CA1261625B - Color developers for pressure-sensitive or heat- sensitive recording papers - Google Patents

Abstract

Abstract of the Disclosure A color developer for use in pressure-sensitive or heat-sensitive recording papers comprise N-monosubstituted sulfonamides which contain at least one electron-withdrawing group within five atoms of the amido group of the sulfonamide.
The N-monosubstituted sulfonamide may be in the form of an N-substituted, N'-mono or di-substituted sulfamide, or a polyfunctional molecule containing such an N-monosubtituted sulfonamide as the functional or impeding group thereof.
The maximum color developing potential if realized when these compounds are used in conjunction with a source of metal or metal compound.

Description

Docket 2752 ~ J
~ichael E. A. ~ Itz

2~6 <
COL~R PEVELOPERS FO~ PRESSU~E-SENSITIVE 0~
~ . .
HEAT-SENSITIYE RE~O~ING PAPERS

Field of the Invention The present invention relates eo novel color developers for u~e in c~rbonless copy p~pers (CCP) and thermal imaging p~per~ ~TP) which will produce a stable intense mark when placed in contact with colorless dye precursors. The present invent~on also relates to record material sheets bearing c~a~n which cont~ins ~uch 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 colored dyestuff or colo~ precursor.
The other co~ponent is an ac~dic material or color developer which is capable of ~orming ~ color ~y reactio~ with the dyestuff or color precursor. Marking of the recording papers is effected by pressure ar heat which transfers one reactant to the other.
Pressure-sensitive recording material consists, for example, of at least one pair of sheets which contain 2t le~st one dyestuff or c~lor precursor,dissolved in an organic solvent,and ~ color developer. The dyestuff or color precur~or effects 8 colored marking at those points where it comes ineo contact wi~h the color developer.
In order to prevent the color precursors csntained in the pressure-sensitive recording msterial from becoming ~5 ~ctive prematurely, they ~re usually separated from the developer. This can advant3ge~0usly be accomplished by ~ocket 2752 incorporating the color precursor~ in fosm-like, ~ponge~ e, or honeycomb~ e structures. Prefer~bly, the color former~
are enclosed in ~icrocspsules which usually can be ruptured by pre~sure.
In ~ common method of manufacture of pressure-~ensitive recording p~pers, '~etter known ~s carbonless copy papers, a layer of pre~sure-rupturable microcapsules containing ~ ~olutio~ of eolorles~ or ælightly colored dyestuff or color precursor, i8 normally co~ted on the backside of ehe front sheet of paper of ~ carbonless copy paper set. This costed back~ide is known as the CB coating. In order to develop an imflge or copy, the CB coating must be ~ated with a paper containing a coating of suit~ble color developer on it6 front. This coated front color developer coating is called the CF eoating. Marking of the pressure-sensitive recording papers is effecting by rupturin~ 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 lt The colorless or slightly colored dyestuff, : 20 or dyestuff precursor, then rescts with the color developer in the areas 8t which the pressure was applied, thereby affecting the colored marking. Such mechanism or the producing tecbnique of pres~ure-sensit'~ve recording papers is well known.
: 25 V~rious developers for use in thermoreactive recording material are also well known. Thermoreactive recording ~aterial ~sually eontains at least one carrier, one color precur60r, one ~olid developer and, optionally, also a binder.
The thermoreactive recording systems comprise, ~or example, 30 heat-sensitive recording and copying materials and papers.

Docket 27~2 .1 .

~ 2 ~ 2~

The~e ~yste~s are used, for ex~mple, for recording information, e.g., ~n electronlc computer~, teleprinters or Eelewriters, or ~n recording and measuring instruments. The image (mark) for~ation can al80 be effeeted manually with a heated pen.
5 L~er beams can slso be used to produce heat-induced marks.
The ther~oreaceive recording m~terial can be so composed that the color presursor i8 disper~ed or di~solved in one b~nder l~yer ~nd the developer is dissolved or dispersed in the binder in ~ 6econd lsyer. Another possibility consists in disper~ing both the color precursor ~nd the developer.
~n one l~yer. By means ~f heat, the binder is softened at spec$fic areas And the color precursor comes into cont~ct with the developer at those points where heat is applied .
and the desired color develops ~t once.
lS Color precursors ~re well knowa to those experienced in the field and ~ny such color former may be used in conjunction with the present invention, e.g., those belonging to the : clssses of the phthalides, fluoranes, spiropy~anes, azomethines, tri~rylmethane-leuco dyes, of the substituted phenoxazines or phenothiazines, ~nd 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)-phth~lides~ 3-(aminophenyl)-3-indolyl-phthalides, 6-diaalkylAmino-2-n-octylaminofluoranes, 6-dialkylamino-25 2-arylaminoflvoranes, 6-dialkyl~mino-3-methyl-2-arylaminofluoranes, ~ 6-dial~ylamino-2- or 3-lower ~lkylfluorsnes, 6-di~lkylamino-2-:~ . dibenzylaminofluor~nes, 6-dialkylamino-2-dibenzylaminofluor~nes, 6-di~thyla~ino-1,3-dimethylfluoranes, the lactonexanthen~s, the leuco~uramines, the 2-(omega substituted vinylene)-3,3-. 30 disubstituted-3-1-1-indoles, 1,3,3-trialkylindolinospirans, ~, Docket 2752 ~26~62~
. .
bi~-5a~inophenyl~-uryl-, phenyl- or carbazolylme~hane~, or benzoyl~l~ucomethylene blu0.
~nown color developers for use in such pressure-sensitive or h~st-~ensitive reeording papers have Included:
(l; novolac phenolic resins made by acid c2talyzed condensation of phenol, resorcinol! pyrogallol, cres~ls, . . xylenols, or alkyl phenols such as p-tertiary butyl phe~olJ~ith aldehydes such ~s formaldehyde, ~cet~ldehyde, benzaldehyde, and butyraldehyde;
(2) Met~l 691t8 of ~romatic carboxylic acid~
with ~n OH group ~t the ortho position, such as zinc salts of salicylic acid, 3,5-di-tert-butyl salicylic Acid, octyl salieylic acid, ~nd l-hydroxy-2-naphthoic acid, and

(3) ac~d-treated clays such as kaolinites 3nd -~tapulgite6.
The search has continued for other developers having high developing power, rapid developing speed, good light resistance and time st~bility. Examples of some colored developers whlch have been developed-in the past which are fio~ew~at related to those of the present invention are disclosed in U.S. p~tent 4,291,901 to Petitpierre and Japanese patent di~closure 197~-lli905.

! 25 Accordingly, it is 8n object of the present invention to prov~de a novel color developer.for use in pressure-sen~itive or he~t-~ensitive recording papers.
It is another ob~ect of the present invention to provide an improved record sheet co~ted wi th such a novel 30 color developer.

