Note: Descriptions are shown in the official language in which they were submitted.
;~ ` Docket 2752
~ ~ Michael E. A. Seitz
637
,i~COLOR ~EVELOPERS FQ~ PRESSURE-SENSITIVE OR
~HEAT-SENSITI~E RECGR~ING PAPERS
.
Field of the Invention
The present invention relates to novel color developers
for use in carbonless copy papers (CCP) and thermal imaging
papers (TP) which will produce a stable intense mark when
placed in contact with colorless dye precursors. The present
invention also relates to record material sheets bearing
a coating which contains such novel color developers.
Back round of the Invention
Pressure-sensitive or heat-sensitive recording
papers r~ly on two components to form color. One component
is a colorless or slightly colore~ dyestuff or color precursor.
The other component is an acidic material or color developer
which is capable of forming a color by reaction with the
dyestuff or color precursor. Marking of the recording papers
is effected by pressure or heat which transfers one reactant
to the other.
Pressure-sensitive recording material consists,
for example, of at least one pair of sheets which contain
at least one dyestuff or co~lor precursor,dissolved in an
organic solvent,and a color developer. The dyestuff or
color precursor effects a colored marking at those points
where it comes into contact with the color developer.
In order to prevent the color precursors contained
in the pressure-sensitive recording material from becoming
active prematurely, they are usually separated from the
developer. This can advantageously be accomplished by
Docket 2752
; 12~46;~7
,. ,
lncorporating the color precursors in foam-like, sponge-like,
or honeycomb-like structures. Preferably, the color formers
are enclosed in microcapsules which usually can be ruptured
by pressure.
S In a common method of man~facture of pressure-sensitive
recording papers, '~etter known as carbonless copy papers,
a layer of pressure-rupturable microcapsules containing
a solution of colorless or slightly colored dyestuff or
color precursor, is normally coated on the backside of the
front sheet of paper of a carbonless copy paper set. This
coated backside is known as the CB coating. In order to
develop an image or copy, the CB coating muse be mated with
a paper containing a coating of suitable color developer
on its front. This coated front color developer coating
is called the CF coating. Marking of the pressure-sensitive
recording papers is effecting by rupturing the capsules
in the CB coating by means of pressure to cause the dyestuff
precursor solution to be exuded onto the front of the mated
sheet below it. The colorless or slightly colored dyestuff,
or dyestuff precursor, then reacts with the color developer
in the areas at which the pressure was applied, thereby
affecting the colored marking. Such mechanism or the producing
technique of pressure-sensit'ive recording papers is well
known.
Various developers for use in thermoreactive recording
material are also well known. Thermoreactive recording
material usually contains at least one carrier, one color
precursor, one solid developer and, optionally, also a binder.
The thermoreactive recording systems comprise, for example,
heat-sensitive recording and copying materials and papers.
`~
~ Docket '7~2
637
.
These systems are used, for example, for recording information,
eOg., in electronic computers, teleprinters or telewriters,
or in reco~ding and measuring instruments. The image (mark)
formation can also be effected manually with a heated pen.
Laser beams can also be used to produce heat-induced marks.
The thermoreactive recording material can be so composed
that the color presursor is dispersed or dissolved in one
binder l~yer and the developer is dissolved or dispersed
in the binder in a second layer. Another possibi~ity consists
in dispersing both the color precursor and the developer
in one layer. By means of heat, the binder is softened
at specific are~s and the color preeursor comes into contact
with the developer a~ those points where heat is applied
and the desired color develops at once.
Color precursors are well known to those experienced
in the field and any such color former may be used in conjunction
with the present invention, e.g., those belonging tc the
classes of the phthalides, fluoranes, spiropyranes, azomethines,
triarylmethane-leuco dyes, sf the substituted phenoxazines
or phenothiazines, and of the chromeno or chromane color
formers. Examples of such suitable color precursors are:
crystal violet lactone, 3,3-(bisamino-phenyl)-phthalides,
3,3-(bisubstituted indolyl)-phthalides, 3-~aminophenyl)-3-indolyl-
phthalides, 6-diaalkylsmino-2-n-octylaminofluoranes, 6-dialkylamino-
2-arylamlnofluoranes, 6-dialkylamino-3-methyl-2-arylaminofluoranes,
6-dialkylamino-2- or 3-lower alkylfluoranes, 6-dialkylamino-2-
dibenzylaminofluoranes, 6-dialkylamino-2-dibenzylaminofluoranes,
6-diethylamino-1,3-dimethylfluoranes, the lactonexanthenes,
the leucoauramines, the 2-(omega substituted vinylene)-3,3-
disubstituted-3-1-1-indoles, 1,3,3-trialkylindolinospirans,
.: Docket 2752 ~
~ 1~214637
~` .
bi8-taminophenyl)-furyl-, phenyl- or carbazolylmethanes,
or benzoyl-leueomethylene blue.
