.sub.6 to C.sub.12 alkyl isomers as previously 
stated in the definition of Formula (I). It is particularly desired that 
the alkyl isomer mixture be derived from the "Oxo" process alcohols. 
The Liquid Organic Solvent Component: 
The solvent ingredient of the composition is not critical and may be 
selected from a wide variety of liquid organic solvents known to have 
utility and compatibility in polymer formulations. Suitable solvents are 
liquid at ambient temperatures and are non-reactive with polymers, 
triazine-type ultraviolet light absorbers, and other optional components. 
Illustrative classes of solvents are alkanes, halogenated alkanes, 
aromatic hydrocarbons, halogenated aromatic hydrocarbons, alcohols, 
aldehydes, esters, ethers, and ketones. Examples of specific compounds 
useful as solvents in the process of the invention are xylene and butyl 
acetate. The utility of any proposed solvent may be easily determined by 
testing the solubility of the triaryl triazine of the invention at ambient 
temperatures. 
It is also possible to use as the solvent ingredient of the composition a 
solvent used as reaction media for the preparation of the mixed isomer 
triaryl triazines of this invention. Alternatively, it is useful to employ 
solvents in the purification step of the triazine synthesis as the 
selected organic solvent ingredient of the stabilizing composition of the 
invention. 
Optional Stabilizer Composition Ingredients: 
The stabilizing composition may contain other ingredients in addition to 
the solvent and triaryl triazine of the invention. For example, the 
stabilizing composition may contain a minor proportion of byproducts from 
the alkylation process used to prepare the triazine, if such byproducts 
are not detrimental to the polymer being stabilized. 
The polymer stabilizing composition of the invention may contain, if 
desired, only triaryl triazines of formula (I), together with a solvent. 
Alternatively, the stabilizing composition may contain a variety of other 
ingredients known to be useful in polymer formulations. Such optional 
ingredients include other UVA stabilizers, antioxidants, and/or hindered 
amine light stabilizers (HALS). It may be desirable to use the UVAs of 
this invention in combination with HALS, much in the same manner as low 
organic solvent soluble triaryl triazines have been used in combination 
with HALS in the prior art (see, for example, U.S. Pat. No. 4,619,956). 
A preferred class of optional HALS ingredients having utility in preparing 
the plastic stabilizing compositions of this invention are broadly 
described as 2,2,6,6-tetraalkylpiperidine hindered amine type light 
stabilizer including their N-oxides, N-hydroxides, and N-alkoxides, or 
their acid addition salts or complexes with metal compounds thereof. Such 
2,2,6,6-tetraalkylpiperidine hindered amine type light stabilizers are 
described in U.S. Pat. Nos. 4,356,307 4,778,837, 4,740,542, and 4,619,956 
the disclosures of which are incorporated herein by reference. 
Also suitable as HALS for use in the composition and method of the 
invention are polymeric compounds of which the recurring structural unit 
contains polyalkylpiperidine radicals, especially polyester, polyethers, 
polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, and 
copolymers thereof which contain such radicals. 
Useful polyalkylpiperidine derivatives also include basic compounds that 
can form salts with acids. Examples of suitable acids for such salt 
formation include but are not limited to inorganic and organic acids such 
as, carboxylic, sulfonic, phosphonic, phosphinic, hydrochloric, boric, 
phosphoric, acetic, salicylic, toluenesulfonic, and benzenephosphonic. 
III. A METHOD OF STABILIZING POLYMERS 
This invention includes an improved method of stabilizing a polymer against 
the action of light, moisture, and oxygen by incorporating into the 
polymer a stabilizingly effective amount of the mixed isomer triaryl 
triazines previously represented by formula (I). 
The mixed isomer triaryl triazines are most conveniently incorporated into 
the polymer by mixing into a polymer containing liquid the concentrated 
liquid stabilizer composition of the invention comprising an organic 
solvent having dissolved therein the mixed isomer triaryl triazines of the 
invention. Liquid additives are particularly convenient for processing 
since they are easily measured, transported, and uniformly dispersed into 
the polymer to be stabilized. Alternatively, the triaryl triazines of 
formula (I) may be added to unstabilized polymer as a solid, but this 
method of addition is not the preferred practice of this invention because 
of the difficulty of uniform addition. 