_ ~ocket 2752 ~2~5~625 .

A furtb~r ob~ect ~f the present invention to provid~
~uc~ ~ color developer with ~xcellent eolor developing properties.
These and other ob~ects of the present invention ~re obtained by mea~s of the novel color developers of the pr~sent ~nventlcu which are, In part, N-monosubstituted sulfon~mides which eontain ~t least one electron-withdr~wing group. Th~ s~ple sulfon~mideæ and n-monoalkyl sulfonamides (RS02NH2 ~nd RS02N~R' respectively) have acidities that are eOo wea~ fo~ these materi~ls to be very useful as primary ~0 color developer~. They ~re useful as film modifiers and/Qr ~eco~dary color developers. However, the addition of an : electron-withdrawing group not more than five (5) atoms ; from the NH group on the sulfonamide increases its acidity (via the inductive effect), ~nd mskes the 8ul fonamides suitable for u e as primary color developers. Where applicable, the pX~ t-log K8, where Ka i~ the scid dissoci~tion const~nt~
of the sulfonyl~mide (-S02-NH-) ~roup ~hould be in the r~nge of 9.5 to 2.5, and preferably in the rsnge of 8 to 4. Suitable electron-withdrawing groups are tho e substituents which ~ posse~s po~Itive Ha~mett or Taft constants. The novel color developers can also be N-monosubstituted, N'-mono or di-substituted ~ulfamide~ [R'''~Rol')-N-S02NHRo'3. Again for the reasons ; . stated ~bovet ~n electron-withdrawing group must be no more th~n 5 atoms from the NH grovp The maXiDUm color developing potential is realized when these N-mono~ubstituted sulfonamides or N,N'-substituted ~ulfamides ~re used in eonjunction with some source of metsl or me~l compound. Specific~lly, the sulfonamines or sulf~mides : may be . . .

Docket 2752 ~ 2~

(1) mixed with or dis~olved in an or~anic metal ~lt ~uGh ~s z~nc oleate, zinc octoate, and zinc ace~te9 (~) precipit~ted onto a metsl oxide hydroxid~, or carbon~te ~uch a~ zinc oxde, zin~ hydroxide, or zinc carbon~te, (3) co-precip~tated from water with soluble met~l s~lt~ e zinc chlor~de, zinc smmonium chloride, or zinc sulfate, or ~ 4) chemically modified by ~ metal so as to incorporate - 10 the ~ee~l into the 8ul fonamide or sul f~mide molecules .
The latter will take the form of organic acid salt formation by reacting elther an extra -S-NH- group or a COOX group in the 8ul fon~m~de or sulfamide w~th a basic , metal oxide or carbon~te. The ~alt may also be formed by reaetion of alkali ~alt of the sulfonamide (or sulfamide) with ~ soluble acidic ~etal s~lt sueh ~s zinc sulf~te.
The above exsmples ~re restricted to zinc for the sake of being conci~e. Other metals such as aluminum, barium, bi~muth; calcium,cerium, cesium~ lithium, magnesium, tin, and tit~nium may be used in place of zinc.

Detailed Descri tion of Preferred Embodiments P.~
The present invehtlon comprehends all compounds which include a ,sulfonyl~mide ~-S02NH-~ group and alsQ include ~n electron-withdr~wing atom or moiety within five atoms of the NH group. However, tbe compound must be free of any bsslc group, for ex~mple, epoxy or NH2~ Any additional groups w~thin the compound must be no more than one csrbon away fro~
an ~ group, or to ~ C'Ot C~N~ or NO~ group. The present invention further excludes ~uch eompounds in which the electron-~ithdrawing --~ Docket 2752 ~ ~6 ~

g~OUp i8 ~ c~rboxy phenyl ~roup connec~ed throu~h the nitrogen AtOm of ~he sulfonylamide group or in which the ~ole electron-~ithdr~wfng ~roup ~s 9 c~rboxyphenyl group. Also excluded 8re ~ompounds hav:ing ~ hydroxy group Oll the opposite side of the amide from the 8ul f~nyl ~roup of the ~ulfonyl~mide grouping.
P3rticul~rly preferred 8ul fonylamide compound~
in accord~nce wi~h the pr~sent invention hav~ electron w~thdr~wing ~roups on both sides of the 6ul fonyl~mide grouping.
Svb~ect to the sbove conditinns, the electron withdr~wing group can be any of ~he following: -NO2, -SO2R, -CN, -SO2Ar, -CQOH, -SO2NH2, -SO2N~R, -SO2NR2, -~, .Cl, -Br, ~ OAr, -COOR, -COOAr, -OR, -OH, -SR, -SH, -COR, -COAr, -C'CR, -Ar, -CH~CR2, wherein R is an alkyl group of up to 18 c~rbon atoms, preferably 3-8 carbon atoms, and Ar is any aryl group, preferably phenyl or naphthyl. The R and Ar groups may be optionally 8ubstituted 8S long as the ~bove conditions &re ~et.
Particul~rly u~eful compounds for use as color developers in accordance. wi.th the present invention are N-mono~ub~tituted sulfonamides represented by formula O H
Rl-S-N-(R2)n-G (I) O ~ .
where Rl ~nd R2 ~re alkyl (branched or Iinear~ preferAbly : with no more than 18 c~rbon ~toms and mos~ preferably with 3-8 carbon ~toms, aryl, preferably phenyl or n~phthyl, or ~ co~bination of both, e~ch of which m~y be substituted or un~ubstituted, s~id ~ubstituents, if any, being 3~ any group other than ~ basic ~roup, such 8S epoxy or NH2,.
and if -NH lt must be no more than on~ c~rbon ~tom aw~y from a SO2, C-O, C~N or NO~ group;

1, --~Docket ~752 ~ ~6~6 ~

G i~ 3n electron withdr~wing group as defi~ above ~nd is ~ot ~ore than five ~toms aws~ from the -NH- g~oup~ with the proviso that : G ~ not -OH or -SH when n is 1 and with the further proviso th~t ~(R2)n-G i~ n~t ~ COOH; ~nd ;n is 0 or 1.
Other ~ulfon~mides useful ~n the practice of the pre~ent invention are those in accordance with formula O H
G-(R2)n-S-N-R
o tl .
wherein n, Rl, R2 and G ~re as defined above with the proviso that Rl i8 aot ~ COOH and with the furthe~ proviso that G is not COOH in formula II whcn all of the following three con-dltions apply: R2 is aryl, n is 1, and Rl does not com-prehend or include an electron-withdrawing group (as defined -~bove for G) within 5 atoms of the NH group.
, Analogous to the ~ul fonamides above, the N-mono-substituted, N'-mono or di-substituted sulfamide color developers, ~hich ~re ~180 particularly useful in accordance with the presen~ Invention, are represented by formula III below:

R ~ 11 ~ ( 2) (III) : O
~: where R2, G ~nd n ~re as defined ~bove and R3 and R~ are as .
defined ~bov~ for Rl and R? although one of ~3 and ~4 m~y~be H; furthermore, when one of R3 and R4 is H, the o.her m~y be an electron withdawing group as defined ; ~bove for G
The u~efulness o~ the N-monosubstituted sulfon~mides as color developers i8 enhanced further by placing eleceron-withdr~wing group6 on both sides of the sulfamoyl group.

