Re.

25,845
United States Patent Office Reissued Aug. 31, 1965
2
cent dyestuffs in a thermoplastic resinous material of the
25,845 type represented by polyvinyl acetate and vinyl acetate
DAYLIGHT FILUORESCENT COMPOSTIONS vinyl chloride copolymers. However, considerable diffi
Gaetano F. D'Alelio, South Bend, Ind., and Robert W. culty has been experienced in the use of thermoplastic res
Voedisch, Morton Grove, Ill., assignors to Lawter inous materials of the type described since the latter soften
Chemicals, Inc., Chicago, Ill., a corporation of Dela under the temperature conditions developed in grinding
Ware
No Drawing. Original No. 3,116,256, dated Dec. 31, down to form the pigment with the results that the mate
1963, Ser. No. 133,548, Aug. 24, 1961. Application for rial is unsuccessfully ground down unless extensive pre
reissue Feb. 19, 1964, Ser. No. 358,390 cautions are taken to minimize temperature rise. Such
12 Claims. (C. 252-301.2) 0. resins are not amenable to commercial practice.
Matter enclosed in heavy brackets appears in the More recently, daylight fluorescent pigments and vehi
original patent but forms no part of this reissue specifi cles have been formulated of a thermoplastic resinous
cation; matter printed in italics indicates the additions material formed of the combination of an aryl monosul
made by reissue. fonamidealdehyde reaction product with a urea or mel
This is a continuation-in-part of application Ser. No. amine formaldehyde condensation reaction product, as
741,224, now abandoned, filed June 11, 1958, and entitled described in copending application Ser. No. 513,596, filed
"Daylight Fluorescent Compositions and Method.' June 6, 1955, and now abandoned, and entitled "Day
This invention relates to daylight fluorescent materials light Fluorescent Compositions and Methods for the
and it relates more particularly to a resinous material em Manufacture of Same,” and as described in the issued
ployed in combination with a daylight fluorescent dye 20 Kazenas Patent No. 2,809,954. As described, urea or
stuff in the preparation of a new and improved pigment melamine formaldehyde is incorporated in the combina
and a vehicle for inks, paints and the like. tion with the , aryl sulfonamide aldehyde to increase the
Fluorescent dyestuffs have heretofore been use in the melting point of the aryl sulfonamide to enable grinding
manufacture of daylight fluorescent pigments and coat in pigment formation but in an amount to avoid conver
ings for use in silk screen printing, letter-press inks, paints 25 sion of the resinous material to an infusible or insoluble
state.
and the like. While fluorescent of the dyestuffs has re While such co-condensation product of urea of mel
mained to impart the desired increase in color intensity amine-formaldehyde with an aryl sulfonamide aldehyde
when such materials have been employed on suitable represents an improvement over the vinyl type thermo
bases or carriers limited to indoor exposure, the fluores 30 plastic resinous systems and over the previously employed
cigenous energy of the dyestuffs has been found to be thermosetting resinous materials, it has been found that
rapidly dissipated when the base treated or coated with a considerable improvements can yet be achieved from the
daylight fluorescent material is subject to exposure to direct standpoint of the friability of the resinous material in
rays of the sun and to elements existing in the ambient the manufacture of pigment; in the light-fastness of the
atmosphere. In some instances, the fluorescence is lost material to prevent deterioration upon exposure in use; in
within the matter of a few days of outdoor exposure. the thermal stability of the material in pigmentation, manu
Considerable research has been expended with a view facture and use of the coating compositions or inks, and
towards increasing the fluorescent life of the various day in the wetting characteristics of the various inks, especially
light fluorescent materials employed in ink or other coat the letter-press inks.
ing compositions and particularly with respect to their 40 Thus it is an object of this invention to produce and to
stability for outdoor exposure. To the present, some suc provide a method for producing daylight fluorescent pig
cess has been achieved by compounding the dyestuff with ments, inks and coating compositions wherein the pig
a resinous material in which the dyestuff is soluble to ment has a higher melting point and friability and where
form a pigment to be incorporated in an ink or paint com in the final products have improved thermal stability, light
position. The resinous material is believed to provide a fastness and wet-out characteristics.
