The present invention provides a novel, non-formaldehyde thermoset fluorescent pigment which is useful to color plastics, particularly flexible vinyl, which is solvent resistant, particularly to acetone. Moreover, the pigment does not bleed in plastics. The pigment comprises a polymer matrix and a fluorescent dye. The polymer matrix has a molecular weight of greater than about 330, preferably greater than about 1000. Embodiments which lack the water insoluble resin, have a molecular weight greater than about 330, preferably greater than about 500. The polymer matrix contains: from about 15 to 50 mole percent, preferably 30 to 40 mole percent, of a carboxylate functional oligomer; 30 to 80 mole percent, preferably 50 to 60 mole percent, of a metal ion; and 0 to 40 mole percent, preferably about 1 to 40 mole percent, more preferably from 1 to 30 mole percent, most preferably from about 3 to 10 mole percent of a water insoluble resin. In embodiments where no water insoluble resin is used, the metal is present from at least 51 mole percent. The oligomer comprises from about 10 to about 60 mole percent, preferably 20 to 35 mole percent of a first monomer, 40 to 90 mole percent, preferably 65 to 80 mole percent of second monomer. The weight average molecular weight of the oligomer is 330 to 2000, preferably about 560 to 600. The invention also relates to a novel method for producing the fluorescent pigments.

BACKGROUND OF THE INVENTION 
Several different types of fluorescent pigments are currently used for 
coloring flexible vinyl. One type is a thermoplastic pigment in which the 
pigment itself melts then dissolves and releases dye into the vinyl. 
Unfortunately, plastics colored with such soluble fluorescent pigment 
exhibit severe color migration and such, and often stick to equipment 
during processing. 
Thermoset fluorescent pigments for coloring flexible vinyl include a 
toluene-sulfonamide-melamine pigment and a benzogaunamine pigment. The TSA 
melamine pigments, while they do not melt, migrate color when processed in 
vinyl. The benzoguanamine pigments are typically made in dispersion. 
Dispersion technique makes it difficult to efficiently produce pigment in 
bulk; yields are typically about 30% solids. Furthermore the pigment needs 
to be filtered, dried, and pulverized. The multiple steps are time 
consuming and costly. In addition, benzoguanamine is a relatively 
expensive raw material. 
Furthermore, both the toluene/sulfonamide/melamine and a benzogaunamine 
pigment contain formaldehyde, which is not environmentally friendly and is 
released when the plastic is heated. 
Other conventional fluorescent pigments are not suitable substitutes for 
the benzoguanamine/formaldehyde based pigments because of the tendency of 
such pigments to melt into the plastic and consequently bleed dye. Also 
when conventional pigments are exposed to solvents such as acetone the 
pigments tend to dissolve and to bleed dye into the plastic. 
It is desirable to have a fluorescent pigment which does not bleed dye in 
flexible vinyl, does not contain formaldehyde, and resists solvents, 
particularly acetone. In addition, it would be desirable to be able to 
prepare such a pigment in a bulk process with yields above 30%. 
SUMMARY OF THE INVENTION 
The present invention provides a novel, non-formaldehyde thermoset 
fluorescent pigment which is useful to color plastics, particularly 
flexible vinyl, which is solvent resistant, particularly to acetone. 
Moreover, the pigment does not bleed in plastics. The pigment comprises 
from about 85 to 99.95 weight percent of a polymer matrix and a 
fluorescent dye. The polymer matrix has a molecular weight of greater than 
about 330, preferably greater than about 1000. Embodiments which lack the 
water insoluble resin, have a molecular weight greater than about 330, 
preferably greater than about 500. The polymer matrix contains: from about 
15 to 50 mole percent, preferably 30 to 40 mole percent, of a carboxylate 
functional oligomer, also referred to herein as the "oligomer,"; 30 to 80 
mole percent, preferably 50 to 60 mole percent, of a metal ion; and 0 to 
40 mole percent, preferably about 1 to 40 mole percent, more preferably 
from 1 to 30 mole percent, most preferably from about 3 to 10 mole percent 
of a water insoluble resin. In embodiments where no water insoluble resin 
is used, the metal is present from at least 51 mole percent. 
The oligomer comprises from about 10 to about 60 mole percent, preferably 
20 to 35 mole percent of a first monomer, 40 to 90 mole percent, 
preferably 65 to 80 mole percent of second monomer. The weight average 
molecular weight of the oligomer is 330 to 2000, preferably about 560 to 
600. 
The invention also relates to a novel method for producing the fluorescent 
pigments which method is referred to herein as the "bulk two-step method." 
DETAILED DESCRIPTION OF THE INVENTION 
The present invention provides a non-formaldehyde fluorescent pigment which 
is useful to color plastics, particularly flexible plastics, along with 
organic solvent based systems such as, for example, inks. The fluorescent 
pigments are less preferred in water based systems. The fluorescent 
pigment is solvent resistant, that is the pigment will not dissolve or 
swell and the dye will not significantly bleed in a variety of solvents, 
including esters such as ethyl acetate, isopropyl acetate, also ketones 
such as acetone, methyl ethyl ketone, and highly polar solvents such as 
dimethylformamide. Thus the pigment is useful in a variety of coatings and 
paints, particularly those containing such solvents. Moreover, the pigment 
does not bleed in plastics, particularly flexible plastics, that is, 
plastics containing plasticizer. 
The preferred embodiments the pigment possess increased water resistance 
due to the presence of the optional water insoluble resin. The fluorescent 
pigment is particularly useful in flexible plastics, organic solvent 
systems and inks, especially vinyl ink. 
The fluorescent pigment is stable in products such as inks, there is no 
gain in viscosity and no color shift, that is, the color remains the same. 