O ~ ;

Docket 2752 ~ 2~ ~6 ~ ~

Preferred such compounds useful in the practice of the pre~ent invention sre represented by for~ula IV:
O H
G'-(R2)n-S-N-(R2)n-G (IV) wherein n, R2 and G sre 8S defined sbove ~Ind G' iB ~n electron wie~drswi~g group ~s defined above with respect to G.
While the ~ubstituents with respect to formulse I-IY and the remainder of the ~eneric formula ~s discucsed ~bove may include sny unction~1 group not specifically proscribed, it particularly may include additional -S02NH-~~l~yl, aryl ~nd electron withdrawing (as defined sbove for G) groups, and may~ in fact, be a polymer containing repeating units of any of the above.
Examples of compounds within formula (I) are 8S
follows: H
N-(phenyl sulfonyl)-p-toluenesulfonamide CsH5S02-N-S02C6H4~H3 N-phenyl-be~zene 6Ul fonamide ~ S02-N ~

:

~ Docket 2752 62~
~1 o n-butyl-N-(phenyl6ulfonyl~-p~minobenzoate ~ so2-h ~ C~OC4Hg . . H H ~
N-~-(p-toluenesvlfonyl3-DL-phenylalanine CH3- ~ S02 1 ~ CH2 :: S
N-(c~rboxymethyl)-p-toluene~ulfonamide CH3- ~ S02-N-CH2C02H

N-[o-(p-toluenesulfonamido) phenyl]-p-toluene~ul~onamide ;: H
~ ~ 2 ~

With re6pect to ex~mples of compounds of formula (II), it ~hould be noted that in Japanese patent disclosure 1979-111905, comparative compound example 3, i.e. N-(oct~decyl)-o-carboxybenzene ~ulfonamide, iE t~ught as being a poor developer j p3rticularly in comp~rison with the anthr~nilic developers dls losed by the Jspanese patent. It has surprisingly been discovered, however, that the addition of another electron withdrawing group, this time on the nitrogen side of the sulfon~mide, further increases the color developing.property and such compoun~ thus become preferred compounds of the present invention.
Exa~ples of compounds in formula (~I) including the above de6cribed preferred co~pounds ~re as follows:
.25 n-butyl-N-(o-ear~oxyphenylsulfonyl)-p-amino-benzoate '~ ~ S0 NH ~ C~ C H
N-(o-carboxyphenyl 6ul fonyl)-4-aminobenzophenone 02-NH-~_ io `~ocket 2752 ~ ~6~ 6 ,, .
N-(o-carboxyphenyl~ulfonyl)4~aminobenz2ne~ulfonsmide : ~ 52 ~ 2 2 ~-(4-n-butylphe!nyl~-o-carboxybenzenesulfonamide ~ S02-NH ~ -(CH2)3-C~3 N-~4-oc~ylphenyl)-o-carboxybenzenesulfon.~mide co2~
~ S02-NH- ~ -(CH2)7-~H3 N-(4-dodecylpheny:l)-o-carboxyben~enesulfonamide ~02H

~ S02-NH- ~ -(CH2)11 3 ,15 ~-(2,4-diethylphenyl)-o-carboxybenzenesulfonamide ~ S02-NH ~ CH2 3 ; 20 With respect to all of the above acids, the preferred form i8 that of the metsl salt, particularly an alkaline e~rth metal s~lt, ~nd more particularly a zinc salt.
Example~ of formul~ (III) are:
N (di~ethylsulf~moyl)-p-toluenesulfonamide ~ 25 CH3 B H B
: ~ ~S-N-S- ~ CH3 ~3 11 11 O O
N-phe~yl-N'-i~opropyl6ulfQmide ~ H Q H

~3 o Docket 2752 ~Z~ 25 , N-benzoyl-N'~isopropyls~lfa~ide CX3 1 ~ ISl N ~
C~3 0 .
N-phenyl-N',N'-dimethylsulf~mide CH~

O

N-(dimethyl 6ul famoyl)-~-aminophenylacetic acid 3~N-s-N~
..

N-(o-(N',N'-di~ethylsulfa~oylamido)-phenyl)-dimethylsulfa~ide CH~

~;-g-~ 3 With respect to compounds under formula (IV), note the co~pounds ~lready'set forth hereinabove as examples ~ u~der form~la ~II).
; 25 In ~ddit~on to the above formula~, an infinite number of polyfunctional molecules can be synthesized.
:~ ~owever, the fun~tional group or repeating unit in each of these ~olecules would 6till be ~ N-monosubstituted sulfonamide or ~ul~mide ~s depicted in formulas (I) through ~IV).
For instance, the polysulfonamides prepared from aromatic ,, ~

Docket 2752 ~ 5 d~6ulfonyl chlorIde~ ~nd ~romstic di~mlnes, such ~s poly-conden~te of benzene di~ulfonyl chloride &nd p,p'-di~mino-diphenylmethane ~al~o called methylene dianiline):

ClO2 2~ 2~Cl) ~l H O
. ~ 2 ~ 2 ~ 2 t " 2~ 11 ~ 2 ~

With respect to the above re~ction scheme, the molecular weight c~n be controlled by carboxymethoxybenzene sulfonyl chlorlde dS 8 reaction terminstor. Another such a poly-condensate ~8 the prod~ct of a mild, selective hydrolysis of the methyl esters of the reaction product of two moles carboxymethoxy benzene 6ulfonyl chloride (CBC from Sherwin-Williams Co.) with trimethylene glycol di-p-aminobenzoate (Polacure*740M from Polaroid Corporation), trimethylene bi6 (N-o-carboxylphenylsulfonyl)-p-aminobenzo~te O H O O H O

~ ~-N- ~ -C-O-(CH2)3-O-C- ~ N B ~
2 . CO2H
An even ~uperior compound is the complex of mixed zinc ~alt that result~ from reacting the above compound with more ba&ic zinc s~lt~.
The synthesis of ~11 of the above compounds is quite tr~ightforw~rd. They are prepared by reacting the appropri~e ~ulfonyl ~or ~ulfsmoyl) chloride with ~n ~mine, ~mide, or sulfonamide. ~he reaction (for amines) can be performed in an ~queous ~olution or 6uspension by using the Schotten-Baum~nn techn~que with sodium carbon~te ~s ba~e (~ee Scheifele and ~.F. Detsr, Org. Syn. Coll. Vol. 4, *Registered Trademark Docket 2752 3LZ~6;~
34 (1963)). Altern~tively, the reaction (for amides and sulfonamides) ~ay be pe~formed in ~n inert solvent such ~ ~cetonitrile (see E. Muller, ed.
Metho_en der Or ~ (Houben-Weyl), vol. 9, 4th ~d., Georg Thieme Yerlag, Stuttgart, West Germ~ny, pp.
398-404, 605-648 ~1955)~.
The following compounds are further examples of the pre~ent invention:

N-toluenesulfonyl~ minophenylacetic acid (N-toluenesulonyl-~-phenyl~lycine) COO~
~ CH3 ~ -so2-: ~ H
.~
., . .
N-phenylsulfonyl-~-aminophenylacetic acid COOH
~-SO2 1 1 ~ , H H

M-(m-carbo~ybenzoyl)-p-toluenesulfonamide H o COOH
CH ~ so I e ~

_.25 ~-~m-carboxy benzoyl~-benzenesulfonamide N-(m-carboxybenzoyl) -N' ,N ' -dimethylsulfamide ..

N-~o-carboxybenzoyl)-p-toluenesulfonamide H ~OOH
CH3- ~ -SO2-N-C~

Docke~ 2752 ~261625 N-(o-c~rboxyb~nzoyl~benzenesulfon~mide N-(o-c~boxyb~nzoyl)-N',N'-dimethylsulf~mide N-(m-nltrobenzoyl)-p-toluen~ ~ulfon~mi~e o ,, 11 .
.~10 N-~m-nitrobenzoyl)-benzenesulfonamide . N-(m-nitrobenzoyl)-N',N'-dimethylsulfamide N-(p-nitrobenzoyl)-p-toluenesulfonamide ll : ~ C ~ O N
H

N-(p-nitrobenzoyl)-ben~enesulfonamide N-(p-nitrobenzoyl)-N',N'-dimethylsulfamide N-(phenylsulfonyl)-p-toluenesulfonamide CH3 ~ -5O2-N-SO2 ~

; N-(phenylsulfonyl)-benzenesulfonamide . .
4t4'-oxybis[N-(phenylsulfonyl)-benzenesulfonamide]
H H
~ SO2-~-SO2 ~ _o_ ~ -SO2-N~

Docket 2752 ~ 2~ ~ 6 ~
It should be noted that the most preferred electron withdrawing groups t~ ~nd G') ~re -S02R; -COOH; ~OR;
-COOR; -COR; -N02; -CN; ~nd the h~lides. The most preferred ~t of electron-withdrawing groups are -S02R; -COOH; -OR;
-COOR; ~nd -COR.
I The followin~ prepar~tive example s~ow~ a methvd of ~ynthe~i~ of one of ~he compound~ used in ~he present invention.
It 6hould be under6tood that all of the other compounds csn be msde by ~snalogous synthe~i6 or in manners which are 31ready 10 known to the prior ~rt, or could be derived from methods known to the prior Art without undue experimentation. Through-out all o the present examples and claims all percentages sse by weight unless otherwise indicated.

Preparati~e Example - Preparation of N-(p-n-butylphenyl)-o-c a r boxybenzene s ul fonsmi de ~C-OCH3 H5C4 ~ NH2 ~ ~ S02-Cl ~ ~Na2C03 ~-OCH3 ~ S2 - N ~ -C4H~+ 2NaHC03 ~ NaCl (1) ~a The fir~t ~t~ge of the reaction (as shown in reaction scheone I hereinabove! is c,arried out by dissolving 254.4 ~
(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 (1 molei) of p-n-butyl-aniline (97~ purity) and 281.6 ~ of carbomethoxybenzene ~ulfonyl chloride (commercially avsilable under the name CBC~ are added altern~tely in five portions each. The dual i, , 'i . ..

Docket 2752 ~6 ~

~ddition of the fIve portlons of each reactant are timed at spproximately 5 minute intervals. That is, 31A6 ml of butylaniline is added and followed directly by the addition of 56.32 g of CBC. After 5 minutes have passed, the next portions ~re sdded again in immediate succession, i.e., 31.6 ml butyl~niline followed by 56.32 g CBC. This continues until ~11 five portion~ of each reactant have been added.
Sodium hydroxide may be added in csse 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 80~C and held for 25 minutes, and the mixture then cooled to room temperature.

~ ~ O~
~C-OCH3 C-OCH3 2-N ~ C4H5 + NaHC03 ~ S2 ~ C4H
N~
+ 2NaCl + CO2t + H2O (II) Reaction scheme II is carried out by slowly adding the cooled reaction mixture into ~ 4 liter beaker containin~
250 ml water &nd 300 ml of hydrochloric acid (37%), and equipped with an efficient ~tirrer, taking care that the mixture does not foam over. The dispersion is ohilled in a refrigerator over night. The crude N-(p-n-butylphenyl)-o-carbo~ethoxy ben~ene sulfonamide settles on the bottom of the beaker ~ a brownish, viscous mass. The water layer is poured off and replaced by a solution of 80g sodium ~ydroxide in 1.5 Iiter of waeer. The resulting solution is heated for 2 hours at 85C to hydrolize the methyl ester (reaction sehem2 III).

~.~
:. ..... . ..

`Docket 2752 ~26~2~;
.~ o ~-OCH3 ~C-ONa ~S02-NH~Hs~ ~S2 1 ~C4H5 + CH30H (III) Na The solution is f~ltered 3t room temper~ture to remove a very 8111~ll amount o~ black precipitate. The 601ution : i8 a~ain poured into a 4 liter beaker containing 25V ml wster ~nd 300 ml hydrochloric acid (37Z). (Reaction scheme IV~

~; ~C-~Na ~C OH
""", ~/ ,_ S02~ b ~ S02-NH ~ -C4H5l ~2NaCl (IV) Na The product i8 isolated by filtration using a 15 Buchner funnel, and is washed wi th water on the ~il ter.
The filtrate is sllowed to ~ir dry, and then pulverized to a 1 ight brown to beige powder . The yield is approximately 90Z (based on butylaniline~ ~nd purity is approximately 96~. The prvcedure could be ~implified by consolidating 20 reactions I dnd III, ~ well . as II ~nd IV, thereby avoiding the difficult to handle methyl ester. The procedure is an adaptation of the rel2ted preparation of p-toluenes~lfonyl anthranilic acid ~s submitted by H.J. Scheifele, Jr. and D.F. DeTar in Or&snic Synthesis, Collective,volume 4, p.
:
~; 25 37 (1963).