protective coating for the dyestuff to minimize its destruc The described improvements are secured, in accordance
tion or deterioration upon exposure to normal atmospheric with the practice of this invention, by the formulation of
conditions. a daylight fluorescent pigment or vehicle with a resinous
Very few of the large number of resinous materials base formed of the co-condensation reaction product of
available on the market have been found to be capable of 50 benzoguanamine (2,4-diamino-6-phenyl triazine-1-3-5)
use in the formulation of pigments or vehicles containing and formaldehyde with an aryl sulfonamide and formal
the daylight fluorescent dyestuff. Some success has been dehyde wherein the benzoguanamine is present in an
achieved by the incorporation of the daylight fluorescent amount less than 100 percent by weight of the aryl sul
material in the matrix of a thermosetting resinous prod fonamide and wherein the benzoguanamine is present perf
uct, such as the condensation reaction product of urea or 55 erably in an amount within the range of 30-60 percent by
melamine with a formaldehyde or a condensation prod weight of the aryl sulfonamide. Within the foregoing
uct formed by the reaction of a polybasic acid and a poly range, a desired increase in melting point is achieved when
hydric alcohol, as in the polyester resins. When formu an amount of benzoguanamine is employed within the
lated of such thermosetting resinous materials, the day range of 30-50% of the aryl sulfonamide, but best re
light fluorescent dyestuff is embodied in the resinous sys 60 sults are secured with the described combination when
tem while the latter is in a fuid state for solution or dis the amount of benzoguanamine is greater than 50 and up
tribution therein. In the manufacture of a pigment, the to 60 mol percent of the aryl sulfonamide, using 183
resinous carrier is subsequently advanced to an infusible 171 as the molecular weight of p-toluene sulfonamide and
and insoluble stage where it can be ground down to the 187 as the molecular weight of benzoguanamine.
desirable particle size. As used herein, the term "daylight fluorescent dyestuffs"
While daylight fluorescence is extended by pigmentation is meant to include such materials as xylene Red B (2,4
in the manner described, the life of the daylight fluores disulfo benzoic acid or 2.5 disulfo benzoic acid), Rhoda
cent material still remains insufficient from the standpoint mine 6 GDN (ethyl ester of m-monoethylamine phenolph
of the cost of the pigment and the cost of the ink or coat thalein hydrochloride), Azosol Yellow 6 GF (4 amino
ing composition fabricated thereof. 70 1.8 naphthol 2',4' dimethyl phenyl imide), Brilliant Sul
The fluorescent life of the pigment or coating has also foflavine FFA (3 sulfo 4 amino 1.8 naphthol 4 methyl
been improved by the formulation of the daylight fluores phenyl imide sodium salt), Rhodamine BX (meta-diethyl
 25,845
3 4.
amino phenolphthalein hydrochloride) having the gen The foregoing materials are mixed and then ground
eral formula over a three-roll mill. The resulting daylight fluorescent
ink may be printed on conventional letter-press equip
ck Dean
O
ment, preferably using a composition roller.
EXAMPLE 3
Preparation of daylight fluorescent pigment (orange)
booH N(Cls)
59.18 percent by weight toluene sulfonamide formalde
O hyde resin (Santolite MHP)
It will be understood that the above are merely rep 28.00 percent by weight benzoguanamine
resentative and that other recognized daylight fluorescent 10.00 percent by weight paraformaldehyde (91% purity)
dyestuffs may also be included under the term which will 0.72 percent by weight Rhodamine BX
hereinafter be employed in the specification and in the 0.66 percent by weight Rhodamine 7G
claims. 5 1.44 percent by weight Brilliant Yellow 6G base
As the aryl sulfonamide, use is preferably made of p The procedure which is followed in the formulation of
toluene sulfonamide but use can also be made of a mix
ture of o- and p-toluene sulfonamide other aromatic mono the pigment corresponds to that which is set forth in Ex
sulfonamides having two reactive hydrogens as further rep ample 1. The resulting product is a daylight fluorescent
resented by benzene sulfonamide, naphthalene trisulfon orange resin which is hard and friable and which is easily
amide and substituted sulfonamides of the types described.