Indeed, the fluorescent pigment has good color stability even at elevated 
temperatures, for example even above 260.degree. C. The fluorescent 
pigment when used in plastic demonstrates little or no plate out and, 
since the fluorescent pigment lacks formaldehyde, there is no formaldehyde 
out-gassing. Thus, the fluorescent pigment is useful in plastics such as, 
for example high density polyethylene, low density polyethylene, and 
styrene. The fluorescent pigment has a degradation point of less than 
250.degree. C. 
The invention also relates to a novel method for producing the fluorescent 
pigments which method is referred to herein as the "bulk two-step method." 
About two to three times the solids percent, that is up to about to 60 to 
80 solids percent, is achievable with the novel bulk two step method as 
compared to conventional dispersion techniques. Moreover, a filtration 
step, which is necessary with conventional dispersion methods, is not 
needed with the bulk two step method. 
The Polymer Matrix 
The polymer matrix has the general formula: 
EQU R--(COOH).sub.a (COO.sup.-).sub.b M.sub.m X.sub.o 
where: 
R has from 18 to 100 carbon atoms, preferably 25 to 50 carbon atoms; and 
contains ester linkages or amide linkages, or both; 
a is a number from 0 to 6, preferably from 0 to 2; 
b is a number from 2 to 8, preferably from 2 to 4, wherein a+b is a number 
from 2 to 8; 
m is a number from 0.5 to 6, preferably from 1 to 2; 
o is a number from 0 to 3, preferably 0.5 to 1; 
M is the metal; 
X is the water insoluble resin. 
The group R--(COOH).sub.a (COO.sup.-).sub.b is the oligomer which has a 
weight average molecular weight of from about 330 to 2000, preferably from 
about 330 to 1000, more preferably about 600; and a carboxylic acid 
equivalent weight of from about 80 to 1000, preferably from about 120 to 
400. The polymer matrix embodiment which contains the water insoluble 
resin has a molecular weight of greater than about 330, preferably greater 
than about 1000. Polymer matrix embodiments which lack the water insoluble 
resin, have a molecular weight greater than about 330, preferably greater 
than about 500. 
The polymer matrix contains from about 15 to 50 mole percent, preferably 
from about 30 to 40 mole percent, of the oligomer, from about 50 to 80 
mole percent, preferably 50 to 60 mole percent, of a metal, and from about 
0 to 40 mole percent, preferably about 1 to 40 mole percent, more 
preferably from 1 to 30 mole percent, most preferably from about 3 to 10 
mole percent of a water insoluble resin. 
The oligomer comprises polymerized units of from about 25 to about 66 mole 
percent of a first monomer, about 10 to 40 mole percent of second monomer. 
The weight average molecular weight of the oligomer is about 330 to 2000, 
preferably about 330 to 1000, more preferably about 600. 
The fluorescent pigment, more specifically, the oligomer, contains amide 
linkages or ester linkages or both. An amide linkage is formed from the 
condensation reaction between a carboxylic acid group on one monomer 
molecule and an amine group on an adjacent monomer molecule. The ester 
linkages are formed by the condensation reaction between a carboxylic acid 
group on one monomer molecule and an alcohol group on an adjacent monomer 
molecule. In certain embodiments amide but no ester linkages are present; 
such pigments are "amide" pigments. In certain embodiments ester but no 
amide linkages are present; such pigments are "ester" pigments. Where the 
pigment contains both ester and amide linkages it is referred to as a 
"polyamide-ester" pigment. 
The Monomers 
Monomers containing carboxyl groups used to create amide linkages and ester 
linkages include dicarboxylic acids, polyfunctional carboxylic acids, 
carboxyl-alcohols, and carboxyamines. Monomers used as a source of alcohol 
groups used to create ester linkages include alkanolamines, 
carboxyl-alcohols, difunctional alcohols, and polyfunctional alcohols. 
Monomers used as a source of amine groups to create the amide linkages 
include: diamines, polyfunctional amines, carboxyl-amines, and 
alkanolamines. The pigments of the present invention contain a first 
monomer an aromatic carboxylic acid and a second monomer containing at 
least one amine group or one alcohol. A molar excess of carboxylic acid 
groups or the anhydrides esters or acid chlorides, thereof, to the alcohol 
and amine groups is necessary to provide residual carboxylic acid groups 
with which the metal ions can complex. The molar ratio of carboxylic acid 
groups to the alcohol and amine groups is 1.1:1.0 to 5:1, preferably from 
1.2:1.0 to 4:1.0. 
The First Monomer: the Aromatic Carboxylic Acid Monomers 
The aromatic carboxylic acid monomer is a carboxylic acid or ester or 
anhydride or acid chloride thereof. As used herein, the term "aromatic 
carboxylic acid monomer" includes not only carboxylic acids but also the 
ester, anhydride and acid chloride derivatives thereof, unless otherwise 
noted. The aromatic carboxylic acid monomer has at least two carboxylic 
acid groups and has the following formula: 
EQU HOOC--R'--COOH 
where R' is a mono-cyclic or bicyclic arylene group of from 6 to 10 carbon 
atoms optionally having up to six ring substitutions which may be the same 
or different, selected from the group consisting of C.sub.1 -C.sub.5 alkyl 
groups. Preferably, the aromatic carboxylic acid monomer has 6 to 24, 
preferably 8 to 17 carbon atoms. Aromatic carboxylic anhydrides are 
preferred. 
Representative aromatic carboxylic acid monomers include, for example, 
phthalic acid, 2,6-naphthalene dicarboxylic acid, phthalic anhydride, 
trimellitic anhydride, benzophenone tetracarboxylic acid dianhydride, 
pyromellitic anhydride, isophthalic acid, terephthalic acid, trimellitic 
acid. Also suitable are the alkyl esters of the aforementioned carboxylic 
acids, including for example, dimethyl phthalate and 
dimethylterephthalate. Mixtures of aromatic carboxylic acid monomers are 
also suitable. 