The following examples show methods of formulating eoating~ containing the developers of the present invention for ~pplication to pressure-sensitive recording papers.
The coatings are formulated to be porous. This permeability ,.,. ~

Docket 2752 ~2Gi~6Z5 18 u~u~lly obt~ined through the u e of filler~, ~uch ss ~luminu~ oxide, zinc oxide, ~ilicon dioxide, cl~y or organic tlhixotropes . The binders ~re predominantly saturated ~1 iph~tic or aromatic compounds. The number of extraneous, organ~c, S polar groups in ~he final, dried coating are kept to ~n ~bsolute mini~um. ~cid ~,roups ~nd their aletal 6alts ~re ehe notable exceptions. The color developer ~hould be the predominant, non fugitive, polar m~terial in the CF coating.
For ex~mple, in the ~oisture ~et ink below, the full color developing potenti~l appears only after the solvents (diethylene glycol, triacetin, and absorbed water) leave the film during the ~etting process. It will be understood that other fillers, binders and colvent~ can be used to complete the compo~itions of the present invention,all as are conventional in this nrt and well known.

Example 1 - An Aqueous Coatin~
S.4~ trimethylene bis(N-(o-csrboxylphenylsulfonyl)-p-aminobenzoate~ W8S added to 3.7% ammonium hydroxide in 26%
aqueous solution ~nd 50% water, and mixed until completely dis~olved. Thereupon lOZ Pencoate*RBB 725 (an oxidized ~tarch from Penick ~nd Ford, Division of Pacific Resin~ ~nd ; Chemicals, Inc.), lZ zinc.ammonium chloride and 30Z zinc oxide were added and mixed thoroughly in a hi~h speed mixer or ~ill.
A6 an ~lternative to the ab~ve approach of in~or-poration, the 6ulfonamide tor it~ zinc salt) m~y be pulverized : in ~ ball mill, and then imply mixed with the rest of the component~. If zinc salt is ~sed, then the ZnO may be replaced by hydrated ~lumin~.

*Registered Trademark ,;~

-~~ocket 2752 1 2~ 5 Example 2 A Let~er ress Coatin~ - Moisture Set Ink A ~ettle was charged with 24.7% diethylene gly~ol and 24.7X triacetin (glyceryl triaeetate). 5% Lacros 2~4 ~an ac~d modified rosin resin from Crosby C:hemicals, Inc.) 5 wa~ ~dded and heated to 95C for 30 minutes or unti~ dis- -solved. Thereupon, 30.0% n-butyl-N-(-o-carboxyphenylsulfon.yl)-p-~minobenzoate was ~dded and, upon dissolution, 4.0% Kadox*
15 (z~nc oxide - chemical grade from New Jersey Zinc Co.) was added. T~e temperature w~s ~ain~ained at 100-105C
for one hour, ~lthough ~ longer heating period may be required f~ more inert gr~des of ZnO. 5.0Z diethylene glyc~l mono-stearate, 5.0~ zinc octoate snd 0.1% benzotriazole were added in quick succession and cooled ~o 65C. Then 1~5%
(or less, if preferred) Crayvalac*SF (organic thixotrope from Cra-Vac Industrie, Inc.) was added and disper~ed thoroughly with ~ high speed mixer1 and drained through a mesh filter.
The active ingredient is the zinc salt n-butyl-N-(-o-carboxy-:~ phenylsulfonyl) p-aminobenzoate.

Example 3 - A Flexo-Gravure Coating -. 20 10~ tr;methylene bis(N-o-carboxyphenylsulfonyl)-p-~minobenzoate) ~nd 16.0% Lacros 294 were dissolved in 62% ethyl ~lcohol. To this solution, 10,0% zinc octoate (18% Zn) were ~dded while ~tirring. Into this clear solution were di6persed 2.0~ Alum;na Oxide*C (fumed aluminum oxide from Deguss~ Corp,) or 2.Q~ ~umed silica (trade name "Aerosil"*
200 or R 972 from Degus~s Co~p.).

Example 4 - Transfer Litho (Letter ress) Ink ~ P _ A mixture of 37.0% mineral 6eal oil and 30,3%
zinc octoate ~96% pure with remainder as mineral seal oil) *Registered Trademark 20 A

Docket 2752 ~2~;~6~S
i~ heated to 100C ~nd hen 10.2X zinc resinate (Poly Tac*
100 from Reichhold Chemicals Inc.) is added. After ~ clear ~ol~tion i obtained, 18X N-(p-n-butylphenyl)-o-carboxy-benzene sulfonamide prepared by the method of the preparative example sbove, is ~dded. 2.2X zinc oxide ~Kadox 15 from ~ew Jersy Zinc Co.) is di~persed into the solution and the solution i~ he~ted for 1-1/2 hours at 100-117C. The mixture i~ cooled down to ~0C ~nd 1.5X Cravalac*SF is dispersed with ~ h~gh ~peed ~ixer. If the texture of the ink is too coar~e, the ink is pas~ed through a 3-roll mill. The color develGper is present in the form of a fine dispersion.

Examples 5 ~nd 6 ' Following the same ~eneral procedure as set forth in example 4, other transfer litho (letterpress) inks can be made using different ~ulfon~mides. Two examples of same showin~ the relative amounts of components are set for~h hereinbelow in Table 1:
Table 1 Examples 5 6 - -~
20 _ Components _ _ _ wt.% wt.%
~liner~l seal oil 33.7 32.4 Zinc octo~ee 28.0 25.4 Zinc resin~te 6.7 5.9 N-(4-n-octylphenyl-o-carboxy-be~7.enesul~ona~inde 2~.4 0 N-(4-n-dodecylphenyl~-o-carboxy-benzenesulfonamide 0 32.4 2inc oxide 2.7 2.9 ~ Sr~v~l~c SF 1.5 1.1 The color developers fn S and 6 ~re present in solution.
Table 2 shows the color developin~ power of the products of example~ 4, 5 and 6, dS ~ompared to a commercial product:

*Registered Trademark 21 ~ .

ocket 27s2 ~ 12gGi~Ç25 l I ~
U O ~ V ~ r U
S~ ~ P~ ID P3 ~W

~ Z +l tl _ +~
:~ el:~ o~ r~) ~1 t-~
,. _ _ _ , "
. ~ O l ~ .C ,v v' ~ '~J~ ~ ~ =
ZO +1 ~+1 _ +1 . Z J ~ ~ ~ ~
_ _ __ , O ~V~r,, ~ .
t~ ~ P4~ P~

¦~ ~ ---- ----~1 o~ z +1 +1 +~ ~1 ~ ~
~ ~; Z ~ u~ ~D . .~

; ~ _ _ _ D ~ r ~ ~ fi ~6 Ei ~ C ~ O .D
C ~ ~ ~) ~) ~ v ~ O :~
V~ ~D ~ ~ ~ ~ ~ ~ Oa~
0 O ,0 O ~0 0~ ~
_ _ _ o~v~~ _l O Q _- 'c C O
~.) O ~ O ~ u ~: 3 :~ __ __ a~ 6 S~
6 ~" D ~d . X ~C .C
~4 ~C tL~ a~ ~I "
~J ~ ~D ~ ~ SL ; C ~ U
Q~ ~ ) CL
O C~ C~ ~
1~ 61 ~X t~Z . ,.
_ ~ocket 2752 3~6~16;25 =~
The following iR a comparison proving the 6uperiority of the co~pounds of the presen invention to those o compar~tive eompound 3 in J~panese patent upplication 1979-111995.