20 ground down on a three-roll mill to a fine pigment. It
If desired, the aryl sulfonamide can be incorporated as has a softening point of 264 F. (129° C.) as determined
such or as a pre-condensation reaction product with an by the ball and ring method.
aldehyde, such as formalledhyde, to an intermediate stage EXAMPLE 4
of polymeric growth. Ordinarily the two can be reacted 25 Preparation of daylight fluorescent pigment (orange)
in equimolecular proportions but it is often desirable to
make use of an excess of the aldehyde, such as an amount 48.50 percent by weight of a mixture of o- and p-toluene
up to 200 percent in excess. sulfonamide (Santicizer 9)
As the aldehyde, it is preferred to make use of formal 25.00 percent by weight benzoguanamine
dehyde or its equivalent of paraformaldehyde although 30 18.00 percent by weight paraformaldehyde (91% purity)
other aldehydes such as benzaldehyde, glyoxal, pyruvic 6.00 percent by weight water
aldehyde, and acetaldehyde can be used but with less de 0.63 percent by weight Rhodamine BX
sirable results from the standpoint of friability and hard 0.59 percent by weight Rhodamine 7G
SS 1.28 percent by weight Brilliant Yellow 6G base
The following will represent the practice of this inven 35 The Santicizer 9, a product of Monsanto Chemical Com
tion in the manufacture of pigments and vehicles, and the pany, Was reduced to a molten state at about 260 F, in a
fabrication of paints and ink compositions therefrom: reaction vessel which is equipped with a heavy duty mixer.
EXAMPLE 1. The paraformaldehyde was added with resultant cooling
Preparation of an ink vehicle 4. and the temperature was brought back slowly to about
240 F. over a period of 10-15 minutes. To the clear
73.38 percent by weight toluene sulfonamide formalde solution the dyestuffs were added and after the dyestuffs
hyde resin (Santolite MHP-Monsanto Chemical Com were dissolved, the benzoguanamine was slowly added and
pany) the temperature gradually brought back to about 240° F.
14.00 percent by weight benzoguanamine The Rhodamine BX dissolved in the water was added and
6.00 percent by weight paraformaldehyde the batch temperature was then gradually raised to 290°
4.00 percent by weight water F. Over a period of 2-2-2 hours. The materials were then
0.66 percent by weight Rhodamine BX poured into a tray and cooled. The final product which
0.62 percent by weight Rhodamine 7G was a very friable and highly resinous material was found
1.34 percent by weight Brilliant Yellow 6G base to have a softening point of 312 F. (155° C.). The resin
Procedure 50 can be easily ground to form a fine daylight fluorescent
orange pigment.
The toluene sulfonamide aldehyde resin in an inter
mediate stage is reduced to a molten state and heated to a EXAMPLES
temperature of about 270 F. with agitatation. The ben Preparation of a silk screen lacquer from the pigments of
zoguanamine is added and the mixture is held at a tem 55 Example 3 or 4
perature within the range of 260-270 F. until solution is
effected (about 10 minutes). The dyestuffs are added and 55.0 percent by weight polyacrylic resin solution (Acry
dissolved and then the batch is allowed to cool to a tem loid F-10)
perature of about 240 F. after which the paraformalde 40.0 percent by weight pigment from Example 3 or 4
hyde is slowly incorporated. The batch is then raised in 60 0.8 percent by weight dried expanded silica gel (Santocel
temperature to about 290 F. over a period of from 2-2% 54)
hours and then poured into a tray for cooling and solidifi 4.2 percent by weight mineral spirits
cation. The resulting daylight fluorescent resinous ma The ingredients are mixed and ground down over a
terial is hard and brittle and has a softening point of 210 three-roll mill. The resulting silk screen ink has a bril
F. (99 C.) as determined by the ball and ring method. liant orange shade and can be effectively used in silkscreen
EXAMPLE 2 printing or the like.
Preparation of a letter-press ink of the vehicle EXAMPLE 6
in Example 1
51.0 percent by weight resin from Example 1 70
Preparation of daylight fluorescent yellow pigment
28.0 percent by weight butyl Carbitol acetate 40.7 percent by weight toluene sulfonamide-formaldehyde
18.0 percent by weight pigment of the orange fluorescent resin (Santolite MHP)
dye embodied in a polyvalent metal-alkyd resin complex 30.5 percent by weight benzoguanamine
as prepared by the French Patent 1,064,955 26.4 percent by weight formalin (37% formaldehyde)
3.0 percent by weight dried silica gel (Santocel) 2.4 percent by weight Brilliant Yellow 6G base
 25,845
5 6
The procedure for preparation is similar to that of Ex sistant to attack by elements normally coming into con
ample 1 with the formalin being introduced in the same tact therewith. All of these are important to extend the
point in the reaction as was the paraformaldehyde. The utility and life of the daylight fluorescent materials as
softening point of the resin was 132° C. (Ball and Ring a printing ink or coating composition.
method). It may be ground to a daylight fluorescent yel It will be understood that changes may be made in
low pigment which is suitable for use in the silk screen ink the details of formulation without departing from the
composition as set forth in Example 5. spirit of the invention, especially as defined in the foll
EXAMPLE 7 lowing claims.
