U.S. patent number 3,916,069 [Application Number 05/347,193] was granted by the patent office on 1975-10-28 for reduced styryl/cyanine dye.
This patent grant is currently assigned to Minnesota Mining and Manufacturing Company. Invention is credited to George V. D. Tiers, Joseph A. Wiese, Jr..
United States Patent |
3,916,069 |
Tiers , et al. |
October 28, 1975 |
Reduced styryl/cyanine dye
Abstract
Dihydroheterocyclic amines having a N-hydrocarbyl substitution
and a 2-(or 4-) (omega-(nuclearly substituted cyclic)) vinylenyl
substitution are described. These compounds are oxidized in an
acidic environment to produce styryl and cyanine dyes.
Inventors: |
Tiers; George V. D. (St. Paul,
MN), Wiese, Jr.; Joseph A. (St. Paul, MN) |
Assignee: |
Minnesota Mining and Manufacturing
Company (St. Paul, MN)
|
Family
ID: |
23362704 |
Appl.
No.: |
05/347,193 |
Filed: |
April 2, 1973 |
Current U.S.
Class: |
430/338; 430/343;
544/143; 546/176; 548/150; 548/156; 548/217; 430/344; 546/165;
546/329; 548/152; 548/159; 548/255; 548/440; 548/455; 548/468;
548/490; 548/509; 548/511; 546/277.4 |
Current CPC
Class: |
G03C
1/732 (20130101); G03C 1/675 (20130101); G03C
1/733 (20130101) |
Current International
Class: |
G03C
1/73 (20060101); G03C 1/675 (20060101); B41M
005/00 (); B41M 005/20 () |
Field of
Search: |
;96/1.6,129 ;260/240.9
;117/36.7 ;250/475 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Chemical Berichte, Vol. 65, pages 1737-1742 (1932)..
|
Primary Examiner: Herbert, Jr.; Thomas J.
Attorney, Agent or Firm: Alexander, Sell, Steldt &
DeLaHunt
Claims
What is claimed is:
1. A normally stable electron beam recording sheet having an
electron beam-sensitive layer comprising a polymeric binder and
substantially colorless oxidizable dye-progenitor consisting of
N-hydrocarbyl substituted dihydroheterocyclic amine having an
omega-(nuclearly substituted cyclic) vinylenyl substituent in the 2
or 4 position; said layer comprising anionogen yielding halide
anion on exposure to the radiation of an electron beam.
2. Sheet of claim 1 wherein said N-hydrocarbyl-substituted
dihydroheterocyclic amine having an omega-(nuclearly substituted
cyclic) vinylenyl substituent on the 2 or 4 position contains a
halogen atom which is removable upon bombardment with an electron
beam as said anionogen.
3. Sheet of claim 1 wherein said binder contains a halogen atom
removable by electron bombardment as said anionogen.
4. Sheet of claim 1 wherein said layer includes anionogen component
in addition to said binder and said N-hydrocarbyl-substituted
dihydroheterocyclic amine having an omega-(nuclearly-substituted
cyclic) vinylenyl substituent in the 2 or 4 position.
5. Sheet of claim 1 wherein the N-hydrocarbyl group is alkyl of 1-6
carbon atoms.
6. Sheet of claim 1 wherein dihydroheterocyclic amine is
1,3,3-trimethyl indoline having its substituent in the 2
position.
7. The normally stable electron beam recording sheet of claim 1
wherein the N-hydrocarbyl substituted dihydroheterocyclic amine is
2-(4-(dimethylamino)styryl)-1,3,3-trimethylindoline.
Description
The present invention relates to derivatives of dihydroheterocyclic
amines which are N-heterocycles in which the nitrogen and one other
member are in a reduced state. More particularly, it relates to
N-hydrocarbylsubstituted dihydroheterocyclic amines having a 2-(or
4-) (omega(-nuclearly substituted cyclic)) -vinylenyl substituent
and to processes for the preparation of such amines.