The Second Monomer 
The Diamine Monomers 
The diamine monomers are the preferred monomer for the source of amine 
groups. The diamine monomers have the general formula: 
EQU H.sub.2 N--R"--NH.sub.2 
wherein R" is a straight or branched chain alkylene group of from 2 to 20 
carbon atoms, or a cycloalkylene group of from 5 to 6 carbon atoms 
optionally having up to three ring substitutions which may be the same or 
different, such substitution groups selected from the group consisting of 
C.sub.1 -C.sub.5 alkyl groups. 
Representative diamine monomers include, for example, ethylenediamine, 
1-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane, (also referred to 
herein as isophoronediamine), hexamethylenediamine, 1,12-dodecanediamine, 
2-methylpentamethylenediamine, 2-ethyltetramethylenediamine, 
1,2-diaminocyclohexane, 1,3-diaminocyclohexane, cis 
1,4-diaminocyclohexane, piperazine, 2methyl-1,5-diamino pentane and trans 
1,4-diaminocyclohexane. The isophoronediamine and 
2-methylpentamethylenediamine are preferred. Mixtures of diamine monomers 
are also suitable. 
The Polyamine Monomers 
The polyamine monomers typically have the same general structure as the 
diamine monomers, but contain at least one additional amine group. 
Representative polyamine monomers include, for example, diethylene 
triamine and triethylene tetraamine. Mixtures of polyamines are also 
suitable. 
The Carboxyl-Amine Monomers 
The carboxyamine monomers contain at least one amine group and at least one 
carboxylic acid group. Carboxyamine monomers include, for example, 
p-aminobenzoic acid, and lactams, such as caprolactame. Mixtures of 
carboxyamine monomers are also suitable. 
The Alkanolamine Monomers 
The alkanolamine monomers have the general formula: 
EQU OH--R"'--NH.sub.2 
wherein R"' is a straight or branched chain alkylene group having 2 to 8 
carbon atoms. Representative alkanolamine monomers include ethanolamine, 
butanolamine, n-propanolamine, and isopropanolamine. Secondary amino 
alcohols are also suitable; representative secondary alcohols include, for 
example, diethanolamine, and diisopropanol amine. Monoethanolamine and 
monoisopropanolamine are preferred. Mixtures of alkanolamine monomers are 
also suitable. 
The Polyfunctional Alkanolamine Monomers 
The polyfunctional alkanolamine monomers have the same general structure as 
the alkanolamine monomers, but contain at least one additional functional 
group such as an amine group or alcohol group or carboxylic acid group. 
Mixtures of alkanolamine monomers are also suitable. 
The Difunctional Alcohol Monomers 
The difunctional alcohol monomers have the general formula: 
EQU HO--R""'--OH 
wherein R""' is: a straight or branched chain alkylene group having 2 to 20 
carbon atoms; a cycloalkylene group having 5 to 6 carbon atoms and 
optionally having up to three ring substitutions, which may be the same or 
different, said ring substitution groups containing alkyl groups having 1 
to 5 carbon atoms. 
Representative difunctional alcohol monomers include, for example: 
cyclohexandimethanol, ethylene glycol and propylene glycol. Mixtures of 
difunctional alcohol monomers are also suitable. 
The Polyfunctional Alcohol Monomers 
The polyfunctional alcohol monomers have the same general structure as the 
difunctional alcohol monomers, but contain at least one additional alcohol 
group. Mixtures of polyfunctional alcohol monomers are also suitable. 
Illustrative polyhydric alcohol monomers include, for example, glycerol, 
tris(2-hydroxyethyl)isocyanurate trimethylolpropane, pentaerythritol 
available from Celanese, and dipentaerythritol. 
The Carboxyl-Alcohol Monomers 
The carboxyl alcohol monomers have the general formula: 
EQU HO--R"""--COOH 
wherein R""" is: a straight or branched chain alkylene group having 2 to 20 
carbon atoms; a cycloalkylene group having 5 to 6 carbon atoms and 
optionally having up to three ring substitutions, which may be the same or 
different, said ring substitution groups containing alkyl groups having 1 
to 5 carbon atoms. 
The carboxyl-alcohol monomers contain at least one carboxyl group and at 
least one alcohol. The carboxyl-alcohol monomers include, for example, 
p-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid and salicylic acid, 
and caprolactone. 
Optional Monomers 
Optionally the oligomer contains polymerized units of a dicarboxylic acid 
monomer which is: a dicarboxylic acid or ester or anhydride or acid 
chloride derivative thereof; or a polyfunctional carboxylic acid or ester 
or anhydride or acid chloride derivative thereof. The dicarboxylic acid 
monomer has the general formula: 
EQU HOOC--R""--COOH 
wherein R"" is: a non-aromatic, straight or branched chain alkylene group 
of from 0 to 20 carbon atoms; a cycloalkylene group of from 5 to 6 carbon 
atoms optionally having up to three ring substitutions, which may be the 
same or different, such substitution groups selected from the group 
consisting of C.sub.1 -C.sub.5 alkyl groups. 
Representative dicarboxylic acid monomers or ester or anhydride derivatives 
include, for example, succinic acid, succinic anhydride, glutaric acid, 
adipic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic 
acid, glutaric acid, cyclohexane dicarboxylic acid, dimethyladipate, 
dimethylglutarate, maleic acid, maleic anhydride, diethyloxalate and 
dimethylsuccinate. Mixtures of dicarboxylic acid monomers are also 
suitable. 
The polyfunctional carboxylic acid monomers have the same general structure 
as the dicarboxylic acid monomers, but contain at least one additional 
carboxylic acid group. Mixtures of carboxylic acid monomers are also 
suitable. 
The oligomer optionally contains polymerized units of an aliphatic or 
aromatic isocyanate monomer or mixtures thereof, particularly where the 
oligomer is made by the bulk two step method. The isocyanate monomer forms 
urethane linkages when it reacts with alcohol groups and urea linkages 
when it reacts with amine groups on the oligomer. Suitable isocyanates 
include, for example, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, 
isophoronediisocyante, and methylenebis(phenyl isocyanate). 