Known color developers for use in such pressure-sensitive
or heat-sensitive recording pspers have included:
(1; novolac phenolic resins madé by acid catalyzed
condensation of phenol, resorcinol, pyro~allol, cresols,
xylenols, or alkyl phenols such as p-tertiary butyl
phenol~with aldehydes such as formaldehyde, acetaldehyde,
benzaldehyde, and butyraldehyde;
(2) Metal salts of aromatic carboxylic acid~
with an OH group at the ortho position, such
as zinc salts of salicylic acid,3,5-di-tert-butyl
~alicylic acid, octyl salicylic acid, and 1-hydroxy-
2-naphChoic acid, and
(3) acid-treated clays such as kaolinites and
attapulgites.
The search has continued for other developers
having high developing power, rapid developing speed, good
light resistance and time stability. Examples of some colored
developers which have been developed in the past which are
somewhat related to those of the present invention are disclosed
in U.S. patent 4,291,901 to Petitpierre and Japanese patent
dlsclosure 1979-111905.
Summary of the Invention
~5 Accordingly, it is an object of the present invention
to provide a novel color developer.for use in pressure-sensitive
or he~t-sensitive recording papers.
It is another object of the present invention
to provide an improved record sheet coated with such a novel
30 color developer.
Docket 2752
63'7
A further object of the present invention to provide
such a color developer with excellent color developing properties.
These and other objects of the present invention
are obtsined by means of the novel color developers of the
present invention which are, in part, N-monosubstituted
sulfonamides which contain at least one electron withdrawing
group. The simple sulfonamides and n-monoalkyl sulfonamides
tRSO2NH2 and RSO2NHR' respectively) have acidities that
are too weak for these materials to be very useful as primary
color developers. They are useful as Eilm modifiers and/or
secondary color developers. However, the addition of an
electron-withdrawing group not more than five ~5~ atoms
from the NH group on the sulfonami~e increases its acidity
(via the inductive effect) J and makes the sulfonamides suitable
for use 85 primary color developers. Where applicable,
the pKa (-log Ka~ where Ka is the acid dissociation constant)
of the sulfonylamide (-SO2-NH-) group should be in the range
of 9.5 to 2.5, and preferably in the range of 8 to 4. Suitable
electron-withdrawing groups are those substituents which
possess positive Hammett or Taft constants. The novel color
developers can also be N-monosubstituted, N'-mono or di-substituted
sùlfamides [R'''(Ro")~N~SO2NHRo']. Again for the reasons
s~ated above, an electron-withdrawing group must be no more
than 5 atoms from the NH group.
The maximum color developing potentiàl is realized
when these N-monosubstituted sulfonamides or N,N'-substituted
sulfamides are used in conjunction with some source of metal
or metal compound. Specifically, the sulfonamines or sulfamides
may be
,, :
'.
Docket 2752
463~
(1) mixed with or dissolved in an organic metal
salt such as zinc oleate, zinc octoate, and zinc acetate,
(2) precipit~ted onto a metal oxide hydroxide,
or carbonate such 8S zinc oxide, zinc hydroxide, or zinc
carbonate,
(3) co precipitated from water with soluble metal
salts like zinc chloride, zinc ammonium chloride, or zinc
sulfate, or
(4) chemically modified by a metal so as to incorvorate
the metal into the sulfonamide or sulfamide molecules.
The latter will take the form of organic acid
salt formation by reacting either an extra -S-NH- group or a
COOX group in the sulfonamide or sulfamide wth a basic
metal oxide or carbonate. The salt may also be formed by
reaction of alkali salt of the sulfonamide (or sulfamide)
wi~h a soluble acidic metal salt such as zinc sulfate.
The above examples are restricted to zinc for the sake
of being concise. Other metals such as aluminum, barium,
bismuth, calcium,cerium, cesiùm, lithium, magnesium, tin,
and titanium may be used in place of zinc.
Detailed Description of Preferred Embodiments
. .