Many types of polymers may be stabilized by the method of the invention. 
Such polymers include acrylics, alkyds, polyesters, polyurethanes, 
polysiloxanes, polyolefins, polycarbonates, polyamides, polyvinyl halides, 
styrenics, and epoxies. 
The stabilization method is typically practiced by incorporating the 
triaryl triazine ingredient into the polymer in amounts of from about 0.01 
to about 5 wt % based on the weight of total polymer in the composition. 
In those instances where a HALS is additionally used said HALS is also 
incorporated into the polymer in amounts of from about 0.01 to about 5 wt 
% based on the weight of total polymer in the composition. 
In addition to the incorporation of the triaryl triazines into the polymers 
either alone or optionally with HALS, other known stabilizers and 
co-stabilizers can also be used. These stabilizers can be, for example: 
1. Antioxidants which are alkylated phenols, alkylated hydroquinones, 
hydroxylated thiophenyl ethers, alkylidene-bisphenols, acylaminophenols, 
esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with 
monohydric or polyhydric alcohols, and amides of 
beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid; 
2. Other ultraviolet light stabilizers; 
3. Metal deactivators; 
4. Phosphites and phosphines; 
5. Compounds which decompose peroxides; 
6. Nucleating agents; 
7. Fillers; and 
8. Other additives, for example, plasticizers, lubricants, emulsifiers, 
pigments, fluorescent whitening agents, flameproofing agents, antistatic 
agents and blowing agents. 
The polymers which can be stabilized according to the method of this 
invention include those which form films and coatings, and those from 
which molded articles are produced. Preferably acid catalyzed thermoset 
acrylic or alkyd coatings are stabilized, most preferably high solids 
thermoset acrylic coatings are stabilized by the method of this invention. 
IV. COATED ARTICLE AND METHOD OF MAKING 
This invention is an improved method of making a coated article by applying 
to a substrate a polymer stabilized with the novel triaryl triazines of 
this invention. 
The stabilized polymer may be in the form of a solution, dispersion, 
emulsion, invert emulsion, or hot melt and is applied by any conventional 
process such as padding, dipping, brushing, and spraying. 
The substrate receiving the stabilized polymer to form a coated article may 
be metallic or non-metallic, for example, aluminum, steel, glass, or 
plastic. 
After applying the polymer to the substrate the coating may be cured (if 
crosslinkable), usually by application of heat to form a coated article. 
The use of saturated or nearly saturated solutions of concentrated 
stabilizing composition (comprising solvent and novel triazine) is 
preferred since less solvent (and consequently lower level of volatile 
organic components) will be introduced into a polymer, coating or film to 
be stabilized. 
The following examples are provided for the purpose of illustration only 
and should not be construed as limiting the invention in any way as 
variations of the invention are possible which do not depart from the 
scope of the appended claims. 
EXAMPLE 1 
A mixture of 
2,4-di-(2,4-dimethylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5-triazine (40 g), 
mixed isomeric octyl chlorides, analysis 95% C.sub.8, (16 g), potassium 
iodide (0.7 g), PEG 400.RTM. (polyethylene glycol, molecular weight 
380-420, available from Aldrich Chemicals, Milwaukee, Wis.) (4 g), sodium 
hydroxide (4 g) dissolved in methyl isobutyl ketone was heated under 
reflux (122.degree. C.) for 16 hours. After cooling to 80.degree. C., the 
reaction mixture was acidified with dilute hydrochloric acid, and the 
resulting aqueous layer was removed. The organic layer was washed twice 
with warm water (75 ml for each washing) and the volatiles were removed in 
vacuo under reduced pressure. The residue (45 g) was dissolved in xylene 
(10 g) and decolorized with activated charcoal and filtered to give 
2,4-di-(2,4-di-methylphenyl)-6-(2-hydroxy-4-O-(mixed 
alkyl)phenyl)-1,3,5-triazine; (where "mixed alkyl" was an isomeric mixture 
of C.sub.8 alkyl groups) as an amber solution (50 g). 
