Note: Descriptions are shown in the official language in which they were submitted.
BACKGROUND OF THE INVEN~ION
This invention relates to recording members
containing heat-reactive components and, more particularly,
to recording members capable of being used in thermographic
copying, thermal printing, event recordin~, and as trans-
parencies for overhead pro~ection.
Heat sensitive sheets containing the cyclic
polyketo compounds of this invention, useful ~or copying
and recording and characterized by an ability to form a mark
of contrasting color when heated to an activation temperature
of 50C, are known in the art. They are used in thermographic
processes wherein a recording member is positioned on a graphic
original and exposed to infrared radiation to cause a selective
heating of the dark areas of the original sufficient to form
a copy thereof on the heat sensitive member. The thermally
responsive members have also been used to record the heated
portions of a thermal print-head and to record a colored
trace when contacted by the hot stylus of a thermal recorder.
The ninhydrinamine reaction wherein ninhydrin reacts with
amino acids, primary amines, and certain derivatives of mor-
pholine, piperidine, and pyrrolidine to give the dye commonly
referred to as Ruhrman's purple is well known. Isatin reacts
with these same amines to give isatin blue. Alloxan reacts
with the amines to give a red dye. These rea~tions have
been used in numerous inventions for thermally responsive copy
and recording papers and films. Lawton, U. S. Patent
No.3,736,166 used ninhydrin with various morpholine and
piperidine derivatives to prepare transparencie~ for overhead
projection. Lawton, U.S. Patent No~3,293,061 combined ninhydrin
or hydrindantin with isatin-amine condensates to provide
thermographic copy sheets~ ~auman and Lawton reacted ninhydrin
or hydrindantin with complexes of amines and flavans or
phenolic compounds to make thermographic copy sheet~, see
u. S. Patent No.3,149,9gl and U. S. Patent No.3,149,992.
Huffman, U.S. Patent No.3,664,a5~ combined ninhydrin with
the adducts of morpholine or piperidine and organic acids in
thermal recording members. Sus, U.S. Patent No.3,024,362
combined hydrindantin with amino acids or salts of primary
~nines with organic carboxylic and sulfonic acids to make
a thermocopy paper. Allen, U.S. Patent No.2,967,785 used
the adducts of morpholine or piperidine with isatin or
ninhydrin as the color forming material in thermocopy
papers. Small, U.S. Patent No.3,573,958 combined an amine
with a halide or organometallic halide of germanium, silicone,
lead, and tin with hydrindantin to provide a heat sensi~ive
recording sheet. In each case the normal dye formations of
Ruhrman's purple with ninhydrin, red dye with alloxan, and
isatin blue were obtained.
It is often desirabl~ and an objective of this
invention to obtain colored records which have colors
differing from those normally obtained with the above cyclic
polyketo compounds.
Undesirable odors and fumes are obtained by the
heat dissociation or decomposition of the complexes, salts,
or adducts during the imaging process. There is a problem
of image bleaching during excessive heating, on aging, or
prolonged exposure to ultxaviolet containing light.
Other types of heat sensitive recording sheets
are also well known in the art. This invention is related
to the use of a leuco or colorless fo~n of a dye material
and a phenolic material which reacts with the leuco material
to form a colored dye. There are many systems of this
type represented in the ~atent literature.
References ~or these systel~s include:
(1) ~hthalides, naphthalides, fluorans
Typical of these are Crystal Violet Lactone or
3,3-bis-(p-dimethylaminophenyl)-6-dimethylamino phthalide
and malachite green lactone or 3,3-bis(p-dimethylaminophenyl-
phthalide). The reactions of these and many related
phthalides with phenolics are d~escribed in Adachi, U.S.
Patent No.3,895,173; Schwab, U.S. Patent No.3,322,557;
Kohmura et al., U. S. Patent No.3,859,112; Hayashi et al.,
U.S. Patent No.3,773,542; Futaki et al., U.S. Patent No.
3,846,153; Baum, U.SO Patent No.3,539,375; Shimazu, U.S.
Patent No.3,864,684; Adachi et al., U~ S. Patent No.3,843,384;
Futaki et al., U.S. Patent No.3,829,401; Futaki et al.,
U.S. Patent No.3,825,432; Higachi et al, U.S. Patent
No.3,816,838; Nagashima et al., U-.-S. Patent No.3,792,481;
Blose et al., U.S. Patent No.3,746,675.
Typical examples of the lactones which are listed
in the patents as reacting with phenolic materials to produce
a color include the following:
TABLE
3,3-bis~p-dimethylamillophen~ 6-dimethylaminophthalide
3,3-bis(p-dimethylamillophenylphthalide)
3,3-bis[p-di(n-butylaminopheny~)phthalide~
Rhodamin~. lact~ne
3-[2-methyl 4-~diethylamino)phenyl] 3-(1,2-dimethyl-
-3-indolyl)phthalide
3-(p-dimethylaminophenyl)-3~ ethyl-2-methyl-3-indolyl)-
4,5,6,7-tetrachlorophthalide
3,3-bis(l~ethyl-2-methylindol-3-yl)phthalide
3-(4-morpholinophenyl)-3-~1,2-dimethylindol-3-yl)-