We claim:
Preparation of daylight fluorescentletter-press ink O 1. A daylight fluorescent material consisting essential
43.0 percent by weight quickset varnish ly of the combination of a daylight fluorescent dyestuff
18.4 percent by weightgloss varnish in a resinous base formed by the co-condensation of an
36.5 percent by weight pigment of Example 6 aryl sulfonamide aldehyde and benzoguanamine and
0.6 percent by weight cobalt naphthenate (6%) aldehyde wherein the aryl sulfonamide is selected from
1.5 percent by weight phthalocyanine green 15 the group consisting of p-toluene sulfonamide and o
toluene sulfonamide and mixtures thereof and wherein
This material is mixed and then milled on a roller the aldehyde is selected from the group consisting of
mill. Several passes are taken until a Hegman Gage formaldehyde and paraformaldehyde, wherein the day
reading of 7 NS is obtained. The resulting product can light fluorescent dyestuff is present in an amount suffi
be printed on any conventional letter-press. 20 cient to impart daylight fluorescence and the benzoguana
The following table will set forth some of the work mine is present in an amount within the range of more
that we have performed with reference to the ratio of than 50 but less than 60 mol percent of the aryl sulfona
benzoguanamine to the aryl sulfonamide or the aryl mide.
sulfonamidealdehyde condensation reaction product and 2. A daylight fluorescent material consisting essential
with further reference to the ratio of benzoguanamine 25 ly of the combination of a daylight fluorescent dyestuff
with formaldehyde and the resulting effect on the soften in a resinous base formed by the co-condensation of an
ing point as determined by the Ball and Ring method. aryl sulfonamide formaldehyde and benzoguanamine and
formaldehyde wherein the aryl sulfonamide is selected
Other softening from the group consisting of p-toluene sulfonamide and
Resin No,
Santoite
MP Ben 20-
Paraform- point, bail and 30
aldehyde ring o-toluene Sulfonamide and mixtures thereof, wherein
(grams) guanannine 91% (gram the daylight fluorescent dyestuff is present in an amount
moles)
Deg. F. Deg. C. sufficient to impart daylight fluorescence and the benzo
guanamine is present in an amount within the range of
2 0.2 0.8 225 1. more than 50 but less than 60 mol percent of the aryl
. 0, 4 29 14 sulfonamide.
2
200
0.5
.5
.
0.75
264
28
19
148
3. A daylight fluorescent material as claimed in claim
2. ,5 0.75 26 19 1 in which the aryl sulfonamide and the aldehyde are
VIII------------ 2. 0.55 1. Ole 260 127 Separately reacted by condensation to an intermediate
stage of polymeric growth.
In the foregoing table, 187 grams was used as the 40 4. A daylight fluorescent material as claimed in claim
gram-mole weight of benzoguanamine and 30 grams was 1 in which the benzoguanamine and the aldehyde for
used as the gram-mole weight of paraformaldehyde. A reaction therewith are present in the ratio of 1 molecular
factor of .9 was used with the paraformaldehyde-this weight of benzoguanamine to 1.4-4 molecular weights of
being the purity factor of the formaldehyde in para the aldehyde.