The oligomer optionally contains polymerized units of an aliphatic 
monofunctional carboxylic or aromatic mono-functional carboxylic acid 
monomer or the acid chlorides, esters, or anhydrides thereof, such as for 
example benzoic acid, and stearic acid. 
The Metal 
The polymer matrix also contains metal ions which complex to at least some 
of the residual carboxylic acids on the oligomer to form the polymer 
matrix. 
Divalent metals are most preferable, but trivalent metals are also 
suitable. Monovalent metal ions are also suitable; however, the monovalent 
metal ions produce fluorescent pigments having decreased water resistance 
and are least preferred. Magnesium and zinc ions are most preferred. 
To complex the metal ion to the oligomer, metal salts are added during the 
preparation of the matrix. Metal salts containing labile counter ions, 
such as oxides, hydroxides, formates, acetates, or propionates are 
preferred; oxides and hydroxides are the preferred counter ion. 
Suitable metal salts include for example, Group I hydroxides, Group I 
acetates, Group I propionates, Group II oxides, acetates, propionates, 
transition metal oxides, hydroxides, acetates and propionates, Group III 
hydroxides. The preferred oxides are the Group II oxides. The preferred 
metal salts are zinc and magnesium salts, most preferably zinc oxide and 
magnesium oxide. 
Other suitable salts include for example, zinc acetate, zinc propionate, 
magnesium acetate, magnesium propionate, calcium oxide, calcium acetate, 
calcium propionate, aluminum oxide, aluminum hydroxide, sodium hydroxide, 
sodium acetate, sodium propionate. 
The amount of metal employed depends on the quantity of free carboxylic 
acid groups on the oligomer. Where the metal ion has a valence of two and 
an average of three carboxylate groups are present on the oligomer, it is 
preferred that 1.5 metal ions per oligomer be employed for the fluorescent 
pigments. The number of moles of metal salt added to the oligomer to form 
the oligomer is from 50 to 200%, preferably from 75 to 100%, of the number 
derived from the following equation: 
EQU N.sub.M =(E.sub.c -E.sub.a -E.sub.o +E.sub.i)/n.sub.m 
where: 
N.sub.m is the number of moles metal salt; 
E.sub.c is the number of equivalents carboxylic acid; 
E.sub.a is the number of equivalents of amine; 
E.sub.o is the number of equivalents alcohol; 
E.sub.i is the equivalents of isocyanate; and 
n.sub.m is the oxidation state of the metal ion. 
The Water Insoluble Resin 
The optional water insoluble resin is a non-polar resin having a weight 
average molecular weight of from about 200 to 10,000, preferably about 
5000, more preferably about 350 to 1200. The water insoluble resin is 
preferably halogenated, preferably chlorinated or brominated and 
preferably has at least two functional groups, either epoxy groups or 
carboxyl groups or a mixture thereof. The functional groups on the water 
insoluble resin react with either the functional groups on the oligomer 
and/or with the metal ion of the polymer matrix. The water insoluble resin 
preferably has more than two functional groups, has a melting point below 
100.degree. C. The water insoluble resin forms ionic bonds with the metal 
ions of the polymer matrix. The water insoluble resin also is believed to 
react with the oligomer by condensation of the functional on the water 
insoluble resin, to the carboxylic acid groups or anhydrides thereof, on 
the oligomer. The water insoluble resin enhances the water resistance of 
the pigment. If the water insoluble resin is not present in the polymer 
matrix of the fluorescent pigment, the pigment is still suitable to color 
vinyl; however, the pigment tends to absorb water. Preferable water 
insoluble resins include carboxylic acid resins and epoxy resins such as 
for example, bisphenol A based epoxies and epoxy novolacs. 
The carboxylic acid water insoluble resins have a molecular weight of from 
about 600 to 10,000, preferably from about 1,000 to 4,000 and an acid 
number of from about 100 to 300. Suitable carboxylic acid water insoluble 
resins include, for example, acrylic resins, styrenated acrylic resins and 
styrene-maleic resins having acid numbers from about 100 to 300, 
preferably from about 200 to 300. Also suitable are polyester resins 
preferably having a molecular weight from about 800 to 1,500 and an acid 
number from about 150 to 300, preferably from 220 to 300. 
Preferably, the water insoluble resins with epoxy functional groups have a 
number average molecular weight of from about 200 to about 8000, more 
preferably about 400 to about 1000, and epoxy equivalent of from about 75 
to about 1000, more preferably about 190 to about 450, and an average 
epoxy functionality of from about 1 to about 6, more preferably about 2 to 
about 4. 
Preferably, the water insoluble resins with epoxy functional groups have a 
number average molecular weight of from about 200 to about 8000, more 
preferably about 400 to about 1000, and epoxy equivalent of from about 75 
to about 1000, more preferably about 190 to about 450, and an average 
epoxy functionality of from about 1 to about 6, more preferably about 2 to 
about 4. 
A preferred water insoluble resin is an epoxy novolac resin having a number 
average molecular weight of about 640, an epoxy equivalent of 176 to 181, 
an average epoxy functionality of 3.6. Another preferred water insoluble 
resin is an epoxy novolac resin having a number of average molecular 
weight of about 1270, an epoxy equivalent of 235, an average epoxy 
functionality of 4.4. 
Where the water insoluble resin is employed, a conventional epoxy 
accelerator such as, for example, N,N-dimethyloctylamine is preferably 
used to prepare the polymer matrix. 
When the fluorescent pigment is prepared by the bulk two step process, a 
water insoluble resin is selected that is dispersable in the aqueous 
oligomeric solution. A water insoluble resin is less preferred for 
pigments made according to the suspension technique. 