4,5,6,7-tetrachlorophthalide
3~ benzyl-2-methylindol-3-yl)-8-(methyl-2-methylindol-
3-yl~phthalide
5-nitro-3,3-bis~4-dimethylaminophenyl)phthalide
5-amino-3,3-bis(4-dimethylaminophenyl)phthalide
5-benzoylamino-3,3-bis-(4-dimethylaminophenyl)phthalide
3,3-bis(p-dimethylaminophenyl)-4,5,6~7-tetrachloro-
phthalide
3,3-bis(p-diethylaminophenyl)-6-dimethylaminophthalide
3,3-bis(p~dimethylaminophenyl)-6-aminophthalide
3,3-bislp-dimethylaminophenyl)-6-(p-toluenesulfonamide)
phthalide
3,3-bis~p-dimethylaminophenyl)-6-nitrophthalide
3,3-bis(p-dimethylaminophenyl)-6-monethylaminophthalide
3,3-bis~p-dimethylaminophenyl)-S-chlorophthalide
3,3-bis(p-dimethylaminophenyl)-6-ethoxyphthalide
3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide
3-(4-diethylaminophenyl)-3-(1,2-dimethylindol-3-yl)
naphthalide
3-(4-diethylaminophenyl)-3~ phenylpyrrol-3-yl)
naphthalide
3-diethylamino-7-dibenzyl~minofluo~an
3-diethylamino-7-(N-methylanilino)fluoxan
3-dimethylamino-6~methoxyfluoran
3-diethylamino-6-methyl-7-ehlorofluoran
3-morpholino-5,6~ben~ofluoran
7-acetamino~3 dimethylaminofluoxan
3-dimethylamino 5,7 dimethy~fluoran
3,6-bis~ ~-methoxyethoxyfluoran
3,6-bis-~ -cyanoethoxyfluoran
l-amino~3,6,7-trimethylfluoran
3-dibutylamino-6 methyl~7 chloro1uoran
3-diethylaminoo7-dihenzylaminofluoran
3-diethylamino /-(N-methyl-p-toluidino)fllloran
3-dimethylamino-7-chlorofluoran
3-(diethylamino)-6-methyl-7-anilinofluoran
3,7-bis~diethylamino)fluoran
3,6-dimethoxyfluoran
3-diamylamino-6-chlorofluoran
2',6'-bistdiethylamino1flu~ran
2'-~benzylamino)-6'-~di~thylamino)-3',4"-henzofluoran
3-(ethyl-p-tolylamino)-7-(methylphenylamino~fluoran
3-cyclohexylamino-6-chloro~luoran
3-diethylamino-5-methyl-7-bis(4-methyl~enzyl)aminofluoran
3-diethylamino 6-methyl-7-(p-butylanilino~fluoran
2'-anilino-6'-die~'nylamino-3'-methylfluoran
3-(diethylamino)-7-(N-methylanilino~fluoran
2'-phenylamino-3' methyl-6'-~N-ethyl-N-p-tolylamino)
fluoran
3-diethylamino-7-piperidinofluoran
3-diethylamino 7-phen~lfluoran
--6--
3-diethylamino-5-chloro-7-piperidinofluoran
3 dimethylamino-5-methyl-7~piperidino,fluoran
3-diethylamino-5-methyl 7-piperidino~luoxan
2-(2',4'6'-trimethylphenylamino)-8-diethylamino-3,
4-benzofluoran
2,8-bis(N-ethyl-N-p-tolylamino)fluoran
3~diethylamino-6-methyl--7-o-anisidinofluoran
3-~diethylamino)-6,7~dimethylfluoran
3 dimethylamino~5-methy:L-7-Cbis-t4-methylbenzyl)aminol
fluoran
4-amino~8 ~bis- B-ethoxyethyl)amino]benzo~luoran
N,N'-bis (3'-diethyl~minofluoran~7'yl)piperazi.ne
2-phenylarnino-6-diethylamino1uoran
2-phenylamino-6-dimethylaminofluoran
3'-diethylamino-7'-methylthiofluoran
3,7-bis (diethylamino)-5,6-benzofluoran
3-dimethylamino-7-benzylamino~5,6 ben~ofluoran
3-diethylamino-7-(N-benzyl-N-phenyl)aminofluoran
3-benzylamino 7-diethylaminofluoran
2'-~p-chloroanilino)-6'-diethylaminofluoran
2'-tm-chloroanilino)-3-methyl-6l-diethylaminofluoran
2'-(p-chloro-N methylanilino)-6'-diethylaminofluoran
3 (diethylamino)-5-methyl-7-t~ -phen~lhydrazino~fluoran
3-(diethylamino~-7-bis(l-naphthylmethyl)aminoflUoran
3-tdiethylamino)-7-(2-ph~halimidino)1uoran
3-~diethylamino)-6-methyl-3'-azafluoran
3-diethylamino-5-methyl-7-(diphenylamino~fluoran
3-~dim~thylamino3-7-tdiphenylmethylamino)fluoran
3-(diethylamino~-6-methyl 7-(p,p'-dimethyldiphenyl-
methyl)amino fluoran
3-tdibutylamino)-7-(diphenylmethylamino)fluoran
3-(diethylamino)-7-( ~, ~-dibenzylhydrazino)fluoran
3~(dimethylamino)-7-(p-methoxyben2amido)fluoran
'$~
r
7-anilino-3-(diethylamino)fluoran
2'-(methylphenylamino)-6l-~methyl-p-tolylamino~fluoran
2'-methyl-6'~cyclohexylaminofluoran
2'-~mino-6'-diethylamino-3'~methylfluoran
2'-amino-6'-diethylaminofluoran
2'-(2-carboxyanilino)-6'-diethylaminofluoran
3-dibenzylamino-7-diethylamino~luoran
N-(carboethoxymethyl)aminol-6'-dieth~l~mino~ luar~n
2'-~N-(carboethoxymethyl)-N-methylamino]-6'-diethylamino
fluoran
~hodamine lactam
N-phenyl Rhodamine lactam
Rhodamine anilino lactam
9-p-nitroamino-3,6-bis(diethylamino)~9-Xanthenoyl~
6-benzoic aci~ lactam
9-p-nitroamino-3,6-bis(dimethylamino)-9-thioxantheno~l-
6-benzoic acid lactam
(2) ~Spiropyrans
The following are some o~ the patents which list
typical spiropyrans givlng a color when reacted with phenolic
materials: Talvakar, U.S. Pate~t No.3,445,2~1; Futaki ek alJ
U.S~ Patent No.3,829,401; Kohmura at al., U.S~ Paten~ No~3,859,112;
Hayashi et al, U.S. Patent Mo.3,773,542; Kimura et alr U.S.
Patent No. 3,666,525; Yahagi et al, Japanese Pat. No.73-63,73~;
Futaki et al, Germany Patent No.2,252,845; Komura et al, German
Patent No.2,327,135; Takamizawa et al, Japanese Patent Mo.74-
00,069; RobilLard et al, French Patent No.2,204,151; Haino
et al, Japanese Patent No.75-01,746; Samat et al, German
Patent No.2,522,877; Miyazawa et al, Japanese 75-137,14~;
Takimoto et a:L, Japanese Patent No.75-152,742; Futaki et al,
German Patent No.2,252,845; Miya2awa et alr Japanese Patent
No.75-137,549.
Typical examples of the spiropyrans llsted in the
patents as reacting with phenolic materials to yield colored
dyes include-
TABLE II
.. .. _ .