The N-hydrocarbyl-substituted dihydroheterocyclic amines of the
invention are substantially colorless but when oxidized in an
acidic environment yield compounds exhibiting practically any
desired color of the visible spectrum depending on the choice of
substituents in the molecule. The N-hydrocarbyl-substituted
dihydroheterocyclic amines of the invention find utility in
radiation-sensitive elements.
Non-silver radiation-sensitive elements in which colored images are
produced on exposure of the element to various kinds of radiation
have been described. Such elements generally contain one or more
color progenitors, which form color on protonation, in combination
with an acid progenitor. Thus, in U.S. Pat. Nos. 2,474,084;
2,505,470, and 2,983,756 there are described light-sensitive
elements containing as the color progenitor leuco or carbinol bases
of tri-phenyl-methane or diphenylmethane dyes. These elements
produce colorations limited mainly to the blue to green range of
the visible spectrum. In U.S. Pat. No. 3,102,810, there are
described light-sensitive elements containing as the color
progenitor one or more styryl or leuco dye bases. These latter
elements produce colorations generally limited to the yellow to red
range of the visible spectrum.
Elements containing the above described color progenitors, although
providing colors that are generally dense and relatively stable,
tend to develop color on storage even in the absence of radiation.
Furthermore, the backgrounds of elements that have been imaged tend
to deteriorate and to develop color on storage. This is
disadvantageous as to the stability of the image.
It has now been found that N-hydrocarbyl dihydroheterocyclic amines
having a vinylenyl substituent in the 2-(or 4-) position which has
a nuclearly substituted cyclic group in the omega (distal)
positions are color progenitors which when oxidized in an acidic or
anionogenic environment yield colored products exhibiting
practically any desired color of the visible spectrum depending on
the choice of additional substituents.
The term "hydrocarbyl" will be understood herein as a monovalent
radical of 1 to 10 carbon atoms and hydrogen, including alkyl,
cycloalkyl, phenyl and benzyl and including not more than about 60
atomic weight units of the atom elements, O, N, F, Cl or S.
O, N and S may be in chains as hydroxyethyl, ethoxyethyl,
dimethyaminoethyl, 3-thia pentyl, or the like or in cyclic
structures as morpholino, piperidino, thiazino or the like.
Hydrogen atoms are usually simple substituents.
The term dihydroheterocyclic amine refers to a nitrogen heterocycle
in which the nitrogen and one other atom (usually adjacent) are in
a reduced state as indolenine is related to indole. The term cyclic
itself will be understood to refer particularly to fully
unsaturated cyclic structures as phenyl, pyridine, pyrrole, furan,
thiophene and that reduced forms will in general be named
appropriately.
In radiation sensitive elements containing anionogens, these color
progenitors are storage stable for all practical purposes
indefinitely (i.e., the element does not develop color in areas
that have not been exposed to suitable radiation). More
specifically, the amines of the invention are essentially colorless
N-hydrocarbyl-substituted-2-(or 4-) (omega-(nuclearly substituted
cyclic)vinylenyl) dihydroheterocyclic amines. These many frequently
be referred to herein as substituted heterocyclic amines or as
vinylenyl-substituted heterocyclic amines. They may also be called
2-(or 4-) (omega-(nuclearly substituted cyclic)) vinylenyl
N-hydrocarbyl dihydronitrogen heterocycles. On oxidation in an
acidic environment, these heterocyclic amines produce styryl or
cyanine dyes. A compound mentioned under Beilstein System No. 3493
which is an isomer of a compound of the invention (see FIG. 144)
but in which there are no vinylenyl group is found not to give
clean colors when subjected to radiation.