Fluorescent Dyes 
The fluorescent dyes used in this composition are conventional dyes and 
include, for example, fluorescent organic dyes which are brilliantly 
fluorescent when in solution. These daylight fluorescent type dyes belong 
to the dye families known as rhodamines, fluoresciens, coumarins, 
naphthalimides, benzoxanthenes, acridines, and azos. Suitable fluorescent 
dyes include, for example, Basic Yellow 40, Basic Red 1, Basic Violet 11, 
Basic Violet 10, Basic Violet 16, Acid Yellow 73, Acid Yellow 184, Acid 
Red 50, Acid Red 52, Solvent Yellow 44, Solvent Yellow 131. The 
fluorescent dye comprises from about 0.05 to about 15%, preferably about 
0.5-10% of the total weight of the pigment. One or more fluorescent dyes 
are present in the fluorescent pigment. 
Preparation of the Pigment 
Suspension Method 
A prepolymer dispersion of the first monomer and second monomer is formed 
by reacting monomers in an aqueous dispersion, forming a two phase system 
containing excess amine or hydroxide; typically this is accomplished using 
diisocyanates to form polyurethane or polyureas, dispersed in water. The 
dispersion is then cured with anhydride and metal oxide. The resulting 
pigment dispersion is water insoluble. The pigment is filtered from the 
water, oven-dried and ground to the desired particle size, to break up 
agglomerates. The preferred pigment particle size for use in vinyl is less 
than 20 microns, preferably a mean size of 1-5 microns. The advantage to 
this method is that particles are formed during dispersion and smaller 
median particle sizes with higher crosslink densities can be achieved than 
by mechanical grinding methods. 
Novel Bulk Two-Step Method 
The bulk method is a novel process which comprises first forming an 
oligomer in an aqueous solution, preferably at a temperature 70.degree. to 
130.degree. C., more preferably 90.degree. to 110.degree. C. by combining 
the first monomer and second monomer with water preferably at about 30 to 
90% solids. The monomers are reacted for a time sufficient for the 
exotherm to subside, preferably less than about 10 minutes. Alternatively, 
a premade oligomer is added to water and thoroughly mixed. When no amine 
monomers are used, then the first and second monomers are reacted 
preferably at about 110.degree. to 200.degree. C. for a time sufficient to 
effect esterification, preferably about 15 to 90 minutes. 
Next, the metal salt is added and, optionally, the water insoluble resin is 
added and dispersed in the aqueous solution. The fluorescent dye may be 
added any time, except if monomers contain amine it is preferred that the 
dye be added after the oligomer is formed. The water insoluble resin 
preferably has a melt point below 100.degree. C. The water solubility of 
the water insoluble resin is optionally enhanced by adjustment of pH or 
addition of cosolvents. The dyed prepolymer solution-dispersion mixture 
has the advantage of being liquid rather than solid and is easily handled; 
conventional techniques produce a pigment that solidifies and is difficult 
to remove from vessels. The dyed prepolymer solution-dispersion mixture is 
preferably then cast into a film prior to curing to expose surface area to 
air. The dyed prepolymer solution-dispersion mixture is then cured, at a 
temperature and for a time sufficient to drive off the water, preferably 
in an external vessel. Preferably the cure is accomplished at a 
temperature of preferably about 100.degree. to about 250.degree. C., more 
preferably 100.degree. to about 150.degree. C. and in about 3 to about 150 
minutes, more preferably about 3 to about 10 minutes. 
The cure removes the water from the reaction and causes the water insoluble 
resin, when employed, to bind to the oligomer. Preferably the cure is 
accomplished by a conventional curing techniques including, for example, 
forced air oven heating, microwave heating, radio frequency drying, or 
infrared heating, until the water is driven off so that preferably less 
than 1% remains. Preferably, the cure is accomplished in conventional 
ovens at 160.degree. C.; in a microwave ovens of 100 wattage at "100%" 
power; or in a radio frequency drying unit at 8 Mhz. The resultant pigment 
is ground to the desired particle size. The bulk two step method is the 
preferred method of manufacture of the fluorescent pigments of the present 
invention, and is also useful for making other pigments.

EXAMPLES 
The following examples are illustrative and are not intended to limit the 
scope of the invention. 
Pigments Made by the Bulk Two Step Process 
Example 1 
A reaction vessel equipped with an agitator and heat source was charged 
with 202 g of trimellitic anhydride and 100 g water. Next, 51 g of zinc 
oxide was dispersed in 89 g of isophorone diamine in a separate container 
and slowly added to the trimellitic anhydride/water mixture. The 
temperature of the batch slowly rose to 100.degree. C. and the batch began 
to reflux. Then 9 g of Basic Yellow 40, 0.45 g of Basic Violet 11 and 1.5 
g of Basic Red 1 were added to the batch under continued agitation. After 
5 minutes, the batch was dumped and cured at 180.degree. C. in a 
convection oven, then ground to a 5 grind on a Hegman gauge. The resultant 
pigment was orange, had a melt point in excess of 290.degree. C. 
Example 2 
To a reaction vessel equipped as in Example 1, 68 g piperazine was added to 
192 g trimellitic anhydride and 100 g water. After the reaction subsided, 
40 g magnesium oxide was slowly added to the vessel. A strong reflux was 
observed during the addition. 4 g Basic Yellow 40 was added to the batch. 
The batch was dumped and cured in an oven at 170.degree. C. for 1 hour. 
The resultant pigment was yellow. 
Example 3 
A resin was prepared in Example 1 except that the material was cured slowly 
by pouring the hot preresin with hot agitation onto 480 g 
diisooctylphthalate at a temperature above 140.degree. C. The resultant 
dispersion was then wet milled to achieve a dispersion containing 
approximately 40% pigment solids with a mean particle size of about 5 
microns. 