6'-chloro-8'-methoxybenzoindolinospiropyran
benzothiazolinospiropyran
benzo-~ -naphthospiropyran
3-methyl-di- ~-naph~hospiropyran
1,3,3-txime~hyl-6'-chloro~8~~methoxyindoli.nohenzo-
spir~opyran
6'chloro-8'-methoxyindolinobenæospiropyran
6-chloro-8~methoxy-1',3',3'~trimethylspixo(1-benzo-
pyran-2,2'-indoline)
spiro (l-banzopyran-2,2l-naph~hopyran)
8'-methoxybenzoindolinospiropyran
1,3,3-trimethyl-4,7,8'-trimethoxy r (2'H~ benzopyran)-
2,2'-indoline]
6-chloro-8'-methyl-1,3,3-trimethylbenzoindolino-
spiropyran
2-ethyl-3,3l-spirobinaphthopyran
3-phenyl-di- ~-naphthospiropyran
di- ~-naphthospiropyran
3-ethyl-di-~ -napththospiropyran
3,3'-dichlorospirodinaphthopyran
1,3,3-trimethyl~6'-nitrospiro(2'H-l'-benzopyran-2,
2'-indoline)
1,3,3-trimethyl-8'-nitrospiro(2'H-l'-benzopyran-2 r
2'-indoline)
1,3,3-trimethyl-6'-nitro-8'-methoxyspiro(2'~-1'-ben~o-
pyran-2,2'-indoline)
1,3,3-trimethyl 5'-nitro-8'-methoxyspirot2'~I-l'-benzo-
pyran-2,2'indoline)
3,7 bist3',6'-dimethoxy-9'-spiroxanthyl)pyromellitide
_g_ .
Typical examples of phenolic materials listed in
the patent literature as reacting with ~he leuco compounds
such as the phtalides, naphthal.ides, f luorans, and spiropyrans
to form colored dyes include:
.
TP.ELE I I I
4,4'-isopropylidene diphenol
4/4'-isopropylidene-bis~2 methylphenol)
4,4~-isopropylidene-bis~2-phenylph~nol)
4,4'~isopropylidene bis~2-t.butylphenol)
4,4'-sec.butylidene-diphenol
4,4'-sec.but~lidene-bis(2-methylphenol)
4,4'-cyclohexylidene-diphenol
4,4'-cyclohexylidene-bis~2~isopropylphenol)
4/4'-ethylidene-diphenol
2,2'-methylene-bis(5-methylphenoI)
4,4'-ethylidene-bis(2-methylphenol)
4j4'-(1-methylpen~ylidene)diphènol
4,4'-(methylisopentylidene)diphenol
4,4'-~1-methylhexylidene)diphenol
4,4'-(1-ethylbutylidene)diphenol
4,4'-[ethylpropylidene~-bis(2-meth~lphenol)
4,4'-isopropylidenedicatechol
4,4'-benzylidene diphenol
4,4'-isopropylidene-bis(2-chlorophenol)
2,2'-dihydroxydiphenyl
2,2'-methylene-bis(4-chlorophenol)
. . ' :
2,2'-methylene-~is(4-methyl-6-t.butylphenol)
4,4'-isopropylidene-bis(2,6-dimethylphenol)
2,2'-thiobis(4,6-dimethylphenol~
4,4'-ethylene diphenol
--10--
$~
4,4'~ methylbenzylidene)diphenGl
4~t. butylphenol
4-phenylphenol
c~ -naphthol
~-naphthol
hydroquinone
pyrocatechol
pyrogallol
phloroglucine
mO cresol
,
There are a number of commercial products which
use the above-described combinations of leuco dyes and
phenolic derivatives. These have fnund applications in
thermal copying paper using thermal copie~s. Thermally
responsive sheets using these materials have also been used
with computer-driven thermal printers~ Sensitized papers
containing a combination of leuco dyes and phenolic materials
are used in chart recording instruments wherein a colored
trace record is o~tained by contacting the paper with a
hot pen or stylus. There are certain inherent disadvantages
found with the leuco dye-phenolic combinations. Complaints
are received on background staining, fading of the record
mark, flooding of the image, moisture sensitivity, odor,
pressure sensitivity causing accidental marking by paper
clips and the like, railroading, and burnout on chart
recording papers. Many of the phenolic materials described
in the patents are toxic or irritating and cannot be used.
These same leuco dye-phenolic color-forming systems are
used in the "carbonless" pressure marking papers and the
reactants are kept separate by microencapsulation or by
being contained in separate layers. Prsssure contact of
these materials results in dye formation. This property
is also inherent in the thermal papers and excess pressure
will cause accidental markingO Also, for this same reason,
the reactants must be ground separately and a solvent or
resin binder-solvsnt combination which will dissolve or
partially dissolve one or both of the co-reactants will result
in premature dye formation in the coating mix. The object
of this invention is to eliminate or minimize the problems
incured with the leuco dye-phenolic thermal color reacting
systems. Another objectlve is to minimize the sublimation or migration of
of the phenolic material which has caused problems with staining and change
in sensitivity. Still another objective is the manufacture of thermal record
sheets with improved image sharpness and definition.
This invention relates to a heat-sensitive recording composition
comprising (a) a phenol selected from Table IV of the specification; (b) an
amine or an amide; (c) a mixture of heat-sensitive color precursors
comprising: (1) a cyclic polyketo compound reactive with amines and amides
at elevated temperatures to form a color contrasting visibly with a back-
ground color of said composition, and (2) R chromogenic compound reactivewith phenols at elevated temperatures to form a color contrasting visibly
with a background color of said composition, said chromogenic compound
being selected Erom the group consisting of lactone type leuco dyes and
spiropyran type leuco dyes; and (d) binder means for binding the composition
to a substrate.
This invention further relates to a method for producing a heat-
sensitive recording composition comprising the steps of dissolving a binder
in a solvent in which complexes of a phenol and a complexing agent selected
from the group consisting of amines and amides is insoluble, to form a binder-
solvent solution, dispersing in said solution a chromogenic compound reactivewith a phenol at elevated temperatures to develop a color contrasting visibly
with a background color of said composition, said chromogenic compound being
selected from the group consisting of lactone type leuco dyes and spiropyran
type leuco dyes; a cyclic polyketo compound reactive with amines and amides
at elevated temperatures to form a color contrasting visibly with a back-
ground color of said composition; and a hydrogen-bonded molecular complex
of a phenol and a complexing agent selected from the group consisting of
amines and amides, to form a dispersion, applying said dispersion to a
substrate, and evaporating solvent from said dispersion to form a thermo-
sensitive coating adapted to develop a color at elevated temperatures.