l(a) lO~ zinc ~alt of N-~4-dodecylphenyl)-o-carboxybenzene-sulfonamide WaB disfiolved in 50 ml of ethyl acetate, as described in "Application 1" of JP 1979-111905. This solution wa~ applied to 11 lb~ paper ~tock (41g/m2) at a coating weight of 0.2 g/m2. The resulting CFl sheet was mated with commerci~l NCR CB p~per ~15~ nd the 2-ply formset wa~
fed through a min~-cslander set ~t 30 psi pressure to produce : 37 kg/cm. After one hour, the image i~tensity was measured on a BNL-2 Opacime~er from Technidyne Corporation as reflectance percent of the imaged area relatiYe to the sheet.

I(b) A CF2 w~s made and tested ~s ~bove except the co~ting solution contained 10g N-(4-dodecylphenyl)-o-carboxy-benzenesulfon~mide and 10g zi~c octoate in 50 ml e~hyl ~cetate.

2(8) The above p~ocedure l(a) was repeated using the zinc 881t of N-(octadecyl)-o-carboxybenzenesul~onamide as the color developer to produce CF3.

2(b~ A CF4 ~heet wa~ prepared as in l(b) except N-(octsdecyl)-o-car~ybenzene~ulfonamide was used as the color developer.

Results: A low reflectance v~lue, R, represent~ an intense -im~ge.

Docket 2752 3l~6 Tabl e 3 ~ -- .

- -- Ref lec tance CF Sheet ~ Cornmen ts ~ ~ ~_____ _ _________ , ZnlN-4-dodecylphenyl) o- . The preferred color developer~
5 carboxybe~zenesulfonamide]2 58 of the present invention , . , ..
N-(4-dodecylphenyl~-o- 54 car~oxybenzenesulforamide . ...... ,._ __ . _ _ Zn [~-oc~adecyi)-o-lO carboxybenzene~ulfonamide~ 96* The comparative compound 3 CF3* in JP 1479-111905 = .,.. _ N-octsdecyl)-o- 87 carboxybenzenesulfonamide l .... _ ..
Plain 11 lb (41 g/m) 100 Paper stock -- . ... ...... _ ...... __ _ ....
Commercial NCR 46 Phenolic resin used as color CF paper 15~ developer.
Coat weight ~ 0~8-1.2g/m7 * The coating solueion 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 ~nd the invention is not to be considered limited to what is described in the specification.

Claims (15)

WHAT IS CLAIMED IS:

1. In a pressure-sensitive or heat-sensitive recording material including at least one support, a dye precursor and a color developer, the improvement wherein said color developer is a compound including a sulfonylamide (-SO2NH-) group and also including an electron-withdrawing atom or moiety within five atoms of the nitrogen atom of said sulfonylamide group, said compound being free of any basic group, with any addition-al NH groups being no more than one carbon atom away from an SO2, C=O, C?N or NO2 group, with the proviso that the electron-withdrawing group is not a carboxyphenyl group connected through the nitrogen atom of the sulfonyla-mide group, with the further proviso that the sole electron-withdrawing group is not a carboxyphenyl group and with the further proviso that said compound does not include a hydroxy group on the opposite side of the amide from the sulfonyl group of the sulfonylamide group.

2. A recording material in accordance with claim 1, wherein subject to the provisos of claim 1, said electron-withdrawing group is selected from the group consisting of -NO2, -SO2R, CN, -SO2Ar, -COOH, -SO2NH2. -SO2NHR, -SO2NR2, -F, -Cl, -Br, -I, OAr, -COOR, -COOAr, -OR, -OH, -SR, -SH, -COR, -COAr, -C?CR, -Ar, -CH=CR2, wherein R is an optionally substituted alkyl group and Ar is an optionally substituted aryl group.

3. A recording material in accordance with claim 1, wherein said compound has electron-withdrawing groups on both sides of the sulfonylamide grouping.

4. A recording material in accordance with claim 1, wherein said compound is:
an N-monosubstituted sulfonamide of the formula (I) in which R1 and R2 are alkyl, aryl or a combination of alkyl and aryl, each being substituted or unsubstituted, said substituents, if any, being any group other than a basic group and, if -NH; no more than one carbon atom away from a SO2, C=O, C?N or NO2 group, G is an electron-withdrawing group selected from the group consisting of -NO2, -SO2R, -CN, -SO2Ar, -COOH, -SO2NH2, -SO2NHR, -SO2NR2, -F, -Cl, -Br, -I, -OAr, -COOR, -COOAr, -OR, -OH, -SR, -SH, -COR, -COAr, -C?CR, -Ar, -CH=CR2, wherein R is an optionally substituted alkyl group and Ar is an optionally substituted aryl group, G being not more than five atoms away from the amide group of the sulfonylamide grouping, with the proviso that G is not -OH or -SH when n is 1 and with the further proviso that -(R2)n-G is not , and n is 0 or 1;
a sulfonamide of the formula - (II) in which, R1, R2 and G are as defined above, with the proviso that R1 is not , and with the further proviso that G is not COOH when all of the following three conditions apply; R2 is aryl, n is 1, and R1 does not comprehend or include an electron-withdrawing group within five atoms of the amide group of the sulfonylamide grouping;
an N-mono-substituted, N'-mono or di-substituted sulfamide of the formula (III) in which R2, G and n are as defined above, and R3 and R4 are as defined for R1 and R2 or one of R3 and R4 is H, and further in which, when one of R3 and R4 is H, the other may be an electron-withdrawing group as defined above for G;
an N-monosubstituted sulfonamide having electron withdrawing groups on both sides of the sulfamoyl group, of the formula - (IV) in which n, R2 and G are as defined above and G1 is an electron-withdrawing group us defined above with respect to G; or a polyfunctional molecule in which each functional group or the repeating unit is N-monosubstituted sulfonamide or sulfamide depicted in formulas (I) through (IV).