The structure of amines of the invention may be represented by
Structure I: ##SPC1##
wherein Q is a divalent radical of 1 to 4 atoms which joins N to
C.sup.1 when m = 1 or 1, or joins N to C.sup.2 when m = 1 and,
except for auxochromic substituents and hydrogen, consisting
essentially of the nonmetallic atoms necessary to complete a 5 or 6
member dihydroheterocyclic nucleus including at least 1
hydrocarbyl-substituted nitrogen atom; R is hydrocarbyl and
preferably is primary alkyl having 1 to 6 carbon stoms;
##SPC2##
is n vinylenyl groups each composed of two methinyl ##SPC3##
groups and providing a conjugated chain of carbon atoms joined by
alternating double and single bonds; m is 0 or 1; n is an integer
from 1 to 3; and X is a member, unsubstituted or substituted by an
auxochromic substituent, of the group consisting of phenyl, 5 to 6
member heterocyclic nuclei, or a chian of 2 to 4 atoms including 1
to 2 hetero atoms as no more than one half the total atoms of said
chain, which chain taken together with one or the other of the two
closest methinyl groups forms a 5 to 6 member heterocyclic nucleus
and otherwise unused valences of C, C.sup.1 or C.sup.2 are attached
to H except that not more than one may be attached to phenyl or not
more than two may be attached to alkyl of 1-6 carbon atoms. The
auxochromic substituents on phenyl or heterocyclic nuclei include
aryl, alkyl, dialkylamino, dialkylsulfonamido, alkylsulfonyl,
arylsulfonamido, alkoxy, aryloxy, nitro, cyano, alkoxycarbonyl and
halogen as well as divalent benzo or naphthaleno groups, but any
group which is compatible with synthetic methods employed and
influences the absorption spectrum of the oxidized compound may be
employed. It is convenient to designate the two methinyl groups
nearest the X group which form a vinylenyl group as the proximal
and anteproximal methinyl groups. With respect to the
dihydroheterocyclic nucleus they are respectively distal and
antedistal or ultimate and penultimate.
The substituted dihydroheterocyclic amines of the invention have a
dihydroheterocyclic nucleus joined at its 2- or 4- position to an
auxochromically substituted cyclic nucleus either directly or
through divalent linking chain of 1 to 5 methinyl groups. These
amines may be represented by two general structures depending on
whether there is an odd or even number of methinyl groups in the
linking chain; ##SPC4##
In Structures II and III, n' is an integer from 1 - 3 and n" is 0
to 3 and D is a dihydroheterocyclic nucleus, represented by one or
the other of the structural variations shown as Structure IV. The
free valences in the vinylenyl groups are usually attached to H but
one may be attached to hydrocarbyl, preferably methyl, ethyl or
phenyl. ##SPC5##
In Structure IV, R is hydrocarbyl and preferably primary alkyl of 1
- 6 carbon atoms, Q.sup.1 is CR.sup.1 R.sup.1, S, O, Se, or NR in
which each R.sup.1 is H or hydrocarbyl selected from the group
consisting of alkyl or 1 to 6 carbon atoms, phenyl and benzyl and
preferably is methyl and the two Z groups may be individually
hydrogen atoms or together may be either a benzo- or naphtho-
substituent with or without auxochromic substituents as described
above.
In Structure II, A is a monovalent cyclic nucleus having one of the
structural variations designated as Structure V. ##SPC6##
In structure V, R and the two Z's are as defined above, Q.sup.2 is
O, S, Se, NH or NR; Y is H, Cl, F, alkyl of 1 - 6 carbon atoms OH,
OR.sup.2, or NR.sup.3 R.sup.4 ;
Z' is H, Cl, F, alkyl of 1 - 6 carbon atoms, OR.sup.5 or
NR.sub.2.sup.5 ;
Z" is H, Cl, F, alkyl of 1 - 6 carbon atoms or OR.sup.5 ;
Z' and adjacent Z" taken together can be benzo or naphtho with or
without auxochromic substituents;
R.sup.2 is alkyl of 1 - 6 carbon atoms;
R.sup.5 is methyl or ethyl;
R.sup.3 and R.sup.4 are independently hydrocarbyl or taken together
with an adjacent Z" each can be independently 1,2-ethylene,
1,3-propylene or 1,2-phenylene or in conjunction with each other
can form a 5 to 6 membered ring including not more than one oxygen
or one additional nitrogen.