-13 -
,~ ,~....
SUMMARY OF THE INVENTION
I have found that the problems and disadvantages of the above
described thermal recording systems can be minimized or eliminated by using
a combination of leuco dye precursors of the lactone or spiropyran types
with cyclic polyketo compounds such as ninhydrin, hydrindantin, isatin,
alloxan, and their homologs. I have found that the color precursors may
be chemically combined as adducts or chemical complexes of one another which
are light in color but can be converted by heat to a dark colored dye. The
dye thus formed is not typical of either of the co-reactlng color precursors
but rather produces a color additive effect approaching the black dyes
most desired for imaging purposes. I have further found that a similar
additive effect is obtained when the individual color precursors are mixed
together and heated. Presumably, the precursors go through the adduct
or complex forming process during fusion and are converted to the final dye
by further heating. I have further discovered that molecular complexes of
phenolic compounds with amines can be added to the mixtures or adducts of
the combined precursors resulting in an increase in dye intensity of the
image and also providing faster thermal response at lower temperatures
during the imaging process. I have further discovered that certain additives
may be used with the color precursor adducts or complexes,
-13~
~Q9~33
mixtures of the color precursors, or a combination of these
with molecular complexes of phenolics and amines -to further
increase the color intensity of the image and also increase
the rate of thermal response during imaging.
DETAILED DESCRIPTION OF IN~ENTION
Materials
a. Lactones
Crystal Violet lactone (3,3-bis-(p-dimethylamino-
phenyl)-6-dimethylaminophthalide), Malachite Green lactone
(3,3-bis(p-dimethylaminophenyl)phthalide), and 3,3-bis(l-ethyl-
2-methylindol-3-yl) phthalide were obtained from the Hilton-
Davis Co., Cincinnati, Ohio. The 3,3-bis(p-aminophenyl)
phthalide was obtained from the Organic Chemicals Div.,
Eastman Kodak Co., Rochester, NY.
b. Spiropyrans
The indolinospiropyrans were prepared in the normal
manner by well known methods described in the art by refluxing
e~uimolar amounts of the desired Fischer's base, in these ex-
amples 1,3j3-trimethyl-2-methylene indoline or the 5-chloro
derivative of the same with the desired aldehyde, e.g., sa-
licylaldehyde, 5-nitrosalicylaldehyde, 5-bromo-salicylalde-
hyde, 3,5-dibromosalicylaldehyde, and o-vanillin in absolute
alcohol for three to four hours, cooling, filtering, and
washing the precipitate with alcohol and drying. Similarly,
2-methylbenzothiazolium methyl tosylate was reacted with 2-
hydroxy-l-naphthaldehyde and with salicylaldehyde to give the
corresponding spiropyrans. The 3-methyl-di-~ -naph~hospiro-
pyran was obtained in the usual manner by treating 2-hydroxy-
l-naphthaldehyde and methyle~h~l ketone in absolute ethanol
-14-
i
with hydrogen chloride yas and neutralizing the salt formed
with sodium carbonate and recrystallizing the product from
benzene.
c. Adducts or compLexes of lactones or spiropyrans
with cyclic ketones includingninh~drin and isatin.
These were prepared by boiling with stirring for
thirty minutes a mixture of 15 parts of lactone or spiropyran
and 15 parts of ninhydrin or isatin in 250 parts anhydrous de-
natured alcohol. The hot mother liquor was decanted from
the residue, chilled in a cold box to crystallize and precipi-
tate the adduct, and the precipitated adduct was washed with
alcohol and air dried.
d. Complexes
The phenolic material is dissolved in anhydrous
methanol or ethanol to form a 25 percent solution. The hydro-
gen bonding co-reactani amine or amide is added to the alcoholic
solution of the phenolic derivative in molecular equivalents
corresponding to the number of functional hydroxyl groups in
the phenolic compound. For example, two moles of cyclohexyl-
amine are added to one mole of a bisphenol, one mole of amine
is added to one mole of a mono-hydroxy compound, etc. The
mixtures are stirred for a few minutes until they become homo-
geneous. In some cases, a solid complex will form and pre-
cipitate almost immediately, while others must be chilled in
a cold box beforP solid products are obtained. The mixture
containing the precipitated complex is then filtered and
the precipitate is washed with alcohol and allowed to dry.
The following table contains a number of hydrogen-bonded
phenolic complexes which have been prepared in this manner.
-15-
I TABLE IV - AROMATIC HYDROXY COMPLEXES
. _ _ _
Phenol AmineDissociation Temp.C
p,p' biphenol ethylene diamine 136-140
" t.butyl amino ethyl
methacrylate
Bisphenol B ethylenediamine 85-92
" formamide64-66
" t.butyl aminoethyl
methacrylate 94-6
4,4'-isopropylidene bis
~2-isopropylphenol) txiethanolamine 60-63
" ethylene diamine100~4
4,4'-isopropylidene bis