Example 4 
80 g water, 69.1 g tris(2-hydroxyethyl)isocyanurate, 69.1 g 
isophronediamine, 12.6 g magnesium oxide and 25.2 g zinc oxide were 
charged to reactor equipped as in Example 1. 156 g phthalic anhydride was 
added to the reaction over a period of 10 minutes. The temperature of the 
reaction rose to 100.degree. C. 11.9 g Acid Yellow 184, 0.66 g Basic Red 
1, and 0.26 g Basic Violet 10 were then added to the solution. The 
solution was then cured in an oven at 170.degree. C. for one hour. The 
resulting pigment was orange. 
Example 5 
To a reaction vessel equipped with an agitator, 58.4 g of isophrone diamine 
and 50 g of water were added. Under agitation, 20.6 g of isophorone 
diisocyanate was added over ten minutes at 35.degree. C. After an exotherm 
subsided, 10 g of magnesium oxide was added to the reaction. 74 g of 
phthalic anhydride was added and the reaction allowed to exotherm to a 
reflux. 1.0 g of Basic Violet 10 was finally added to the reaction. The 
solution was oven cured at 185.degree. C. for 1 hour to produce a pink 
pigment. 
Pigments Made by the Suspension Method 
Example 6 
To a reaction vessel equipped with an agitator and heat source was charged 
180 g of water and 22 g of 2-methyl-1,5-diaminopentane from Dytek A. In a 
separate container 27.5 g of isophorone-diisocyanate and 0.75 g of Basic 
Violet 10 were mixed. The isophorone-diisocyanate Basic Violet 10 mixture 
was added to the aqueous amine solution at 30.degree. C. over a period of 
10 minutes. 1.0 g of triethylamine was then added to the reaction. 5.0 g 
of magnesium oxide was added to the vessel, 18.5 g of phthalic anhydride. 
The reaction exothermed to 47.degree. C. forming a pigment dispersion. The 
vessel was then heated to boiling to drive the reaction to completion. The 
pigment was filtered and washed with water and acetone to produce a pink 
pigment. 
Pigments Made by the Bulk Two Step Method 
Example 7 
42.5 g isophronediamine, 17 g pentaerythritol, 37.4 g zinc oxide, 10.4 g 
magnesium oxide, and 60 g of water were charged to a reaction vessel 
equipped with a heat source and an agitator. 74 g of phthalic anhydride 
and 96 g trimellitic anhydride were then added and the reaction was 
allowed to exotherm to a reflux. 4.75 g of Basic Yellow 40, 1.0 g of Basic 
Red 1, and 0.53 g of Basic Violet 11 were then added and the reaction was 
cured in a 600 watt carousel microwave for 8 minutes to provide an orange 
pigment that did not melt below 290.degree. C. 
Example 8 
A pigment was prepared as in Example 7, but no pentaerythritol was used, 
and 85 g of the isophronediamine was used. 
Example 9 
A pigment was prepared as in Example 7, but pentaerythritol was omitted, 
and 43.5 g of tris(2-hydroxyethyl)isocyanuric acid was used. 
Example 10 
A pigment was prepared as in Example 9, but 32 g of the water insoluble 
resin, an epoxy novolac resin having a number of average molecular weight 
of about 1270, an epoxy equivalent of 235, an average epoxy functionality 
of 4.4 resin was added during the initial charge. 
Example 11 
A pigment was prepared as in Example 10, but the epoxy novolac resin was 
omitted, and 32 g of the water insoluble resin, an epoxy novolac resin 
having a number average molecular weight of about 640, an epoxy equivalent 
of 176 to 181, an average epoxy functionality of 3.6, and 0.6 g of an 
epoxy accelerator were added. The resulting pigment was orange. 
Example 11A 
A pigment was prepared as in Example 11, except that 4.25 g Basic Yellow 40 
dye was added, and Basic Red 1, and Basic Violet 11 were omitted to 
provide a yellow pigment. 
Example 12 
A pigment was prepared as in Example 11, except 2.5 g Basic Red 1 and 3.0 g 
Basic Violet 11 were used, and Basic Yellow 40 was omitted. 
Example 13 
200 g methanol and 192 g trimellitic anhydride were added to a reactor 
equipped with a heat source and an agitator. The mixture was heated to 
50.degree. C. for 15 minutes until the trimellitic anhydride dissolved. 85 
g of isophorone diamine was slowly added to the reaction, and 55 g of zinc 
acetate was added to the reaction. 5.24 g of Basic Yellow 40, 1.90 g of 
Basic Violet 11, and 2.5 g of Basic Red 1 were added to the reaction. The 
solution was then heated in an oven at 160.degree. C. for 2 hours. The 
resultant pigment was orange. 
Example 14 
40 grams of cyclohexanedimethanol was reacted with 43.5 grams of phthalic 
anhydride and 78.6 grams of trimellitic anhydride. The reaction was heated 
to 140.degree. C. and held at that temperature for 30 minutes. This 
mixture was then cooled to 90.degree. C. by addition of a solution 
containing 60 grams of water and 38.4 grams of isophoronediamine. To the 
reactor, 28 grams of zinc oxide, 6.0 grams of magnesium oxide, 3.0 grams 
of basic red 1, 2.0 grams of basic violet 11 and 80 grams of water were 
added. Then 0.2 mole equivalents of a halogenated epoxy resin and 1.0 
grams of tertiary amine accelerator were added. The resulting solution was 
cured in a microwave oven. The resulting dried pigment was pink. 
Example 15 
40 grams of cyclohexanedimethanol was reacted with 74 grams of phthalic 
anhydride and 96 grams of trimellitic anhydride at 140.degree. C. for 30 
minutes. The reaction was cooled to 90.degree. C. by addition of a 
solution containing 80 grams of water and 42.5 grams of isophorone 
diamine. 37.4 grams of zinc oxide, 10.4 grams of magnesium oxide, 3.5 
grams of basic red 1, and 2.5 grams of basic violet 11 were then added to 
the reactor with 80 grams of water. Then 0.2 mole equivalents of a 
halogenated epoxy resin and 1.0 grams of tertiary amine accelerator was 
added. The resulting solution was cured in a microwave oven. The resulting 
dried pigment was pink. 