This example illustrates the preparation of a concentrated solution, in 
xylene, of an isomeric C.sub.8 mixture alkyl groups in 
2,4-di-(2,4-dimethylphenyl)-6-(2-hydroxy-4-O-(mixed 
alkyl)phenyl)-1,3,5-triazine. The reaction product is an ultraviolet light 
stabilizer product of this invention prepared according to the alkylation 
process of this invention. 
EXAMPLE 2 
The product of Example 1 was heated to 90.degree. C. under vacuum at 50 mm 
of mercury until all volatiles were removed. The residue was the triazine 
of formula (I) with an isomeric mixture of C.sub.8 alkyl groups containing 
2,4-di-(2,4-dimethylphenyl)-6-(2-hydroxy-4-O-(mixed 
alkoxy)phenyl)-1,3,5-triazine as a viscous oil which solidified within one 
month standing at room temperature. 
This example illustrates the preparation of 
2,4-di-(2,4-dimethylphenyl)-6-(2-hydroxy-4-O-(mixed alkyl) 
phenyl)-1,3,5-triazine (where "mixed alkyl" is an isomeric mixture of 
C.sub.8 alkyl groups) as a solid product. 
EXAMPLE 3 
The solubility of the M8T and the prior art N8T in both xylene and butyl 
acetate solvents for temperatures in the range from -20.degree. C. to 
30.degree. C. was determined using a method where a suspension of known 
concentration was adjusted until the solute just dissolved. The sample 
temperatures were measured to .+-.0.1.degree. C. and regulated to 
.+-.0.1.degree. C. in a constant temperature bath. The results of the 
solubility tests are shown in the following Tables 1A and 1B and in FIGS. 
1 and 2. 
TABLE 1A 
______________________________________ 
M8T N8T 
Xylene Xylene 
Temp. .degree.C. 
wt. % Temp. .degree.C. 
wt. % 
______________________________________ 
-9.5 14.4 7.6 6.9 
-4.6 19.7 12.0 9.7 
8.5 37.4 16.4 12.3 
24.1 62.6 25.9 18.2 
24.8 63.2 27.3 19.7 
______________________________________ 
TABLE 1B 
______________________________________ 
M8T N8T 
Butyl Acetate Butyl Acetate 
Temp. .degree.C. 
wt. % Temp. .degree.C. 
wt. % 
______________________________________ 
8.2 27.8 10.9 1.1 
14.4 39.5 18.8 1.9 
20.1 49.8 25.5 2.9 
25.0 58.5 26.1 3.1 
25.5 59.2 37.4 6.5 
______________________________________ 
An additional experiment was performed to compare the M8T and N8T 
stabilizer solubilities at approximately the same temperature (25.degree. 
C.). In addition, the calculated theoretical solubility of each compound 
at 25.degree. C. was determined based on the solubility curve data 
described in this Example and displayed in FIGS. 1 and 2. The results of 
these determinations are shown in Table 1C below: 
TABLE 1C 
______________________________________ 
Solubility 
Solubility 
Experiment Conc. Conc. 25.degree. C. 
Solute Solvent Temp. .degree.C. 
(actual) 
(Calculated) 
______________________________________ 
M8T Xylene 24.8 63.2 63.5 
M8T BA 25.0 58.5 58.3 
N8T Xylene 25.4 17.8 17.9 
N8T BA 25.5 2.94 2.92 
______________________________________ 
BA is butyl acetate 
This example illustrates the much higher solubility, in organic coatings 
solvents, of triaryl triazines which are a product of the invention 
containing an isomeric mixture of C.sub.8 -O-(mixed alkyl) groups compared 
to a similar triaryl triazine prepared with normal octyl halide 
(non-isomeric) which is a product outside the scope of this invention. 
EXAMPLE 4 
1. Test Procedure 
The effectiveness of the light stabilizer systems of the following Examples 
was determined by measuring the gloss retention (ASTM Test Procedure D523) 
and yellowness index (ASTM Test Procedure D1925) of a coating after 
exposure in an accelerated weathering unit such as the QUV (ASTM Test 
Procedure G53). 