(2,6-dibromophenol) diethano~l amine107-145
" triethanolami.ne128-157
" ethylene diamine198-215
" diethylenetriamine 210-215
" propylene diamine. 146~156
" formamide 9S~102
" hydrazine 135 150
" t.-butyl aminoethyl
methacxy~ate 130-5
4~hydroxy propi.ophenone hydrazine 84-90
2,4-dichloro-6-phenylphenol ethylenediamine 100-4
" diethylenetriamine 115-20
" propylenediamine 92-4
2,2'-methylenebis
(3,4,6-trichlorophenol) diethanolamine 75-8
¦ " triethanolamine 118-23
" ethylenediamine 124-7
" diethylenetriamine 90-110
" propylene diamine125-30
" formamide 125-30
" hydrazine 180 4
t-butylamine ethyl
i methacrylate 123-6
2-bromo-4-phenyl phenol ethylenediamine 66-8
" diethylene triamine 78-82
~ " formamide 55-8
I p-phenyl phenol ethylene diamine137-43
1 " die~hylene triamine 99-104
I " propylene diamine77-81
" formamide 90-5
¦ " ~ydrazine 145-150
2,2'-thiobis
(4,6-dichlorophenol) triethanolamine 120-5
" ethylene diamine125-130
" diethylene triamine 15B-164
" propylene diamine142~5
" ormamide 115-25
" hydra~ine 195-200
4,4'-isopropylidenebis
(2,6-dichlorophenol) ethylenediamine 192-5
I " diethylene triamine 210-15
! propylene diamine170-5
" formamide 100-5
" hydxazine 142-6
-16-
I Table IV - Page 2
! Phenol Amine Disso~iation Temp.C
4,4'isopropylidenebis
(2,6-dichlorophenol) t.butyl amine ethyl
~ methacrylate 132-5
¦ 5-chloro-2-hydroxy
benzophenone ethylene diamine 190~4
o-phenylphenol ethylene diamine 55-60
" formamide 50-3
" hydrazine 60-4
Dichlorophene formamide 90-3
2,2'-methylenebis
(4-ethyl-6-t.butylphenol) triethanolamine 58-70
Bisphenol A ethylene diamine 100-4
" propylene diamine 94-100
" t.butylamine ethyl
methacrylate 90-2
4,4'-thiobis
(6-5.butyl-m-cresol) triethanolamine 95-8
" ethylene diamine 106-11
" propylene diamine 125-35
" t.butylamine ethyl
methacrylate 62-5
4,4'-butylidenebis
~6-t.butyl-m-cresol) triethanolamine 68-70
2,2'-methylenebis
(4-methyl-6-t.butylphenol) diethanolamine 62-5
" ethylene diamine 54-8
p-cyclohexyl phenol triethanolamine 35-40
" ethylene diamine 125-30
" die~hylene triamine 70-85
" propylene diamine 88-90
o-cyclohexyl phenol e~hylene diamine 88-93
" hydrazine 75-80
p-t.butyl phenol ethylene diamine 70-3
! propylene diamine 54-7
pO-sec. butyl phenol ethylene diamine 50-4
p-bromophenol formamide 35-8
2,4,6-tribromophenol ethylenediamine 135-8
" propylenediamine 85-9
" formamide 90-3
pentachlorophenol diethanolamine 145-55
" triethanolamine 133-7
" ethylenediamine 115-20
" diethylenetriamine 185-90
" propylene diamine 168-72
" formamide 100-5
" hydrazine 200-5
" t.butyl amine ethyl
methacrylate 115-20
-17-
TABLE IV - Page 3
Phenol Amine Dissociation Temp.C
2,6-dichloroph~nol triethanol~nine g3-6
ethylene diamine110-15
propylenedia~ine100-155
formamide 40-5
hydrazine 115-20
" tobukyl amine ethyl
methacrylate 100-5
2-chloro-4-phenyl phenol ethylene diamine130-5
propylene diamine50-4
" hydrazine 108-12
tetrachlorophenol diethanolamine 110-25
triethanolamine 98-10
ethylene diamine165-70
formamide 85-90
hydrazine 163-5
- " t.butyl-amino-ethyl
methacrylate 95~100
2,4,6-trichlorophenol ethylene diamine105-14
propylene diamine100~5
formamide 85-90
hydrazine 150-7
t.butyl amine ethyl
methacrylate 70-5
ethylenediimino-o-
cresol formamide 105-10
tObutylamine ethyl
methacrylate 118-12
Bisphenol A benzylamine 70-4
4,4'-isopropylidenebis
~2,6-dibromophenol) 2-amino-1-butanol 155-6~
aminoethylensthanolamine 74-85
2-amino-2-ethyl-1,
3-propenediol 130-40
2-amino-2-methyl-1,
3-propenediol 154-60
aminoethyl piperazine 140-50
2-amino-2-methyl-1-
propanol 180-90
2-amino-1-phenyl-1-
propanol 100~30
3-amino propanol 190-5
benzylamine 144-8
chloroacetamide114-22 -
" 3-chloro-N-methyl
acet~nide 80-5
n-decylamine 170-90
1,3-diamino propane 218-225
3-di-n-butyl amino
propylamine 150-8
diethanolamine 140-3
diethyl amino ethoxy
ethanol 180-5
diethylamino propylamine 175-85
N-diethyl amino propyl 1
methyloctadecylamine 88-100
" diethylisopropanolamine 135-42
j -18-
TA~LE IV - Page 4
Phenol Amine Dissociation Temp.C
4,4'-isopropylidenebis
(2,6-dibromophenol) diisopropanolamine 65-75
" diisopropylethanolamine 158-165
" dimeth~ylacetamine 95-100
" dimethylamino pxopyl-
amine 198-202
" dimethylethanol~mine 135-45
" dimethylformamide 60-5
" M-(l,l-dimethyl-2-hydroxy
- ethyl)-2-methyl 1-1,2~
Propane diamine 130-40
" t.-dod~cylaminopro-
' pylamine 90-105
ethanoLamine ],70-80
" ~-ethylethanolamine 90-100
" N-ethyldiethanolamine 137-42
" hexamethy,l phosphoramide 127-30
" n-hexylamine 200-10
" triamine 60-80
! N-2-hydroxyeth
methyl dodecylamine 100-11
" N-hydroxyethyl piperazine
hydroxy ethyl trihydroxy
propyl-ethylene diamine 45-55
iminobispropylamine 210-20
isobutylamine 160-70
" isopropylamine 165-75
" 3-isopropoxypropanol-
amine 165-75
" isopropylamine 160-70
" ' methanediamine 140-5
" methyldiethanolamine 132-6
~ " methyl ethanol amine 143-6
I " N-methyl-bis-amino
propyl~mine 210-20
" polyglycol amine H-ll9 115-20
" polyglycolamine II-176195-205