In Structure III, B is a divalent heterocyclic nucleus having the
structure: ##SPC7##
wherein R, Q.sup.1 and the two Z's are as defined above.
Examples of suitable dihydroheterocyclic nuclei or radicals
(Structures IV) that may be present in the substituted
dihydroheterocyclic amine of the invention include those shown in
FIGS. 1 to 29 inclusive, wherein the names of the respective
structures are:
FIG. Name ______________________________________ 1
1,3,3-trimethyl-2,3-dihydro-2-indolyl 2
1,3,3-triethyl-2,3-dihydro-2-indolyl 3
5-ethoxy-1,3,3-trimethyl-2,3-dihydro-2-indolyl 4
1-methyl-3,3-dibenzyl-2,3-dihydro-2-indolyl 5
5-chloro-1,3,3-trimethyl-2,3-dihydro-2-indolyl 6
5-phenyl-1,3,3-trimethyl-2,3-dihydro-2-indolyl 7
5-diethylamino-1,3,3-trimethyl-2,3-dihydro-2-indolyl 8 5-benzene
sulfonyl-1,3,3-trimethyl-2,3-dihydro- 2-indolyl 9
5-ethoxycarbonyl-1,3,3-trimethyl-2,3-dihydro-2- indolyl 10
5-dimethylamino carbonyl-1,3,3-trimethyl-2,3- dihydro-2-indolyl 11
5-cyano-1,3,3-trimethyl-2,3-dihydro-2-indolyl 12
N-butyl-1,2-dihydro-2-quinolyl 13
6-bromo-1-phenyl-1,2-dihydro-2-quinolyl 14
6-ethoxy-1-ethyl-1,2-dihydro-2-quinolyl 15
1-ethyl-1,2-dihydro-2-(5,6-benzo)-quinolyl 16
3-ethyl-2,3-dihydro-2-benzoxazolyl 17
6-methoxy-3-ethyl-2,3-dihydro-2-benzoxazolyl 18
3-methyl-2,3-dihydro-2-benzothiazolyl 19
6-chloro-3-n-propyl-2,3-dihydro-2-benzothiazolyl 20
6-phenoxy-3-ethyl-2,3-dihydro-2-benzothiazolyl 21
6-methyl-3-phenyl-2,3-dihydro-2-benzothiazolyl 22
6-dimethylaminosulfonyl-3-ethyl-2,3-dihydro-2- benzothiazolyl 23
3-butyl-2,3-dihydro-2[2,1,d]-naphththothiazolyl 24
3,5,6-trimethyl-2,3-dihydro-2-benzothiazolyl 25
3-cyclohexyl-2,3-dihydro-2-benzothiazolyl 26
1,3-dimethyl-1,2-dihydro-2-benzimidazolyl 27
5-methoxy-1,3-diethyl-1,2-dihydro-2-benzimidazolyl 28
3-ethyl-2,3-dihydro-2-benzoselenazolyl 29
6-methoxy-3-ethyl-2,3-dihydro-2-benzoselenazolyl
______________________________________
The substituted dihydroheterocyclic nuclei D, of Structures IV,
exemplified in FIGS. 1 - 29, are attached to cyclic nucleus A (cf.
Structure II) by a divalent bond or a divalent chain having 2, 4,
or 6 methinyl or substituted groups, including as examples:
CH.sub.3 CH.sub.3 CH.sub.3 .vertline. .vertline. .vertline.