2. Basic Clear Coating Formulations 13.0 parts ACRYLOID.RTM. AT-400 brand 
of thermosetting acrylic resin (a trademark of Rohm & Haas Co.) (75% 
solids); 5.25 parts CYMEL.RTM. 303 brand of melamine resin (a trademark of 
American Cyanamid Co.); 0.15 parts CYCAT.RTM. 4040 brand of 
toluenesulfonic acid catalyst (a trademark of American Cyanamid Co.) (40% 
in isopropanol); 3.3 parts xylene; and 3.3 parts butanol. 
3. Coatings Formulations with Stabilizer. 
Three acrylic coating formulations were prepared by adding a hindered amine 
light stabilizer (HALS) and an ultraviolet absorber (UVA) as follows: 
Formulation A 
Formulation A was prepared by adding solid 
2,4-di-(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octoxy-phenyl)-1,3,5-triazine 
(n-octyl triazine) at 2 wt % level based on total resin solids, and by 
adding the hindered amine light stabilizer of formula (IV); 
##STR5## 
at 1 wt % level based on total resin solids, to the basic clear coating 
formulation of Example 4, part 2. 
Formulation B 
Formulation B was prepared by adding the solid product of Example 2 at 2 wt 
% level based on total resin solids and by adding the hindered amine light 
stabilizer of formula (IV) at a 1 wt % level based on total resin solids, 
to the basic clear coating formulation of Example 4, part 2. 
Formulation C 
Formulation C was prepared by adding SANDUVOR.RTM. 3206 ultraviolet 
absorber (represented by formula V), 
##STR6## 
a product of Sandoz Chemicals Corporation, Charlotte, N.C., at 2 wt % 
level based on total resin solids, and by adding TINUVIN.RTM., 440 
hindered amine light stabilizer (represented by formula VI), 
##STR7## 
a product of Ciba-Geigy Corporation, Hawthorne, N.Y., at 1 wt % level 
based on total resin solids, to the basic clear coating formulation of 
Example 4, part 2. 
4. Measurement of Stabilizing Effectiveness 
BONDERITE.RTM. 40 brand of cold rolled steel test panels, coated with a 
primer and a white base coat based on a thermosetting acrylic resin were 
coated with the clear resin formulation described above (containing the 
stabilizer to be evaluated) and cured for 30 min. at 120.degree. C. Clear 
coating thickness was about 2 mils (0.0508 mm). The coated test panels 
were subjected to weathering in a QUV tester. In this test, the samples 
were subjected to alternate cycles of UV light at 70.degree. C. for 8 
hours and a humid atmosphere with no UV light at 50.degree. C. for 4 
hours. Subsequently, the gloss was measured. The gloss retention of the 
cured coatings A, B and C, obtained by curing the formulations A, B and C 
of Example 4, part 3, are summarized in Table 2. 
TABLE 2 
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Gloss Retention of Cured Thermosetting Acrylic Coatings 
Stabilized with Stabilizer Combinations 
% Gloss (20.degree.) After Exposure (QUV) 
2400 3200 4000 
Hours Hours Hours 
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Coating A 98 97 94 
2% n-octyl triazine 
1% HALS 
Coating B 99 99 93 
2% Example 1 product 
1% HALS 
Coating C 92 57 33 
2% SANDUVOR 3206 
1% TINUVIN 440 
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It is concluded from the results in Table 2 that the combination of an 
ultraviolet absorber (UVA) of this invention (viz., the product of Example 
1) with a hindered amine light stabilizer (HALS) gives an effective 
stabilizer system that compares favorably with commercial stabilizer 
systems such as the combination of SANDUVOR.RTM., 3206 and TINUVIN.RTM. 
440. Moreover, the highly organic solvent soluble triazines of this 
invention compare favorably with systems using a HALS together with normal 
octyl triazine ultraviolet absorber. 
Although the present invention has been described with reference to certain 
preferred embodiments, it is apparent that modifications and changes may 
be made therein by those skilled in the art without departing from the 
scope of this invention as defined in by the appended claims.