The present invehtion comprehends all compounds
which include a sulfonylamide (-SO2NH-) group and also include
an electron-withdrawing atom or moiety within five atoms
of the NH group. However, the compound must be free of
any basic group, for example, epoxy or NH2. Any additional NH
groups withïn-the compound must be no more than one carbon away from
an 92 group, or to a C~O, G-N, or ~ group. The present invention
further excludes such compounds in which the electron-withdrawing
Docket 2752
~Z~4637
group is a carboxy phenyl group connected through ~he nitrogen
~tom of the sulfonylamide group or in which the sole electron-
withdrawing ~roup is a carboxyphenyl group. Also excluded
are compounds having
a hydroxy group on the opposite side of the amide from the
sulfonyl group of the sulfonylamide grouping.
Particularly preferred sulonylamide compounds
in accordance with the present invention have electron withdrawing
groups on both sides of the 5ul fonylamide groupingO
Subject to the above conditions, the electron
withdrawing group can be any of the followin~: -NO2, -SO2R,
-CN, -SO2Ar, -COOH, -SO2NH2, -SO2NHR, -SQ2NR2, -F, rCl,
-Br, -I, -OAr~ -COOR, -COOAr, -OR, -OH, -SR, -SH, -COR,
-COAr, -C~CR, -Ar, -CH=CR2, wherein R is an alkyl group of up to 18
carbon atoms, preferably 3-8 carbon atoms, and Ar is any ary]
group, preferably phenyl or naphthyl. The R and Ar groups
may be optionally substituted as long as the above conditions
are met.
Particulsrly useful compounds for use as color
developers in accordance. wi.th the present invention are
N-monosubstituted sulfonamides represented by formula
O H
Rl-S-N-(R2)n-G (I)
where Rl and R2 are alkyl (branched or linear), preferably
with no more than 18 carbon atoms and most preferably
with 3-8 carbon atoms, aryl, preferably phenyl or naphthyl,
or a combination of both, each of which may be substituted
or unsubstituted, said substituents, if any, being
any group other than a basic group, such as epoxy or NH2,
and if -NH- it must be no more than one carbon atom away
from a SO2, C~O, C=N or NO2 group-
. Docket 2752 ~J
637
G is an electron withdrawing group as defined above and is rot more than
fiYe atoms aws~ from the -NH- group, with the proviso that
G is not -OH or -SH when n is l and with ~he further proviso
that ~~R2)n-G is not ~ COOH; and
.n is 0 or 1.
Other sulfonamides useful in the practice of the
present invention are those in accordance with formula
O H
G-(R2)n-S-N-Rl (II)
0
wherein n, Rl, R2 and G are as defined above with the proviso that
Rl is not ~ COOH and with ~he further proviso that G is
not COOH in formula II wh~n all of the following three con-
- ditions apply: R2 is aryl, n is l, and Rl does not com-
prehend or include an electron-withdrawing group (as defined
above for G) within 5 atoms of the NH group.
Analogous to the sulfonamides above, the N-mono-
substituted, N'-mono or di-substituted sulfamide color developers,
which are also particulsrly useful in accordance with the
present lnvention, are represented by formula III below:
3 O H
R 11 1
4~N_s_N_(R2)n-G (III)
o
where R2, G and n are 2S defined above and R3 and R4 are as
defined above for Rl and R2 although ~ne of R3 and R4
may~be H; furthermore, when one of R3 and R4 is H, the
other may be an electron withdawing group as defined
above for G.
The usefulness of the N-monosubstituted sulfonamides
as color developers is enhanced further by placing electron-
withdrawing groups on both sides of the sulfamoyl group.
DockeL 2752
63~
Preferred s~ch compounds useful in the practice of the
present invention are represented by formula IV-
O H
G'-(R2)n-¦S-N-(R2)n-G (IV)
0
wherein n, R2 and 5 are as defined above and G' is an electron
withdrawing group as defined above with respect to G.
While the substituents with respect to formulae
I-IV and the remainder of the generic formula as discussed
above may include any functional group not specifically
proscribed, it partic~larly may include additional -S02NH-,
alkyl, aryl and electron withdrawing (as defined above for
G) groups, and may, in fact, be a polymer containing repeating
units of ~ny of the above.