--CH=CH--, --CH=CH--CH=CH--, --C(C.sub.6 H.sub.5)=CH--, --C=CH--,
--C=CH--C=CH--, ---CH=CH--CH=CH--CH=
Examples of suitable nuclei A, Structure V heterocyclic radicals
include those shown in FIGS. 30 to 58 inclusive wherein the names
associated with the respective structures are:
FIG. Name ______________________________________ 30 2-pyridyl 31
4-quinolyl 32 2-benzothienyl 33 1-methyl-2-benzimidazolyl 34
2-benzoxazolyl 35 3-furyl 36 3-thienyl 37 2-thienyl 38
1-ethyl-3-pyrryl 39 1-methyl-2-pyrryl 40 1-methyl-3-indolyl 41
10-methyl-7-phenothiazinyl 42 4-diethylamino-phenyl 43
4-dimethylamino-.alpha.-naphthyl 44 2-dimethylamino-5-methyl-phenyl
45 4-morpholinyl-phenyl 46 p-anisyl 47 p-hydroxyphenyl 48
o-butoxyphenyl 49 p-phenoxy-phenyl 50 biphenylyl 51 phenyl 52
.alpha.-naphthyl 53 2-ethoxy-3-(diethylamino)-phenyl 54
p-cyanophenyl 55 p-chlorophenyl 56 p-dimethylamino-sulfonyl 57
2,4-dimethoxyphenyl 58 p-thioanisyl
______________________________________
The substituted dihydroheterocyclic nuclei of Structures IV,
exemplified in FIGS. 1 - 29, are attached to Structures VI
heterocycles by a trivalent chain with two points for attachment
having 1, 3, 5, or 7 methinyl groups, i.e., have a monovalent and
divalent end; as shown in FIGS. 59 through 65 inclusive wherein the
names associated with the structures of the respective figures
are:
FIG. Name ______________________________________ 59 methinyl 60
prop-1-en-1-yl-3-ylidene 61 2-methylprop-1-en-1-yl-3-ylidene 62
2-phenylprop-1-en-1-yl-3-ylidene 63
1,3-(2',2'-dimethylpropano)-penta-1,3-dien-1-yl- 5-ylidene 64
penta-1,3-dien-1-yl-5-ylidene 65 hepta-1,3,5-trien-1-yl-7-ylidene
______________________________________
Examples of suitable Structures VI heterocycles include those shown
in FIGS. 66 to 86 which will be seen to be similar in structure to
those of FIGS. 1 - 29 except that they have two valences to a
single carbon atom. This is reflected in the names which for the
structures of the FIGS. 66 - 86 are given below.
______________________________________ FIG. Name
______________________________________ 66
1,3,3-trimethyl-1,2-dihydro-2-indolylidene 67
5-chloro-1,3,3-trimethyl-1,2-dihydro-2-indolylidene 68
5-phenyl-1-ethyl-3,3-dimethyl-2,2-dihydro-2- indolylidene 69
3-methyl-2,3-dihydro-2-oxazolylidene 70
3-phenyl-2,3-dihydro-2-oxazolylidene 71
6-ethoxy-3-methyl-2,3-dihydro-2-oxazolylidene 72
1,3,3-trimethyl-2,3-dihydro-2-pyrrylidene 73
3-methyl-2,3-dihydro-2-thiazylidene 74
1,3-dimethyl-1,2-dihydro-2-benzimidazolylidene 75
3-methyl-2,3-dihydro-2-benzothiazolylidene 76
6-chloro-3-ethyl-2,3-dihydro-2-benzothiazolylidene 77
6-phenyl-3-methyl-2,3-dihydro-2-benzothiazolylidene 78
3-methyl-2,3-dihydro-2-naphthothiazolylidene 79
1-methyl-4-ethyl-1,2-dihydro-2-pyridylidene 80
1-n-hexyl-5-methyl-1,2-dihydro-2-pyridylidene 81
1-methyl-1,2-dihydro-2-pyridylidene 82
1-methyl-1,2-dihydro-2-quinolylidene 83
2-methyl-1,2-dihydro-1-isoquinolylidene 84
1-methyl-1,4-dihydro-4-pyridylidene 85
1-methyl-1,2-dihydro-4-quinolylidene 86
10-methyl-9,10-dihydro-9-acridinylidene
______________________________________
As described by the general structures of the vinylenyl-substituted
heterocyclic amines of the invention have two or three structural
parts illustrated in part in FIGS. 1 - 86. Illustrations of these
structures are provided in FIGS. 87 through 144 the names of the
respective compounds of which are given below.