5. A recording material in accordance with claim 1, whereln said compound is selected from the group consisting of:
N-(phenylsulfonyl)-p-toluenesulfonamide N-phenyl-benzene sulfonamide C3-8 alkyl-N-(phenylsulfonyl)-p-aminobenzoate N-.alpha.-(p-toluenesulfonyl)-DL-phenylalanine N-(carboxymethyl)-p-toluenesulfonamide N-[o-(p-toluenesulfonamido) phenyl]-p-toluenesulfonamide C3-8 alkyl-N-(o-carboxyphenylsulfonyl)-p-amino-benzoate N-(o-carboxyphenylsulfonyl)-4-aminobenzophenone N-(o-carboxyphenylsulfonyl)4-aminobenzenesulfonamide N-(4-C1-18 alkylphenyl)-o-carboxybenzenesulfonamide N-2(2,4-diC3-8 alkylphenyl)-o-carboxybenzenesulfonamide N-(diC1-8 alkylsulfamoyl)-p-toluenesulfonamide N-phenyl-N'-C1-8 alkylsulfamide N-benzoyl-N'-C1-8 alkylsulfamide N-phenyl-N',N'-diC1-8 alkylsulfamide N(diC1-8 alkylsulfamoyl)-.alpha.-aminophenylacetic acid N-(o-(N',N'-diC-3alkylsulfamoylamido)-phenyl-diC1-8alkylsulfamide trimethylene bis (N-c-carboxylphenylsulfonyl)-p-aminobenzoate N-toluenesulfonyl-.alpha.-aminophenylacetic acid N-phenylsulfonyl-.alpha.-aminophenylacetic acid N-(m-carboxybenzoyl)-p-toluenesulfonamide N-(m-carboxybenzoyl)-benzenesulfonamide N-(m-carboxybenzoyl)-N',N'-dimetylsulfamide N-(o-carboxybenzoyl)-p-toluenesulfonamide N-(o-carboxybenzoyl-benzenesulfonamide N-(o-carboxybenzoyl)-N',N'-dimethylsulfamide N-(m-nitrobenzoyl)-p-toluene sulfonamide N-(m-nitrobenzoyl)-benzenesulfonamide N-(m-nitrobenzoyl)-N',N'-dimethylsulfamide N-(p-nitrobenzoyl)-p-toluenesulfonamide N-(p-nitrobenzoyl)-benzenesulfonamide N-(p-nitrobenzoyl)-N',N'-dimethylsulfamide N-(phenylsulfonyl)-benzenesulfonamide; and 4,4'-oxybis[N-(phenylsulfonyl)-benzenesulfonamide].

6. In the method of producing a colored marking by causing a dye precursor to come into contact with a color developer, the improvement wherein solid color developer is a compound including a sulfonylamide (-SO2NH-) group and also including en electron-withdrawing atom or moiety within five atoms of the nitrogen atom of said sulfonylamide group, said compound being free of any basic group, with any additional NH groups being no more than one carbon atom away from an SO2, C=O, C?N or NO2 group, with the proviso that the electron withdrawing group is not a carboxyphenyl group connected through the nitrogen atom of the sulfonylamide group, with the further proviso that the sole electron-withdrawing group is not a carboxyphenyl group and with the further proviso that said compound does not include a hydroxy group on the opposite side of the amide from the sulfonyl group of the sulfonylamide group,

7. A method in accordance with claim 6 , wherein, subject to the provisos of claim 6, said electron-withdrawing group is selected from the group consisting of -NO2, -SO2R, -CN, -SO2Ar, -COOH, -SO2NH2, -SO2NHR, -SO2NR2, -F, Cl, -Br, -I, -OAr, -COOR, -COOAr, -OR, -OH, -SR, -SH, -COR, -COAr, -C?CR, -Ar, -CH=CR2, wherein R is an optionally substituted alkyl group and Ar is an optionally substituted aryl group.

8. A method in accordance with claim 6 , wherein said compound has electron-withdrawing groups on both sides of the sulfonylamide grouping.

9. A method in accordance with claim 6 , wherein said compound is:

an N-monosubstituted sulfonamide of the formula - (I) in which R1 and R2 are alkyl, aryl or a combination of alkyl and aryl, each being substituted or unsubstituted, said substituents, if any, being any group other than a basic group and, if -NH, no more than one carbon atom away from a SO2, C?O, C?N or NO2 group, G is an electron-withdrawing group selected from the group consisting of -NO2, -SO2R, -CN, -SO2Ar, -COOH, -SO2NH2, -SO2NHR, -SO2NR2, -F, -Cl, -Br, -I, -OAr, -COOR -COOAr, -OR, -OH, -SR, -SH, -COR, -COAr, -C?CR, -Ar, -CH?CR2, wherein R is an optionally substituted alkyl group and Ar is an optionally substituted aryl group, G being not more than five atoms away from the amide group of the sulfonylamide grouping, with the proviso that G is not -OH or -SH when n is 1 and with the further proviso that -(R2)n-G is not , and n is 0 or 1;
sulfonamide of the formula - (II) in which, R1, R2 and G are as defined above, with the proviso that R1 is not , and with the further proviso that G is not COOH when all of the following three conditions apply; R2 is aryl, n is 1, and R1 does not comprehend or include an electron-withdrawing group within five atoms of the amide group of the sulfonylamide grouping;

an N-mono-substituted, N'-mono or di-substituted sulfamide of the formula (III) in which R2, G and n are as defined above, and R3 and R4 are as defined for R1 and R2 or one of R3 and R4 is H, and further in which, when one of R3 and R4 is H, the other may be an electron-withdrawing group as defined above for G;
an N-monosubstituted sulfonamide having electron withdrawing groups on both sides of the sulfamoyl group, of the formula - (IV) in which n, R2 and G are as defined above and G1 is an electron-withdrawing group as defined above with, respect to G; or a polyfunctional molecule in which each functional group or the repeating unit is an N-monosubstituted sulfonamide or sulfamide depicted in formulas (I) through (IV).

10. A method in accordance with claim 6, wherein said compound is selected from the group consisting of:
N-(phenylsulfonyl)-p-toluenesulfonamide N-phenyl-benzene sulfonamide C3-8 alkyl-N-(phenylsulfonyl)-p-aminobenzoate N-.alpha.-(p-toluenesulfonyl)-DL-phenylalanine N-(carboxymethyl)-p-toluenesulfonamide N-[o-(p-toluenesulfonamido) phenyl]-p-toluenesulfonamide C3-8 alkyl-N-(o-carboxyphenylsulfonyl)-p-amino-benzoate N-(o-carboryphenylsulfonyl)-4-aminobenzophenone N-(o-carboxyphenylsulfonyl)4-aminobenzenesulfonamide N-(4-C1-18 alkylphenyl)-o-carboxybenzenesulfonamide N-2(2,4-diC3-8 alkylphenyl)-o-carboxybenzenesulfonamide N-(diC1-8 alkylsulfamoyl)-p-toluenesulfonamide N-phenyl-N'-C1-8 alkylsulfamide N-benzoyl-N'-C1-8 alkylsulfamide N-phenyl-N',N'-diC1-8 alkylsulfamide N-diC1-8 alkylsulfamoyl)-.alpha.-aminophenylacetic acid N-(o-(N',N'-diC1-3alkylsulfamoylamido)-phenyl-diC1-8alkylsulfamide trfmethylene bis (N-o-carboxylphenylsulfonyl)-p-aminobenzoate N-toluenesulfonyl-.alpha.-aminophenylacetic acid N-phenylsulfonyl-.alpha.-aminophenylacetic acid N-(m-carboxybenzoyl)-p-toluenesulfonamide N-(,-carboxybenzoyl)-benzenesulfonamide N-(m-carborxybenzoyl)-N'N'-dimethylsulfamide N-(o-carboxybenzoyl)-p-toluenesulfonamide N-(o-carboxybenzoyl-benzenesulfonamide N-(o-carboxybenzoyl)-N',N'-dimethylsulfamide N-(m-nitrobenzoyl)-p-toluene sulfonamide N-(m-nitrobenzoyl)-benzenesulfonamide N-(m-nitrobenzoyl)-N',N'-dimethylsulfamide N-(p-nitrobenzoyl)-p toluenesulfonamide N-(p-nitrobenzoyl)-benzenesulfonamide N-(p-nitrobenzoyl)-N',N'-dimethylsulfamide N-(phenylsulfonyl)-benzenesulfonamide; and 4,4' oxybis[N-(phenylsulfonyl)-benzenesulfonamide].