Examples of compounds within Eormula (I) are as
follows: H
N-(phenyl ~ulfonyl)-p-toluenesulfonamide C6H5S02-N-S02C6H4CH3
N-phenyl-benzene sulfonamide ~ S02-N ~
Docket 2752
ti3~
~1 o
n-butyl-N-(phenylsulfonyl)-p-aminobenzoate ~ S02-N ~ C-OC4H9
H H ~
N-~-(p-toluenesulfonyl)-~L-phenylalanine CH3- ~ so2_~ H2
C02H
H
N-~csrboxymethyl)-p-toluenesulfonamide CH3- ~ -S02-N-CH2CO2H
N-[o-(p-toluenesulfonamido) phenyl]-p-toluenesul~onamide
H
1 0
Wi~h respect to examples of compounds of formul~
(II~, it should be noted that in Japanese patent disclosure
1979-111905, comparstive compound example 3, i.e. N-(octadecyl)-
o-carboxybenzene sulfonamide, is taught as being a poor
developer, particularly in comparison with the anthranilic
developers disclosed by the Japanese patent. It has surprisingly
been discovered, however, that the addition of another electron
withdrawing group, this time on the nitrogen side of the
sulfonamide, further increases the color developing property and
such compoundsthus become preferred compounds of the present invention.
Examples of compounds in formula (II3 including the above
described preferred compounds are as follows:
n-butyl-N-(o-carboxyphenylsulfonyl)-p-amino-benzoate
C02H
~ S02-NH- ~ -C02C4H9
N-(o-carboxyphenylsulfonyl3-4-aminobenzophenone
C02H O
~ S2 -NH-<~)- C~)
- -
Docket 2752 ~ 3~
N-(o-carboxyphenylsulfonyl)4-aminobenzenesulfonamide
C02H
~ 2 ~ 2 2
N-(4-n-butylphenyl)-o-carboxybenzenesulfonamide
~02H
~ S2-NH ~ -(CH2~3-CH3
N-(4-octylphenyl)-o-carboxybenzenesulfon.~mide
CO~H
~ 5O2-NH- ~ -(CH2)7-cH3
N-~4-dodecylphenyl)-o-carboxybenzenesulfonamide
C02H
~ SO2-NH- ~ -(CH2)11 C 3
N-(2,4-diethylphenyl)-o-carboxybenzenesulfonamide
~ -SO2-NH ~ CH2C 3
With respect to all of the above flcids, the preferred
form is that of the metal salt, particularly an alkaline
- earth metal salt, and more particularly a zinc salt.
Examples of formula (III) are:
N-(dimethylsulfamoyl)-p-toluenesulfonamide
CH3 1l I ll
C~H~ N- 11 ~~ CH3
O O
N-phenyl-N'-isopropylsulfamide
H H O H
CH3-C-N-s-N
CH3 O
: . Docket 2752 ~P ~
~ 4637
.
N-benzoyl-N'-isopropylsulfamide
H H O H O
i 1 11 1 11
CH3-C-N-S-N-C-
CH3 ~
N-phenyl-N',NI-dimethylsulfamide
O H
- CH3~ ll
N-(dimethylsulfamoyl)-~-aminophenylacetic acid
~N-S-N-C-
N-(o-(N ,N'-dimethylsulfsmoylamido)-phenyl)-dimethylsulfamide
/~ -I N
With respect to compounds under formula (IV),
note the compounds already set forth hereinabove as examples
under formula (II).
In addition to the above formulas, an infinite
number of polyfunctional molecules can be synthesized.
However, the functional group or repeating unit in each of these
molecules would still be a N-monosubstituted sulfonamide
or sulfamide as depicted in formulas (I) through ~IV).
For instance, the polysulfonamides prepared from aromatic
12
Docket 2752
~'~14637
disulfonyl chlorides and aromatic diamines, such as poly-
condensa~e of benzene disulfonyl chloride and p,p'-diamino-
diphenylme~hane (also called methylene dianiline):
ClO2~2Cl (-~HCl) ~H H O
t o
With respect to the above reaction scheme, the molecular
weight can be controlled by carboxymethoxybenzene sulfonyl
chloride ~s a reaction terminator. Another such a poly-
condensate is the product of a mild, selective hydrolysis
of the methyl esters of the reaction product of two moles
carboxymethoxy benzene sulfonyl chloride (CBC from Sherwin-
Williams Co.) with trimethylene glycol di-p-aminobenzoate
(Polacure 740M from Polaroid Corporation), k
trimethylene bis ~N-o-carboxylphenylsulfonyl)-p-aminobenzoate
O H Q O H O
~ G N ~ -C~-O-(cH2)3-o-c- ~ -N-~ ~
C2H C02H
An even fiuperior compound is the complex of mixed zinc
salt that results from reacting the above compound with
more basic zinc salts.