" polyglycolamine H-221 165-174
" 1,2-propanediamine 150-160
" propylenediamine 148-155
" tetramethylethylene-
diamine 190-200
" tetramethylguanidine 225-235
" triethanolamine 154-8
" triethylene tetramine 200-15
" triisopropanolamine 135~9
p,p'-biphenol hexamethyl phosphoramide 40-50
4rhydroxy propiophenone hydrazine 84-90
2,2'-methylene bis
(2,4,6-trichlorophenol) aminoethylethanolamine165-7
" 2-amino-2-ethyl-1,3-
propanediol 151-70
" 2-amino-2-methyl-1,3-
propanediol 182-4
" benzylamine 210-16
" t.butylaminoethyl
methacrylate 123-6
--19--
~9~
TABLE IV - Page 5
Phenol Amine Dissociation
Temp.C
2,2'-methylene bis
(2,4,6 trichlorophenol) diethanolamine 75-8
Il diethylenetriamine 90-110
2,2'-methylene bis (2,
4,6-trichlorophenol) dimethylethanolamine 183-93
N-ethyldiethanolamine 124-7
ethylene diamine 187-92
" formamide 125-30
" hexamethyl phosphoxamide 85-90
" hydrazine 180-~
" N-methylbisam.ino
propylamine 157-55
" methyldiethanolamine 154-7
2~2'-methylsne bis (2,
4,6-trichlorophenol) methyle~hanolamine 193-200
" polyglycolamine H-176 208-24
" propylenediamine 135-40
" triethanolamine 142-6
2,4-dichloro-6-phenyl phenol diethylen0 triamine 115-20
" ethylene diamine 100-4
" propylenediamine 92-4
2-bromo-4-phenyl phenol benzylamine 85-95
diethylenetriamine 78-82
" ethylenediamine 66-8
" formamide 55-~
" hydrazine 82-8
p-phenyl phenol benzylamine 70
" diethlenetriamine 99-104
ethylenediamine 137-43
" formamide 113-5
" hexamethyl phosphoramide 34-5
" hydrazine lSS-8
" propylene diamine 71-81
" triethylene tetramine 63-5
2,2'-thiobis (4,6-
dichlorophenol) 2-amino-2-ethyl-1,
3-propanediol 125-59
" benzylamine 197-9
diethanolamine 143-7
" diethylene triamine 158-74
" diiosopropanolamine 155-62
" dimethylacetamide 190-3
dimethylethanol amine 120 3
N-ethyldiethanolamine 127-30
" ethylene diamine 125-30
" hydrazine 195-200
iminobispropylamine 50-74
methyldiethanolamine 127-40
. polyglycolamine 210-14
propylene diamine 142-S
" formamide 115-25
triethanolamine 165-8
" triisopropanolamine 151-S
2,2' methylene bis (4-
chlorophenol) benzylamine 60-100
-20-
TABLE IV - Page 6
Phenol Amine Dissociation
2,2' methylene bis ~4- Temp.C
chlorophenol) formamide 90-3
4,4'-isopropylidene bis
(2,6-dichloxophenol~ 2-amino-1-butanol 166-70
" ami.noethylethanolamine 154-8
2-amino-2-ethyl-1,2-
propanediol 166-8
2-amino-2-methyl-1~3-
propanediol 172-5
3-amino propanol 180-90
amylamine 200-10
" aniline 90-6
" benzylamine 145-55
" t~butylaminoethyl
methacrylate 132-5
" cyclohexylamine 190-204
j " n-decylamine 193-8
I " 1,3-diamino propane 230~5
dibutylamine 124-57
3-di-n-butylamine
propylamine 155-64
dibutylmethylamine 120-31
" dicyclohexylamine 202-6
diethanolamine 150-3
" diethylamine . 142-7
" diethylaminoethyl
methacrylate 115-7
" ~ -diethylaminopro-
pionitrile 94-6
" 3-ethylamino propioni-
trile 103-5
di-2-ethylhexylamine 100-5
diethylene triamine 210-15
diethylisopropanolamine 125-35
diisopropylethanolamine 162-4
" diisopropyla~ine 141-52
~ -dimethylamino propio-
nitrile 70-3
" dimethylaminopropyl-
amine 197-2Q3
dimethylethanolamine140-6
di-n-propylamine 142-53
3-t.-dodecylaminopropy-
lamine lG0-5
ethanolamine 96~104
N-ethylcyclohexylamine 161-78
N-ethyldiethanolamine 154-5
ethylene diamine 208-10
N-ethylethanolamine 87-110
formamide 103-8
hexamethylphosphoramide 122-4
n-hexylamine 168-85
hydrazine . 142-6
hydroxyethylethylene
diamine 94-100
iminobispropylamine 220-3
isobutylamine 152-67
isodecylamine 187-95
-21-
TABLE IV - Page 7
Phenol ~mine Dissociation
4,4'-isopropylidene bis Temp.C
¦ (2,6-dichlorophenol) isooctylamine 172-~4
isopropanolamine150-7
3-isopropoxyisopropanol-
amine 160~7
~ -isopropylaminopr~
pionitrile 103-7
3-isopropylamine pro-
pyl~mine 122-7
isoquinoline 102-4
2,6-lutidi~e 125-32
methanediamine 186-90
N-]methyl bis amino
propylamine 219-36
methylaminopropylamine 207-13
methylbenzyla~ine 145~55
N-methyldiethanolamine 148-52
N-methylethanolamine ~5-102
3,3'-methyl iminobis
propylamine 190-9
N-methyl morpholine 120-4
N-methyl-2-pyrrolidone 70-3
morpholine 159-60
phenyldiethanolamine 85-95
phenylethanolamine 88 95
2,2'-phenyliminodiethano-
lamine 55-70
~ -picoline 96-9
polyglycolamine H-ll9 156-63
polyglycolamine H-169 123-33
polyglycolamine H-176 210-18
polyglycolamine H-221196-200
propylenedi~mine 168-75
pyridine 117-30
tetraethylene pentamine 92-102
tributylamine . 103-8
triethylamine 155-64
triethanolamine 139-45
triethylene tetramine215-20
triisopropanolamine 125-30
trimethylenediamine 230-5
dimethylacetamide 132
5-cloro-2-hydroxy benzo-
phenone ethylenediamine 190-4
2,2'-methylene bis (4-ethyl
6~dibutyl phenol) benzylamine . 76-85
triethanolamine ~8-70
o-phenyl phenol ethylenediamine S5-60
formamide 50-3
hydra2ine 60-4
4,4'-isopropyl:idene bis-
phenol benzylamine 80-90
t.butylaminoethyl
methacrylate 30-2
cyclohexylamine 108-10
dibutylamine 120-52
diethylamine 117-53
dimethylamine
propylamine 105-8
-22-
.