Example 16 
34 grams of pentaerythritol was reacted with 148 grams of phthalic 
anhydride at 120.degree. C. for 30 minutes. A solution containing 10 grams 
of magnesium oxide and 20 grams of zinc oxide in 80 grams of water was 
added to the reactor. The resin was dyed using 4.0 grams of basic yellow 
40, 1.0 gram of basic red 1 and 0.4 grams of basic violet 11. Then 0.15 
mole equivalents of a halogenated epoxy resin and 1.0 gram of a tertiary 
amine accelerator was added. The resulting solution was cured in a 
microwave oven. The resulting dried pigment was orange. 
Evaluation of Pigments 
The pigments of Examples 1-13 were evaluated for resistance to acetone. A 
10% dispersion of the pigment in acetone was made, allowed to sit at room 
temperature for 10 minutes, then a drop of the test sample is placed on a 
piece of filter paper and the liquid which separated was examined under 
blacklight for the presence of fluorescent dye. The results are presented 
in Table I. 
The pigments of Examples 11, 11a, and 12 were also evaluated in: xylene, 
isopropyl alcohol, methyl ethyl ketone, mineral spirits, ethyl acetate, 
diacetone alcohol and a mixture of 50% xylene and 50% methyl ethyl ketone. 
1 gram of pigment was added to 10 ml of the solvent and allowed to set for 
either 30 minutes at 100.degree. F. or 7 days at 25.degree. C. The results 
are presented in Table I. 
The pigments of examples 11 and 13 were evaluated for resistance to 
dimethylformamide. The pigments were combined with dimethylformamide at 
room temperature and examined visually after 10 minutes. The results are 
presented in Table I. 
The pigments of examples 1-14 were used to color polyvinylchloride film. 
2.8 grams of fluorescent pigment were combined with 100 grams 
polyvinylchloride and processed in a 2 roll mill at front roll temperature 
of 340.degree. F. and back roll temperature of 270.degree. F. for about 5 
minutes, to form a plastic film. An initial sample of about 15 grams were 
sheared off the mill while the remainder of the plastic remained on the 
mill. The samples were then pressed between 2 stainless steel plates at 
7800 psi, for 10 seconds at 400.degree. F., to provide flat even films. 
The films were then removed from the press and cooled. The 
polyvinylchloride film colored with pigment of examples 1, 4-12, and 
14-15, were examined for bleed; a swatch of pigment polyvinylchloride was 
sandwiched between white polyvinylchloride film then the three film layers 
were sandwiched between glass plates, placed in 50.degree. C. oven for 48 
hours with 709.3 gram weight sandwich. The sample was viewed under 
daylight north and examined for color migration. The results are 
summarized in Table I. 
TABLE I 
______________________________________ 
SUMMARY OF PROPERTIES OF RESINS OF EXAMPLES 1-14 
Other 
Acetone Water.sup.a 
Solvent PVC 
Ex. Resist. Resist. Resist. Bleed 
______________________________________ 
1 1 2 NT none 
2 1 4 NT NT 
3 NT NT NT NT 
4 1 2 NT none 
5 1 2 NT none 
6 1 1 NT none 
7 1 2 NT none 
8 1 2 NT none 
9 1 2 NT none 
10 1 2 NT none 
11 1 2 no bleed in DMF, 
none 
xylene, isopropyl 
alcohol, methyl ethyl 
ketone, mineral 
spirits, ethyl 
acetate, diacetone 
alcohol and a mixture 
of 50% xylene and 50% 
methyl ethyl ketone. 
11a 1 2 no bleed in DMF, 
none 
xylene, isopropyl 
alcohol, methyl ethyl 
ketone, mineral 
spirits, ethyl 
acetate, diacetone 
alcohol and a mixture 
of 50% xylene and 50% 
methyl ethyl ketone. 
12 1 1 no bleed in DMF, 
none 
xylene, isopropyl 
alcohol, methyl ethyl 
ketone, mineral 
spirits, ethyl 
acetate, diacetone 
alcohol and a mixture 
of 50% xylene and 50% 
methyl ethyl ketone. 
13 1 NT NT none 
in 
plast 
isol 
14 1 1 NT none 
15 1 1 NT none 
16 1 2 NT NT 
______________________________________ 
NT not tested 
a resistance to bleed in water or acetone: 
1 no dye bleed 
2 bleeding of dye 
3 particles agglomerate 
4 particles dissolve 
As can be seen from Table I, the pigments of Examples 1-16 are resistant to 
acetone. Acetone resistance is the ability of the pigment to maintain a 
discrete particle and not to leach dye into the acetone. The pigments of 
Examples 1 to 16 do not bleed dye nor do they agglomerate or dissolve. The 
pigments of examples 1 to 16 also outperform conventional pigments. For 
example, GT-14 pigment, a conventional formaldehyde based pigment, has a 2 
rating in acetone. The resistance to bleed in water varied among the 
pigments of Examples 1-15. Accordingly, the pigments are preferred for use 
in organic solvent systems which have little or no water, and in plastics. 
No bleeding was observed in the xylene, isopropyl alcohol, methyl ethyl 
ketone, mineral spirits, ethyl acetate, diacetone alcohol and a mixture of 
50% xylene and 50% methyl ethyl ketone after the 30 minute period. Even 
after 7 days there was no bleeding in white spirit, xylene or ethyl 
acetate. After 7 days there was very slight bleeding in other solvents, 
but less than with conventional formaldehyde pigments. 