The synthesis of all of the above compounds is
quite straightforward. They are prepared by reacting the
appropria~e sulfonyl (or sulfamoyl) chloride with an amine,
amide, or sulfonamide. The reaction (for amines) can be
performed in an aqueous solution or suspension by using
the Schotten-Baumann technique with sodium carbonate as
base (see Scheifele and ~.F. Detar, Org. Syn. Coll. Vol. 4,
~ Docket 2752 ~
`..` lZ14637
34 (1963)). AlternatiYely, the r~action (for amides and
~ulfonamides) may be performed in an inert solvent such
as acetonitrile (see E. Muller, ed.
Methoden der Or~anischer Chemie (Houben-Weyl), vol. 9,
4th ed., Geo~g Thieme Verlag, Stuttgart, West Germany, pp.
398-404, 605-648 (1955)).
The following compounds are further examples of
the present inven~ion:
N-toluenesulfonyl--aminophenylacetic acid
(N-~oluenesulfonyl-~-phenylglycine)
COOH
CH3 ~ -S0
H H
N-phenylsulfonyl-~-aminophenylacetic acid
COOH
S 2 1 1
H H
M-(m-carboXybenzoyl)-p-toluenesulfonamide
H o COOH
CH3- ~ -S2 N `
..25
N-~m-carboxy benzoyl)-benzenesulfonamide
N-~m-carboxybenzoyl)-N',N'-dimethyLsulfamide ..
N-(o-carboxybenzoyl)-p-toluenesulfonamide
H COOH
CH3- ~ -S02-N-C~
. 14
Docket 2752
637
. . .
N-(o-carboxybenzoyl~benzenesulfonamide
N-(o-carboxybenzoyl)-N',N'-dimethylslJlfamide
N-(m-nitrobenzoyl~-p toluene ~ulfonamlde
O
CH3 ~ 2 1 ~
H 2
N (m-nitrobenzoyl)-benzenesulfonamide
. N-(m-nitrobenzoyl)-N',N'-dimethylsulEamide
N (p-nitrobenzoyl)-p-toluenesulfonamide
O
CH3_~>-so~-N-c-~3-o2N
H
N-(p-nitrobenzoyl)-benzenesulfonamide
N-(p-nitrobenzoyl)-N',N'-dimethylsulEamide
N-(phenylsulfonyl)-p-toluenesulfonamide
CH3- ~ -S2-N-s2 ~
N-(phenylsulfonyl)-benzenesulfonamide
4,4'-oxybis[N-(phenylsulfonyl)-benzenesulfonamide]
~ H
~ SO2-~-S02 ~ _o_ ~ -S02-N~Scl2~
Docket 2752
~214637
It should be noted that the most preferred electron
withdrawing groups (G and G') are -$O2R; -COOH; -OR;
-COOR; -COR; -NO2; -CN; and the halides. The most preferred
set of electron-withdrawing groups are -SO2R; -COOH; -OR;
-COOR; and -COR.
The following preparative example shows a method of
synthesifi of one of the compounds used in the present invention.
It should be understood that all of the other compounds can
be made by analogous synthesis or in manners which are already
known to the prior art, or could be derived from methods
known to the prior art without undue experimentation. Through-
out all of the present examples and claims all percentages
are by weigh~ unless otherwise indicated.
Preparative Example ~ Preparation of N-(p-n-butylphenyl)-o-
carboxybenzene sulfonamide
~C-OCH3
H5C4 _ ~ NH2 + ~ SO2-Cl + 2Na2CO3
~C-OCH3
~ S2 - N ~ -C4H5+ 2NaHCO3 + NaCl (1)
Na
The first stage of the reaction (as shown in reaction
scheme I hereinabove~ is carried out by dissolving 254.4 g
~2.4 moles) of sodium carbonate (granular, 99+%, ACS reagent
grade) in 1.5 liters of water. The solution is heated to
50C, and at 50-60C, 149.2 g or 157 ml ~l mole) of p-n-butyl-
aniline (97% purity) and 281.6 g of carbomethoxybenzene
su]fonyl chloride (commercially available under the name
CBC) are added alternately in five portions each. The dual
16
Docket 2752
~;~14637
additions of the five portions of each reactant are timed
at approximately 5 minute intervals. That is, 31.6 ml of
butylaniline is sdded and followed directly by ~he addition
of 56.32 g of CBC. After 5 minutes have passed, the next
portions are added again in immediate succession, i.e.,
31.6 ml butylaniline followed by 56.32 ~ CBC. This continues
until all five portions of each reactant hclve been added.