TABLE IV - Page 8
Dissociation
Phenol ~mi~e
4,4'-isopropylidene bis-
phenol di-n-propylamine 90-100
ethylenediamine 100-4
formamide 66 8
isobutylamine 88-93
methanediamine 128-30
N-methyliminobis~
propylamine 94-8
propylenediamin0 95-100
triethylenetetramine137-~
4,4'-thiobis (6-t.butyl-
- m-cresol) t.butylamino~:ethyl
methacrylate 62~5
cyclohexylamine 78-85
ethylenediamine 112-15
iminobispropylamine85~95
isopropylamine 164-6
propylenediamine 130-6
pyridine 160-5
triethanolamine 95-8
4,4'-butylidene bis
(m-cresol) acatamine 82-3
benzylamine 135
cyclohexylamine 214-7
ethylenediamine 213-7
triethanolamin~ 68-70
2,2'-methylene bis (4-
methyl-6-~.butylphenol) 2-amino-1-butanol 58-64
benzylamine 69-79
decylamine 52-3
1,3-diaminopropane 50-5
N-dibutylethylamine 60-5
diethanolamine 62-5
di-n-hexylamine 81-9
ethylcyclohexylamine92-4
N-ethyl diethanolamine 68-71
isopropylaminoiso-
propylamine 128-32
ethylene diamine 54-8
hexamethyl phosphoramide 58-65
isoquinoline 121-5
N-methyldiethanolamine 127-34
methyl ethanolamine74-84
triamylamine 65-75
triethanolamine 61-5
p-cyclohexyl phenol triethanolamine 35 40
benzylamine 50-5
diethylenetriamine 70-85
ethylene diamine 125-30
hexamethyl phosphoramide 97-109
hydrazine 115-20
propylene diamine 88-90
o-cyclohexyl phenol benxylamine 82-95
ethylene diamine 88-93
hydrazine 75-80
-23-
~0
TABLE IV - Pa~e 9
Dlssociation
Phenol Amine Temp.C
p.t-butyl phenol benzylamine 70-80
~thylenedi~mine70-3
" hydrazine 45-50
" propylenediamine 54-6
p-bromophenol formamide 35-8
2,4-dibromophenol benzylamine 80-5
2,4,6-tribromophenol t.butyl amin~ ethyl
methacrylate 68-71
" benzylamine 125-30
" ethylene diamine 135-8
formamide 90-3
" hydrazine 145-54
" propylene diamine 87-92
Pentachlorophenol benzylamine 155-60
t.-butylaminoethyl
methacrylate 115-20
diethanolamine145-55
" diethylenetriamine 185-90
" ethylenediamine115-20
" formamide 100-105
hexamethyl phosphoramide 79-83
" hydrazine ?00-205
propylenediamine 168-72
" triethanolamine133-7
2,6-dichlorophenol benzylamine 100-5
t.butylaminoethyl
methacrylate 100-5
diethanolamine 83-6
" ethylenediamine110-15
" formamide 40-5
" hydrazine 115-20
" propylenediamine 115-25
2-chloro-4-phenyl phenol benzylamine 95-100
" ethylenedi~mine130-5
" hydrazine 108-12
" propylenediamine 50-4
tetrachlorophenol benzylamine 115-25
" t.butylaminoethyl
methacrylate 95-100
" diethanolamine110-25
" ethylenediamine192-5
" formamide 85~90
" hydra2ine 163-5
" propylenediamine 165-70
" triethanolamine98-104
2,4,6-trichlorophenol benzylamine 120-5
" ~.bu~ylaminoethyl
methacrylate 70-5
" ethylenediamine105-14
formamide 85-~0
hydrazine 150-7
" propylenediamine 100-5
2,4-dichloro-1-naphthol benæylamine 55-60
" diethanolamine65-70
-24-
~9~
TABLE IV - Page 10
Dissociation
Phenol Amine _Temp.C
2,4-dichloro-1-naphthol diethylenetriamine 79-83
formamide 78-82
hydrazine 83~93
2-naph`thol triethanolamine 63-5
" benzylamine 40-5
" ethylenediamine 86-9
formamide 56-59
" hydrazine llO-lZ
4,4-isopropylidene bis
(p-chlorophenol) benzylamine 105-10
formamide 55-60
hexamethyl phosphvramide 46-8
hydrazine 100-112
2,6-dibromo-t.butyl phenol benzylamine 75-80
diethylenetriamine85-96
" ethylenediamine95-105
hydraxine 105-110
propylenediamine95-100
" triethanolamine104-6
p-phenoxy phenol ethylenediamine56-62
" hydraxine 48-56
2,4,5-trichlorophenol benezylamine 118-20
" t.butylaminoethyl
methacrylate 55 60
diethanolamine 105-10
" diethylenetriamine 85-95
" ethylenediamine55-60
" - hydrazine 94-100
" propylenediamine96-104
l,l-di (4-hydroxyphenyl)
cyclohexane diethanolamine100-112
" propylenediamine120-5
l,l-di (3,5-dibromo-4-
hydroxy phenyl) cyclohexane diethanola~ine 149-54
" propylenediamine175-80
3,3-bis ~3,5-dibromo-4-
hydroxy phenyl) pentane propylenediamine 183-g2
2,2-bis (3,.5-dibr~mo-4-
hydroxy phenyl) pentane diethanolamine 110-18
" propylenediamine180-90
bis (3,5-dibromo-4-
hydroxy phenyl) methane diethanolamine 115-23
2,2-bis ~3,5-dibromo-4-
hydroxy phenyl) butane diethanolamine 142-5
" propylenediamine174-6
3,3'-5,5'-tetrabromo-4,4'-
dihydroxy biphenyl diethanolamine 173-80
l-phenyl-l, l-di (3,5-di-
bromo-4-hydroxy phenyl)
ethane diethanolamine 145-50
" propylenediamine . 185-200
2,2-di (3,5-dibromo-4-
hydroxypheny].) 4-methyl-
penetane diethanolamine 115-20
" propylenediamine190-4
-25-
T~BLE IV ~ Page 11
Dissociation
Phenol Amine Tem .~C
P _ ._
2,2-di (3,5 di~romo-4~
hydroxy phenyl) heptane diethanolamine 145-50
" prop~ylenediamine 195-7
l,l-di (3,5-dibromo-4-
hydroxy phenyl) butane diethanolamine 100-15
" propylene diamine 173-7
2,2-di (3,5-dibromo-4-
hydroxy phenyl) octane diet:hanolamine 140-2
l,l-di (3,5-dibromo-4-
hydroxy phenyl~ ethane diethanolamine lOS~10
" propylenediamine 175-8
2,4-dihydroxybenzophenone propylenediamine 212-18
3,5-dichlorosalicylaldehyde diethanolamine 100-5
hexamethyl phosphoramide 70-84
" propylenediamine 135-4S
bisphenol A disalicylate diethanolamine 150-5
" propylenediamine 155~75
tetrachlorohydroquinone diethanolamine 146-50
" propylene diam.ine 175-80
2-hydroxy-5-phenyl-
propiophenone propylenediamine 180-5
2,4,6-tribenzoyl resorcinol diethanolamine 125-30
" propylenediamine over 280
3,5-dibromosalicylaldehyde diethanolamine 90-8
hexamethylphosphoramide 83-95
" propylenediamine 150-2
2-isopropyl-4,6-dinitro-
phenol diethanolamine 105-10
" propylenediamine 188-90
3,4,6-trichloro-2-nitro
phenol diethanolamine 146-50
" propylenediamine 185-90