__________________________________________________________________________
FIG. Name
__________________________________________________________________________
87 2-(4-(dimethylamino)styryl)-1,3,3-trimethylindoline 88
2-(2-chloro-4-dimethylaminostyryl)-1,3,3-trimethyl- indoline 89
2-(4-diethylaminostyryl)-1,3,3-trimethylindoline 90
2-(4-morpholinostyryl)-1,3,3-trimethylindoline 91 2-(3,4-dimethoxy
styryl)-1,3,3-trimethylindoline 92
(2-(4-(ethylbenzylamino)styryl)-1,3,3-trimethylindoline 93
2-(3,5-di-t-butyl-4-hydroxystyryl)-1,3,3-trimethyl- indoline 94
2-(2,3-benzostyryl)-1,3,3-trimethylindoline 95
2-(2-dimethylamino-5-methyl-styryl)-1,3,3- trimethylindoline 96
2-(4-(phenylmethylamino)styryl)-1,3,3-trimethyl- indoline 97
2-(4-bis(2-chloroethyl)amino styryl)-1,3,3- trimethylindoline 98
2-(4-hexyloxystyryl)-1,3,3-trimethylindoline 99
2-(2-ethoxy-4-diethylaminostyryl)-1,3,3-trimethyl- indoline 100
2-(4-dibenzylaminostyryl)-1,3,3-trimethylindoline 101
2-(2-methyl-4-(benzylethylamino)styryl)-1,3,3- trimethylindoline
102 2-(2-(9-ethyl-3-carbazolyl)ethenyl)-1,3,3-trimethyl- indoline
103 2-(2-(N-methyl-2-pyrryl)ethenyl)-1,3,3-trimethyl- indoline 104
2-(2-(N-benzyl-3-indolyl)ethenyl)-1,3,3-trimethyl- indoline 105
2-(2-thienyl-ethenyl)-1,3,3-trimethylindoline 106
2-(2-pyrryl-ethenyl)-1,3,3-trimethylindoline 107
2-(4-(4-dimethylaminophenyl)butadienyl-1,3,3- trimethylindoline 108
2-(4,4-bis(4-dimethylaminophenyl) butadienyl)-1,3,3-
trimethylindoline 109
4-(4-dimethylaminophenyl-styryl)-N-ethyl-1,2-dihydro- pyridine 110
4-(4-(4-dimethylaminophenyl)butadienyl)-N-ethyl-1,2-
dihydropyridine 111 4-(4,4-bis(4-dimethylaminophenyl)butadienyl)-N-
ethyl-1,2-dihydropyridine 112
2-(4-dimethylaminostyryl)-N-ethyl-1,2-dihydro- quinoline 113
2-(4-(4-dimethylaminophenyl)butadienyl)-N-ethyl-1,2-
dihydroquinoline 114
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-N-
ethyl-1,2-dihydroquinoline 115
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-4-
methyl-N-ethyl-1,2-dihydroquinoline 116
2-(4-dimethylaminophenyl)styryl-N-ethyl-2,3-dihydro- benzoxazole
117 2-(4-(4-dimethylaminophenyl)butadienyl)-N-ethyl-
2,3-dihydro-benzoxazole 118
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-N-
ethyl-5-carbethoxy-3,3-dimethyl-indoline 119
2-(4-dimethylaminophenyl)-styryl-N-ethyl-2,3- dihydro-benzothiazole
120 2(4-bis(4-dimethylaminophenyl)butadienyl)-N-
ethyl-2,3-dihydrobenzothiazole 121 2-(4-dimethylamino
styryl)-N-ethyl-2,3-dihydro- naphthothiazole 122
2-(4-(4-dimethylaminophenyl)butadienyl-N-ethyl-
2,3-dihydronaphthothiazole 123
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-N-
ethyl-2,3-dihydronaphthothiazole 124
2-(3(1,3,3-trimethylindolylidene-2)prop-1-enyl-1)-
1,3,3-trimethylindoline 125
2-(5-(1,3,3-trimethylindolylidene-2)penta-1,3-
dienyl-1)-1,3,3-trimethylindoline 126
2-(3-(N-ethyl-1,4-dihydropyridylidene-4)prop-1-