11. In a color developer composition for coat-ing onto sheet material to make pressure-sensitive or heat-sensitive recording compound, a solvent, and other additives to permit coating, the improvement wherein said color developer compound is a compound including a sulfonylamide (-SO2NH-) group and also including an electron-withdrawing atom or moiety within five atoms of the nitrogen atom of said sulfonylamine group, said compound being free of any basic group, with any addi-tional NH groups being no more than one carbon atom away from an SO2, C=O, C=N or NO2 group, with the proviso that the electron withdrawing group is not a carboxyphenyl group connected through the nitrogen atom of the sulfony-lamide group, with the further proviso that the sole electron-withdrawing group is not a carboxyphenyl group and with the further proviso that said compound does not include a hydroxy group on the opposite side of the amide from the sulfonyl group of the sulfonylamide group.

12. A color developer composition in accordance with Claim 11, wherein, subject to the provisos of Claim 11, said electron-withdrawing group is selected from the group consisting -NO2, -SO2R, -CN, -SO2Ar, COOH, -SO2NH2, -SO2NHR, -SO2NR2, -F, -Cl, -Br, -I, -OAr, -COOR, -COOAr, -OR, -OH, -SR, -SH, -COR, -COAr, -C?CR, -Ar, -CH=CR2, wherein R is an optionally substituted aklyl group and Ar is an optionally substituted aryl group.

13. A color developer composition in accordance with Claim 11, wherein said compound has electron-withdraw-ing groups on both sides of the sulfonylamide grouping.

14. A color developer composition in accordance with Claim 11, wherein said compound is:

an N-monosubstituted sulfonamide of the formula - (I) in which R1 and R2 are alkyl, aryl or a combination of alkyl and aryl, each being substituted or unsubstituted, said substituents, if any, being any group other than a basic groups and, if -NH, no more than one carbon atom away from a SO2, C=O. C?N or NO2 group, G is an electron-withdrawing group selected from the group consisting of -NO2, -SO2R, -CN, -SO2Ar, -COOH, -SO2NH2 , -SO2NHR, -SO2NR2, -F , -Cl, -Br, -OAr, -COOR, -COOAr, -OR, -OH, -SR, -SH, -COR, -COAr, -O?CR, -Ar, -CH=CR2, wherein R is an optionally substituted alkyl group and Ar is an optionally substituted aryl group, G being not more than five atoms away from the amide group of the sulfonylamide grouping, with the proviso that G is not -OH or -SH when n is 1 and with the further proviso that -(R2)n-G is not , and n is 0 or 1;

a sulfonamide of the formula - (II) in which, R1, R2 and G are as defined above, with the proviso that R1 is not , and with the further proviso that G is not COOH when all of the following three conditions apply; R2 is aryl; n is 1, and R1 does not comprehend or include an electron-withdrawing group within five atoms of the amide group of the sulfonylamide grouping;

an N-mono-substituted, N'-mono or di-substituted sulfamide of the formula (III) in which R2, G and n are as defined above, and R3 and R4 are as defined for R1 and R2 or one of R3 and R4 is H, and further in which, when one of R3 and R4 is H, the other may be an electron-withdrawing group as defined above for G;
an N-monosubstituted sulfonamide having electron withdrawing groups on both sides of the sulfamoyl group, of the formula -(IV) in which n, R2 and G are as defined above and G1 is an electron-withdrawing group as defined above with respect to G; or a polyfunctional molecule in which each functional group or the repeating unit is an N-monosubstituted sulfonamide or sulfamide depicted in formulas (I) through (IV).

15. A color developer composition in accordance with Claim 11, wherein said compound is selected from the group consisting of:
N-(phenylsulfonyl)-p-toluenesulfonamide N-phenyl-benzene sulfonsamide C3-8 alkyl-N-(phenylsulfonyl)-p-aminobenzoate N-.alpha.-(p-toluenesulfonyl)-DL-phenylalanine N-(carboxymethyl)-p-toluenesulfonamide N-[o-(p-toluenesulfonamido) phenyl]-p-toluenesulfonamide C3-8 alkyl-N-(o-carboxyphenylsulfonyl)-p-amino-benzoate N-(o-carboxyphenylsulfonyl)-4-aminobenzophenone N-(o-carboxyphenylsulfonyl)4-aminobenzenesulfonamide N-(4-C1-18 alkylphenyl)-o-carboxybenzenesulfonamide N-2(2,4-diC3-8 alkylphenyl)-o-carboxybenzenesulfonamide N-(diC1-8 alkylsulfamoyl)-p-toluenesulfonamide N-phenyl-N'-C1-8 alkylsulfamide N-benzoyl-N'-C1-8 alkylsulfamide N-phenyl-N',N'-diC1-8 alkylsulfamide N-diC1-8 alkylsulfamoyl)-.alpha.-aminophenylacetic acid N-(o-(N',N'-diC1-3a1kylsulfamoylamido)-phenyl-diC1-8alkylsulfamide trimethylene bis (N-o-carboxylphenylsulfonyl)-p-aminobenzoate N-toluenesulfonyl-.alpha.-aminophenylacetic acid N-phenylsulfonyl-.alpha.-aminophenylacetic acid N-(m-carboxybenzoyl)-p-toluenesulfonamide N-(m-carboxybenzoyl)-benzenesulfonamide N-(m-carboxybenzoyl)-N',N'-dimethylsulfamide N-(o-carboxyben~oyl3-p-tolueneul fonamide N-(o-carboxybenzoyl)benzenesulfonamide N-(o-carboxybenzoyl)-N',N'-dimethylsulfamide N-(m-nitrobenzoyl)-p-toluene sulfonamide