1,1-methylenebis-2-naphthol diethanolamine 135-40
hexamethylphosphoramide 142-4
propylenediamine 160-5
1,1-di-2-naphthol diethanolamine 158~74
' hexamethylphosphoramîde 112-20
' propylenediamine 120-30
1,l-thio bis l2-naphthol3 diethanol~mine 135-42
" hexamethyl phosphoramide 124-8
" propylenediamine 120-5
p-chlorotrisphenol diethylene triamine 132-8
" hexamethylphosphoramide 149-Sl
l,l-bis (3,5-dichloro-4-
hydroxyphenyl) cyclohexane benzylamine 144-52
l,l-bis ~3,5-dichloro~4-
hydroxy phenyl) cyclohexane diethanolamine 140-3
" diisopropyl ethanolamine 164-8
. dimethyl ethanolamine 169-85
" methyl diethanolamine 131 9
methyl ethanolamine 165-71
polyglycolamine ~-176 192-200
TABLE IV ~ Pa~e 12
Dissociation
Phenol Am~ne Temp.C _
pentabromophenol aminoethylethanolamine 131-3
" 2-amino-2-methyl-1,3-
propanediol 170-9
benzylamine 155-8
" diethanolamine 158-61
diisopropanolamine 178-37
diisopropyle~hanolamine 13a-3
N-ethyldiethanolamine93-8
methyl diethanolamine 120-3
" methyl ethanola~ne 163-5
" triethanolamine 129-34
hydroquinone acetamide 99-105
" . formamide 63-5
" morpholine 64-8
" piperazine 187-95
resorcinol hydrazine 48-55
" pipera~ine 147-52
pyrogallol formamide 55-8
" acetamide 58-65
-27
e. Substrates
The substrates used were a 25 lb/3000 sq. ft.
bleached sulfite paper and 3 mil polyester film.
f. Test equipment
A thermal copier was used for reproduction and also
for preparation of transparencies. A thermal matrix printer
was used to demonstrate printing. A recorder was used to
demonstrate chart recording capabilities.
The preferred embodiment of the invention is the use
of a combination of color formers with a molecular complex
of an amine and a phenolic compound and optionally an accel-
erator. Stabilizers may also be used if so desired.
Preparation of Coatings
The phenolic hydrogen bonded complexes are dispersed
in a solution of a binder and ball-milled or otherwise ground
until a fine particle size, preferably below 10 microns, is
obtained. Any solvent-binder system may be used which does
not dissolve and dissociate the phenolic complex. Some suit-
able systems include water solutions of polyvinyl alcohol,
hydroxyethyl cellulose, and other common water-soluble poly-
meric resins. Methanol or ethanol solutions of nitrocellu-
lose, ethylcellulose, and other alcohol-soluble resins canbe
used. Likewise, hydrocarbon solutions of styrene polymers or
copolymers, acrylate or methacrylate polymers or copolymers,
hydrocarbon resins, elastomeric polymers, and the like, can
2~
~o~
~e u~ed-.- The limits for the concentration are governed by
desirable coating viscosities, dry weight of the coating, and
the like. Concentrations of complexes varyiny between 5 and
50 percent have been found to be convenient.
Similarly~ the leuco dye color-forming material is
also dispersed by ball-milling or by other convenien~ means
in a solvent-binder system which will not dissol~e and dis- .
sociate the pehnolic molecular complex. The r~active ingredients
are ground separately in this case to permit the more convenient
variation o the ratios of the co-reactin~ leuco dyes and
phenolic complexes. ~owever~ this is nvt a requirement.as the
leuco d~es and phenolic complexes have been grDund together
without encountering any signs of mix instability or loss of
the markin~ characteristics of the dried coating.. This is not
true when the leuco dye~ for example Crystal Violet Lactone,
is ground wi-t~ the free ~henolic material. The ground mixture
~ecomes hiyhly colored and is useless as a ~oatîng material~
Coatin~ ~pplications
.
. The mix-tures.of gxinds of the leuco dyes and molecular
~omplexes of phenolic materials were applied by Meyer rod to
a 25 lb/ 3000 s~.ft sulfite base paper and allowed to air~dry~
Dry coating weights of the thermosensi~ive coatings were varied
from 1.5 lb/3000 s~.ft to over 10 lb/3000 sq~tO and useful
records were made with each coating.
Specific Examples
.
The ingredients are individually dispersed by ball-
milling as a 15 percent concentration in a 5 percent solution
-2~-
of polyvinyl alcohol in water. These are combined in the
ratios indicated in the -table and coated onto the substrate
with a No. 16 wire wound Meyer rod and air dried. The
coated substrates were imaged :in the test equipment to yive
the colors indicated in the table.
COLOR PRECURSORS
Spiropyrans
Code Base Aldehyde
A 2-methylbenzothiazolium methyl tosylate 2-hydroxyl-1-naphthaldehyde
B " " " salicylaldehyde
C 5-chloro-2-methylene-1,3,3-trimethyl-
indoline salicylaldehyde
D " 5-nitrosalicylaldehyde
E " 5-bromosalicylaldehyde
F " 3,5-dibromosalicylaldehyde
G 2-methylene-1,3,3-trimethylindoline 5-nitrosalicylaldehyde
H " o-vanillin
I 3-methyl-di-~ -naphthospiropyran
Lactones
J Crystal Violet lactone
K 3,3-bis-p-aminophenylphthalide
L 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide
M Malachite Green lactone
Cyclic Polyketones
I Ninhydrin
II EydrindantLn
III Isatin
IV Alloxan
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Activators may be added to the heat-sensitive compo-
sitions of the invention to lower the activation temper-
atures of the above systems and to intensify the image
mark. Some preferred activato:rs are ureas and ~hioureas
such as phenylurea, phen~lthiourea and allylurea;
carbanilide; thiocarbanilide; zinc acetoacetonate; fatty
acid salts of zinc such as zinc stearate and zinc palm-
itate; and salicylanilde.
-38-