The pigments of Examples 11, 11a, 12 were also added to polyvinylchloride 
at high pigment concentrations; 20 parts pigment were combined with 52 
parts polyvinylchloride, 3 parts of the plasticizer, dioctylphthalate and 
2 parts stabilizer. The dry blend was processed on a 2 roll mill at 
175.degree. C. for 60 minutes, to form colored polyvinylchloride films or 
foils. The plastic did not stick to the rolls during processing. The 
pigments did not change color or degrade during the 60 minute cycle. The 
"foils" obtained above were then covered with a white polyvinylchloride 
foil, pressed on a press at 10,000 psi at a starting temperature of 
200.degree. F. The press was cooled over night to 25.degree. C. There was 
minimal bleeding; significantly less than occurs with conventional 
formaldehyde pigments. 
The pigment of Example 12 was evaluated for plateout during injection 
molding. The pigment was combined with high density polyethylene to a 
pigment concentration of 1%. Next, 3000 g of the colored HDPE samples were 
run through on injection mold running at 450.degree. F. No plateout was 
evident on the interior of the mold. 
The 3 g of the pigments of Examples 1 and 13 were combined with 97 g of a 
vinyl plastisol formulation, drawn down on Chromecoat coated stock paper 
to a thickness of about 6 mils, then cured at 180.degree. C. to provide a 
vinyl film. The pigments were examined for dye bleed onto the chromocoat 
surface. Neither of the samples displayed bleeding. 
The pigments of Examples 1, and 4 to 12 were also evaluated for color and 
heat stability in polyvinylchloride. Samples of polyvinylchloride film 
colored with the pigments of Examples 1, and 4 to 12 were combined with 
powdered Pantasote Kohinor 2478, a clear plasticized vinyl, processed on 
the mill at 175.degree.-180.degree. C., to form colored films, and 
collected at various times. The samples were collected as the film came 
out of the mill, and thereafter at 15 minutes, 30 minutes and 45 minutes. 
These samples remained on the mill at a temperature of 180.degree. F. The 
samples were compared to the sample initially collected and viewed under 
daylight northern illumination. There was no color loss in the samples 
collected at 15 and 30 minutes and less than 5% color loss in the sample 
collected at 45 minutes, indicating that the pigment was stable to 
prolonged exposure to heat. 
The polyvinylchloride film sample of film colored with pigment 11A and 12 
were also put into a fadometer and examined at 16 hours. The film colored 
with the pigments retained approximately 60% of color. 
A blowpin plateout test was performed with pigment from Example 11. First, 
a color concentrate was made by extruding a dry mixture of 25% pigment, 
75% MN-718 LDPE from Quantum Chemical through a Killion Lab extruder at 
375.degree. F. The extruded concentrate was chopped into pellets. The 
color concentrate was then combined with LC-73202 HDPE from Quantum 
Chemical at a concentration of 8%. A total of 20 lbs. of resin and 
concentrate was molded at 450.degree. F. Plateout values of conventional 
pigments are offered for comparison. The results are shown in Table II. 
TABLE II 
______________________________________ 
BLOWPIN PLATEOUT RESULTS 
Resin Plateout (mg) 
______________________________________ 
unpigmented HDPE 0.5 
Example 11 0.7 
conventional polyamide 
24 
thermoplastic pigment 
conventional polyamide 
4.8 
/polyester thermoplastic 
pigment 
conventional polyamide 
3.9 
thermoplastic pigment 
______________________________________ 
The pigment of Example 11 exhibits low plate out in blow molding 
applications as compared to comparative conventional pigments which do not 
contain formaldehyde. Indeed, the plateout value for the pigment of 
Example 11 is similar to the plateout value for unpigmented plastic. While 
conventional formaldehyde based thermoset pigments exhibit less plateout 
than conventional non-formaldehyde pigments, they tend to outgas 
formaldehyde particularly at temperatures above 400.degree. F. Thus, the 
pigments of the present invention demonstrate the low plateout values 
typical of formaldehyde pigments but without the formaldehyde outgassing. 
A fluorescent vinyl screen ink was prepared by combining 40.30 parts of the 
pigment of Example 11, 54 parts of a clear ink base of polyvinylchloride 
solubilized in glycol ether acetate. The ink was then placed in an oven 
for one week at 50.degree. C. Control samples of ink containing the 
pigment of Example 11 were left at ambient temperatures. For comparison, a 
conventional thermoset fluorescent pigment was also placed in the oven for 
one week. The ink of Example 11 had a strong clear color as compared to 
the conventional pigment. The viscosities were measured initially and at 
the end of the one week period. Samples of the ink containing the pigment 
of Example 11 and the conventional ink were also placed in an oven for one 
week at 122.degree. F. 
Initially, both the ink containing the pigment of Example 11 and the 
conventional thermoset ink had a viscosity of 3500 cps. However, at the 
end of one week in the 50.degree. C. oven, the ink containing the pigment 
of Example 11 had a viscosity of 3000 cps. In contrast, the conventional 
ink had a viscosity of 14250 cps, a 407% increase in viscosity, which 
rendered it unusable. The ink containing the pigment of Example 11 was 
substantially less lightfast than the conventional pigment, after five 
hours exposure to a carbon arc lamp. After one week in the 50.degree. C. 
oven, the ink containing the pigment of Example 11 displayed only a slight 
shift in color toward yellow as compared to the ink which remained at 
ambient temperature. In contrast, the conventional ink which was heated to 
50.degree. C. for one week displayed a substantial shift toward yellow 
when compared to the conventional ink which remained in ambient 
temperature. The ink containing the pigment of Example 11 which was heated 
for one week at 122.degree. F. was stable and displayed only a slight soft 
settle. In contrast, the conventional ink had small lumps throughout the 
batch, which indicated swelling of the pigment particles. 
While the pigments disclosed herein are useful to color and coat, rigid 
vinyl, flexible vinyl, A type and C type gravure inks, other plastics 
particularly plastics which are injection and blowmolded including for 
example, high density polyethylene, low density polyethylene, polystyrene, 
polyethyleneterephthalate, and polycarbonate; solvent based paints and 
coatings. 
Although one embodiment of this invention has been shown and described, 
various adaptations and modifications can be made without departing from 
the scope of the invention as defined in the appended claims.