formaldehyde of a commercial grade. Assuming that 5. A daylight fluorescent material as claimed in claim
Santolite MHP comprises the reaction product of p-tolu 1 in which the benzoguanamine and the aldehyde are
ene Sulfonamide with from 1 to 2 moles of formaldehyde, present for reaction therewith in the ratio of 1 molecular
the amount of p-toluene sulfonamide will be calculated weight of benzoguanamine to 1.4-2 molecular weights of
to be slightly more than 1 mole per 200 grams of Santo the aldehyde,
lite MHP. Thus, an amount of benzoguanamine equiv 50 6. A daylight fluorescent pigment formed of the com
alent to 0.5 gram-mole per 200 grams of Santolite MHP bination of the daylight fluorescent dyestuff embodied in
will correspond to a mole ratio of benzoguanamine to a completely condensed and particulated resinous base
aryl sulfonamide which is slightly greater less than formed by the co-condensation of an aryl sulfonamide
0.550 mol percent while the 0.55 mole gram of benzo aldehyde and benzoguanamine-aldehyde wherein the aryl
guanamine in the foregoing table will correspond to 55 sulfonamide is selected from the group consisting of p
about 0.56 56 to 0.57 57 mole percent of the aryl toluene Sulfonamide, o-toluene sulfonamide and mixtures
sulfonamide. thereof, wherein the aldehyde is selected from the group
For pigment formulation, it is desirable to make use consisting of formaldehyde and paraformaldehyde and
of the harder and more friable resins, as represented by wherein the daylight fluorescent dyestuff is present in an
the resins identified by the number V, VI, VII and VIII, 60 amount sufficient to impart daylight fluorescence and the
each of which has a softening point above 245 F. The benzoguanamine is present in an amount within the range
other resinous systems as well as the resins previously of more than 50 and up to 60 mol percent of the aryl
referred to can advantageously be employed in a dis sulfonamide.
solved state in a carrier for letter-press or other printing 7. A daylight fluorescent pigment as claimed in claim
inks. 6 in which the aldehyde is added as a component sepa
It will be apparent from the foregoing that we have rate and apart from the benzoguanamine and the aryl
produced a new and improved daylight fluorescent com sulfonamide.
position in the form of a vehicle or pigment and paints 8. A daylight fluorescent pigment as claimed in claim
or ink compositions formulated thereof characterized 6 wherein the sulfonamide is incorporated in an inter
by greater life stability, improved friability and hardness, mediate stage of condensation reaction with formal
better wetting out characteristics and improved light dehyde.
fastness. It has been found further that the system 9. A daylight fluorescent pigment is claimed in claim 6
that is formed is highly resistant to attack by alkali which in which the benzoguanamine and the aldehyde present
therefore enables pigments to be incorporated in emul for reaction there with is embodied in the ratio of 1 mole
sion paints and inks. The coatings are also more re- 5 benzoguanamine to 1.4 to 4 mols of the aldehyde.
 25,845
7 8
10. A daylight fluorescent vehicle consisting essentially aldehyde, wherein the aryl sulfonamide is selected from
of a fluid carrier, a daylight fluorescent dyestuff and a the group consisting of p-toluene sulfonamide and o
substantially complete condensed thermoplastic resinous toluene sulfonamide and mixtures thereof and wherein
material which is present in the system and formed of the aldehyde is selected from the group consisting of
the co-condensation reaction of an aryl sulfonamide and formaldehyde and paraformaldehyde, wherein the day
aldehyde and benzoguanamine and aldehyde wherein the light fluorescent dyestuff is present in an amount sufficient
aryl sulfonamide is selected from the group consisting of to inapart daylight fluorescence and the benzoguanamine
p-toluene sulfonamide, o-toluene sulfonamide and mix is present in an amount within the range of more than
tures thereof, wherein the aldehyde is selected from the 50 mol percent of the arylsulfonamide up to an amount
group consisting of formaldehyde and paraformaldehyde 10 less than 100 percent by weight of the aryl sulfonamide.
and wherein the daylight fluorescent dyestuff is present
in an amount sufficient to impart daylight fluorescence References Cited by the Examiner
and the benzoguanamine is present in the ratio of more The following references, cited by the Examiner, are
than 50 and up to 60 mol percent of the arylsulfonamide. of record in the patented file of this patent or the original
11. A daylight fluorescent vehicle as claimed in claim 5 patent.
10 in which the benzoguanamine and the aldehyde UNITED STATES PATENTS
present for reaction therewith are present in the ratio of 1 2,794,008 5/57 Ginsler -------------- 252-45.2
mol benzoguanamine to 1.2 to 4 mols of the aldehyde 2,809,957 10/57 Kazenas ------------ 252-301.2
in the form of formaldehyde. 2,938,873 5/60 Kazenas ------------ 252-301.2
12. A daylight fluorescent material consisting essen 20
tially of the combination of a daylight fluorescent dyestuff TOBIAS E. LEVOW, Primary Examiner.
in a resinous base formed by the co-condensation of
an aryl sulfonamide aldehyde and benzoguanamine and MAURICE A. BRINDISI, Examiner.