Sodium hydroxide may be added in case carbon dioxide is
evolved which occurs if an insufficient amount of sodium
carbonate is present.
After all of the reactants have been added, the
temperature is raised to 80C and held for 25 minutes, and
the mixture then cooled to room temperature.
.,
0~ O~
C-OCH3 `C-OCH3
2-N~C4H5 + NaHC03 - ~ ~so2-NH~c4H5
Na
+ 2NaCl + C2t + H2O (II)
Reaction scheme II is carried out by slowly adding
the cooled reaction mixture into a 4 liter beaker containing
250 ml water and 300 ml of hydrochioric acid (37%), and
equipped with an efficient stirrer, taking care that the
mixture does not foam over. The dispersion is chilled in
a refrigerator over night. The crude N-(p-n-butylphenyl)-o-
carbomethoxy benzene sulfonamide settles on the bottom of
the beaker as a brownish, viscous mass. The water layer
is poured off and replaced by a solution of 80g sodium hydroxide
in 1.5 liter of water. The resulting solution is heated
for 2 hours at 85C to hydrolize the methyl ester (reaction
scheme III).
Docket 2752 1214637
C-OCH3 ~C-ONa
S02-NH ~ C4H5 2NaQH~ ~ S02~ N ~ C4H5 ~ CH30H (III)
Na
The solution is filtered at room temperature to
remove a very small amount of black precipitate. The solution
is a~ain poured into a 4 liter beaker containing 250 ml water
and 300 ml hydrochloric acid t37%). (Reaction scheme IV)
~-ONa O~C-OH
2-l ~ C4H5 ~ S02-NH ~ -c4~5l ~2NaCl (IV)
Na
The pro~uct is isolated by filtration using a
Buchner funnel, and is washed with water on the filter.
The filtrate is allowed to air dry, and then pulverized
to a light brown to beige powder. The yield is approximately
90% ~based on butylaniline) and purity is approximately
95%. The procedure could be,simplified by consolidating
reactions I and III, as well as II and IV, thereby avoiding
the difflcult to handle methyl ester. The procedure is
an adaptation of the related preparation of p-toluenesulfonyl
anthranilic acid as submitted by H.J. Scheifele, Jr. and
D.F. DeTar in Organic Synthesis, Collective,volume 4, p.
-
37 (1963).
The following éxamples show methods of formulatingcoatings containing the developers of the present invention
for application to pressure-sensitive recording papers.
The coatings are formulated to be porous. This permeability
18
~, .
Docket 2752 1214~3 7
is usually obtained through the use of fillers, such as
aluminum oxide, zinc oxide, silicon dioxide, clay or organic
thixotropes. The binders are predominantly saturated aliphatic
or aromatic compounds. The number of extraneous, organ~c,
polar groups in the final, dried coating are kept to an
absolute minimum. Acid groups and their metal salts are
the notable exceptions. The color developer should be the
predominant, non-fugitive, polar material in the CF coating.
For example, in the moisture set ink below, the full color
developing potential appears only after the solvents (diethylene
glycol, triacetin, and absorbed water) leave the film during
the setting process. It will be understood that other fillers,
binders and solvents can be used to complete the compositions
of the ptesent invention,all as are conventional in this
art and well known.
Example 1 - An Aq~ous Coatin~
5.4% trimethylene bis(N-(o-carboxylphenylsulfonyl)-
p-aminobenzoate) was added to 3.7% ammonium hydroxide in 26~/o
aqueous solution and 50% water, and mixed until completely
dissolved. Thereupon 10% Pencoate RBB 725 (an oxidized
starch from Penick and Ford, Division of Pacific Resins and
Chemicals, Inc.), l~b zinc ammonium chloride and 30% zinc
oxide were added and mixed thoroughly in a high speed mixer
or mill.
As an alternative to the above approach of incor-
poration, the sulfonamide (or its zinc salt) may be pulverized
in a ball mill, and then simply mixed with the rest of the
components. If zinc salt is used, then the ZnO may be replaced
by hydrated alumina.