enyl-1)-1,3,3-trimethylindoline 127
2-(3-(N-ethyl-2,3-dihydrobenzothiazoylidene-2)-
prop-1-enyl-1)-1,3,3-trimethylindoline 128
2-(3-(N-ethyl-2,3-dihydroquinolylidene-2)prop-1-
enyl-1)-1,3,3-trimethylindoline 129
4-(3(N-ethyl-1,4-dihydropyridylidene-4)prop-1-enyl-1)-
N-ethyl-1,2-dihydropyridine 130
4-(3(N-butyl-1,4-dihydropyridylidene-4)prop-1-enyl-1)-
N-butyl-1,2-dihydropyridine 131
2-(3-(N-ethyl-1,2-dihydroquinolylidene-2)prop-1-
enyl-1)-N-ethyl-1,2-dihydroquinoline 132
4-(3-(N-ethyl-1,4-dihydroquinolylidene-4)prop-1-
enyl-1)N-ethyl-1,2-dihydroquinoline 133
4-(3-(N-ethyl-1,4-dihydroquinolydidene-4)2-methyl
prop-1-enyl-1)-N-ethyl-1,2-dihydroquinoline 134
2-(6-methyl-N-ethyl-1,4-dihydroquinolylidene)-4)-
methinyl)-6-methyl-N-ethyl-1,2-dihydroquinoline 135
2-(N-ethyl-1,4-dihydroquinolyidene-4) methinyl-N-
ethyl-1,2-dihydroquinoline 136
2-(3-(N-ethyl-2,3-dihydrobenzothiazolylidene-2)-2-
methyl-prop-1-enyl-1)-N-ethyl-2,3-dihydrobenzo- thiazole 137
4-(3-(N-ethyl-1,4-quinolylidene-4)-prop-1-enyl-1)-
N-ethyl-1,2-dihydroquinoline 138
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-1,3,3-
trimethyl-5-carbonamidoindoline 139
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-1,3,3-
trimethyl-5-cyanoindoline 140
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-1,3,3-
trimethyl-5-methylsulfonylindoline 141
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-1,3,3-
trimethyl-5-dimethylsulfonamidoindoline 142
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-1,3,3-
trimethyl-5-ethoxyindoline 143
2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-1,3,3-
trimethyl-5-nitroindoline 144 2-(3-
1,3,3-trimethylindolinylidene)-2-phenyl prop-
1-enyl-1)-1,3,3-trimethylindoline
__________________________________________________________________________
The preferred substituted dihydroheterocyclic amines are those
amines which are defined as N-(lower alkyl)-substituted-2-(or 4-)
[(omega-dihydrocarbyl-aminocyclic)-vinylenyl]dihydroheterocyclic
amines. These substituted dihydroheterocyclic amines are preferred
because on acid oxidation they yield dyes having deep tinctorial
strength, i.e., a 1 mil (25 micron) thick resin coating containing
1 part by weight of dye per 10 parts by weight of colorless resin
has an optical density of at least 1. Because of their stability
toward adventitious discoloration, the preferred
dihydroheterocyclic amines of the invention are those of Structure
III above with 5 membered rings and particularly where Q.sup.1 is
-C(CH.sub.3).sub.2 and the dyes of Structure II above wherein
cyclid nucleus A has the Structures V as follows: ##SPC8##
wherein Q.sup.1, R, Z, Z', Z" are as defined above and Y' is
NR.sup.6 R.sup.7, ##SPC9##
wherein R.sup.6 and R.sup.7 are hydrocarbyl.
The substituted dihydro-heterocyclic amines of the invention are
conveniently prepared by the reduction of a corresponding dye.