19
'
Docket 2752
3~
Example 2 - A Letterpress Coatin~ - Moisture Set Ink
.
A kettle was charged with 24.7% diethylene glycol
and 24.7% triacetin (glyceryl triacetate). S~O Lacros 2~4
~an acid modified rosin resin from Crosby Chemlcals, Inc.)
was added and heated to 95C for 30 minutes or unti~ dis-
solved. Thereupon, 30.0% n-butyl-N-(-o-carboxyphenylsulfonyl)-
p-aminobenzoate was added and, upon dissolution, 4.0% Kadox
15 (zinc oxide - chemical grade from New Jersey Zinc Co.)
was added. The temperature was maintained at 100-105C
for one hour, although a longer heating period may be required
for more inert grades of ZnO. 5.0~O diethylene glycol mono-
stearate, 5.0~ zinc octoate snd 0.1% benzotriazole were
added in quick succession and cooled to 65C. Then 1.5%
(or less, if preferred) Crayvalac SF (organic thixotrope
from Cra-Vac Industrie, Inc.) was added and dispersed thoroughly
with a high speed mixer, and drained through a mesh filter.
The active ingredient is the zinc salt n-butyl-N-(-o-carboxy-
phenylsulfonyl)-p-aminobenzo te.
Example 3 - A Flexo-Gravure Coating
10% trimethylene bis(N-o-carboxyphenylsulfonyl)-
p-aminobenzoate) and 16.0% Lacros 294 were dissolved in
62% ethyl alcohol. To this solution, 10.0% zinc octoate
(18~ Zn) were added while stirring. Into this clear solution
were dispersed 2.0% Alumina Oxide C (fumed aluminum oxide
from Degussa Corp.) or 2.0% fumed silica ttrade name "Aerosil"
200 or R 972 from Degussa Corp.).
Example 4 - Transfer Litho tLetterpress) Ink
__
A mixture of 37.0% mineral seal oil and 30.3%
zinc octoate (9S% pure with remainder as mineral seal oil)
Docket 2752 1214~37
is heated to 100C and then 10.2% zinc resinate (Poly Tac
100 from Reichhold Chemicals Inc.) is added. After a clear
solution is obtained, 18% N-(p-n-butylphenyl)-o-carboxy-
benzene sulfonamide prepared by the method of the preparative -~
example above, is added. 2.2% zinc oxide (Kadox 15 from
New Jersy Zinc Co.) is dispersed into the solution and the
solution is heated for l-l/2 hours at 100-117C. The mixture
is cooled down to 80C and 1.5% Cravalac SE is dispersed
with a high speed mixer. If the texture Or the ink is too
coarse, the ink is passed through a 3-roll mill. The color
developer is present in the form of a fine dispersion.
Examples 5 and 6
Following the same general procedure as set forth
in example 4, other transfer litho (letterpress) inks can
be made using different sulfonamides. Two examples of same
showing the relative amounts of components are set forth
hereinbelow in Table l:
Table l
ExamDles 5 6
Components wt.% wt.%
. ~ . _ . _
~lineral seal oil 33.7 32.4
Zinc octoate 28.0 25.4
Zinc resinate 6.7 5.9
N-(4-n-octylphenyl-o-carboxy-
benzenesulfonaminde 26.4 0
N-(4-n-dodecylphenyl)-o-carboxy-
benzenesulfonamide 0 :32.4
Zinc oxide 2.7 2.9
Cravalac SF __ l.l
The color developers in 5 and 6 are present in solution.
Table 2 shows the color developing power of the products
of examples 4, 5 and 6, as compared to a con-mercial product:
- Do cke t 2 7 5 2 ~ 4~37
~ l ~
v. 1~ r ,C
O u~ ~: ~n
_ .,1 ~~ ~ ~ ~r~
~1 O ~ ~I t~ t) C
a~ ~ ~ _ ~ ~ aJ ;~
l ~ ~ ~ ._ a~ _
~a~ _. _ _ ,~\
_
+ I t I + I + I
_I
E~ z; r~ r7 ~ ~
~_ ~ l l l .'
O r r.
.) ~ U~ ~ ~11~ ~q ~
~_ O ~ ~ .,~ ~J ~, ~J
~ C~ ~ t~ ~ t~ ~ ~1
C~ ~ ~ ~ ~
_ . _
l O ~ ~ C~l
c~:: 2; +1 +~ +1 +1
. Z ~1 u~ ~ ~ ~r I
. . .
~ ~ _~
_~ o ~ a~ ' a) aJ
_
~) O O
~, o ~ ;~ m a~
c~ ~ _
~ . _
_.
D
n~ ~ O c~l ~ c~
E~ Z +l +l +l +l
~ ~ ~ ~ ~ u
Z Z ~ u~ `D ~ .C~
_ _ 3
D C E
u D t~
3 c~ c~ c~J O O
QO ~: Ei 6 E~i ::~ C `J
C 1-1 t~ W ~0 O-,~ tl~ O :~
u~ Q~ ~ .,, Q, ~
J_l ~ ~D 0~ ` ~ tO ~ V O C)
ta O . . . ~J O O ~ 1' 3
O O . O ¢~)~ ~ O
C.) C~
I U ~, r
Ul . U
3 l " ,~ c o
coo c~ ~ ~ c ,~ o
C ~ O Ei ~ _ `J . E
~ o _- ~ ~ c~ _, ~ ~ a~ u
~C~ ~ ~0 . . . l~.D U ~ o
, O O o oo U~ C
0 ~ o . C
O C:~ o ~ u ~ a~ ~ ~
3 ~ ~0
u L ~ E
Ll D ~r~
.~ , ~ V
~ ~ ~ C~ ~ ~
l l l ~: ~ ~ u~ C
~ U~ ~ ~ 1:~ ' ~ V
aJ ~ ~ t~ ~ ~ I'
_1 r-~ ~ L~ I C
E E . E E c~ ~1 U P~ --v ~: ~
~ t~ ~ O Z
~:~ ~1 ~ t~ ~ ~
_
Docket 2752
~ 3 7
Example 7 -_Comparative Exam~le
The following is a comparison proving the superiority
of the compounds of the present invention to those of comparative
compound 3 in Japanese patent application 1'379-111905.
l(a) 10g zinc salt of N-(4-dodecylphenyl)-o-carboxybenzene-
sulfonamide wa~ dissolved in 50 ml of ethyl acetate, as
described in "Application 1" of JP 1979-111905. This solution
was applied to 11 lb. paper stock (41g/m2) at a coating
weight of 0.2 glm2. The resulting CFl sheet was mated with
commercial NCR CB paper (15~), and the 2-ply formset was
fed through a mini-calander set at 30 psi pressure to produce
37 kg/cm. After one hour, the ima8e intensity was measured
on a BNL-2 Opacimeter from Technidyne Corporation as reflectance
percen~ of the imaged area relative to the sheet.
l(b) A CF2 was made and tested as above except the
coating solution contained 10g N-(4-dodecylphenyl)-o-carboxy-
benzenesulfonamide and 10g zinc octoate in 50 ml ethyl acetate.
2(a~ The above procedure l(a) was repeated using the
zinc salt of N-(octadecyl)-o-carboxybenzenesulfonamide as
the color developer to produce CF3.
2(b) A CF4 sheet was prepared as in l(b) except N-(octadecyl)-
o-carb~ybenzenesulfonamide was used as the color developer.
Results: A low reflectance value 9 R, represent~ an intense
image.
23
Docket 2752 1214~37
Table 3
. . . _ .
Reflectance
CF Sheet % Comments
. __
Zn[N-4-dodecylphenyl~-o- The preferred color developers
carboxybenzenesulfQnamide]2 58of,the present invention
CFl
_ .
N-(4-dodecylphenyl)-o- 54
carboxybenzenesulforamide
CF2
Zn [N-octadecyl)-o-
10 carboxybenzenesulfonamide]2 96*The comparative compound 3
CF3* in JP 1979-111905
--- _ ................. .
N-octadecyl)-o- 87
carboxybenzenesulfonamide
CF4
_ . ....
Plain 11 lb ~41 g/m) 100
Paper sto,ck
. _ _
Commercial NCR 46 Phenolic resin used as color
CF paper 15# developer.
_ Coat weight ~ 0.8-1.2~/m2
.
* The coating solution of CF3 was not homogeneous. As a result,
CF2 and CF 4 is better comparison
The preferred color developer is significantly better than
the comparative compound 3.
It will be obvious to those skilled in the art
that various changes may be'made without departing from
the scope of the invention and the invention is not to be
considered limited to what is described in ~he specification.
24