Thus, the substituted dihydroheterocyclic amines of Structure II
are obtained by the reduction of styryl dyes and the amines of
Structure III by the reduction of cyanine dyes as is illustrated
for the reduction of a cyanine dye in FIG. 145 which shows the
formation of
2-(3-(1-ethyl-3,3-dimethylindolylidene-2)prop-1-enyl-1)-1-ethyl-3,3-dimeth
ylindoline from the indolinium chloride.
The cyanine dyes which are precursors to the substituted
heterocyclic amines (Structures III) of the invention are readily
available. Some can be purchased commercially and all are readily
prepared by procedures that are well known in the art (see, for
example, Cyanine Dyes and Related Compounds, Hamer, Interscience
Publishers (1964)). Those cyanine dyes having a single methine
group joining the quaternized heterocycle and a heterocyclic
nucleus, the methincyanines are prepared, among other ways, by the
condensation of an N-heterocyclic quaternary salt having a reactive
methylene group in the 2-position with a quaternary salt of
N-heterocyclic compound as shown in Equation 2 in FIG. 146.
The carbocyanine or trimethincyanine dyes are prepared by the
condensation of a methine group former such as ethylorthoformate
with two equivalents of a single N-heterocyclic quaternary salt
having a reactive group in the 2-position to obtain a symmetrical
carbocyanine dye or first with one equivalent of one such salt and
then one equivalent of another such salt to obtain unsymmetrical
carbocyanine dyes such as is shown in Equation 3, in FIG. 147.
Pentamethincyanine and higher methinecyanine dyes are prepared in a
manner similar to the carbocyanine dyes by substituting the methine
group-former i.e., ethyl orthoformate, with a polymethine group
former such as 1-anilino-3-aniloprop-1ene-or
1-anilino-5-anilopenta-1,3-dine, as Equation 4 illustrated in FIG.
148.
The styryl dyes are also readily avialble. They may be prepared by
procedures well known in the art. Thus, styryl dyes which are
precursors for the substituted heterocyclic amines of Structure II
may be prepared in one procedure by condensation of an
N-heterocyclic quaternary salt having a reactive group in the
2-position with aldehydes or ketones having the structures of FIGS.
149 and 150 wherein Z,Z', Z", Y', and Q.sup.2 are as defined
before; p is 0 to 3; and R.sup.8 represents substituents such as
hydrogen, methyl or phenyl that may be on the vinylene chain.
The reduction of polymethine dyes to the substituted heterocyclic
amines of the invention as is illustrated in FIG. 145 is
accomplished using any reducing agent having sufficient reducing
power. A reducing agent has sufficient reducing power if, when
added to a solution of the dye, it will discharge the dye color
from the solution. One generally useful reducing agent is sodium
borohydride. The reduction of the polymethine dyes is carried out
by the addition of the selected reducing agent in small portions to
a solution of the dye in a solvent at a temperature of from about
0.degree. to 50.degree. C. allowing sufficient time between
additions for the reducing agent to react before the next portion
is added. No additional reducing agent is added after color is
completely discharged from the dye solution. Preferably, the
temperature is maintained at from about 15.degree. to 30.degree. C.
in which range the reaction usually proceeds rapidly but with
minimization of any tendency for the reduction of unsaturation in
the dye molecule other than at the quaternized nitrogen. In
producing the amine of the invention, sufficient reducing agent is
required to provide 2 atoms of hydrogen per molecule of dye. Lesser
amounts may be used where the dye is not pure and greater amounts
may be required in some instances in a range of from about 1.8 to
about 4 atoms of hydrogen per molecule of dye. It is desirable that
the dye be of sufficient purity that the color is discharged after
the addition of sufficient reducing agent to provide 1.9 to 2.1
atoms of hydrogen per molecule of dye.
Solvents in which the reaction may be carried out are those
solvents in which the dyes are soluble and which are not reduced by
the reducing agent at a rate appreciably faster than are the dyes.
Examples of such solvents include water, aqueous alcohol, methanol,
ethanol, acetone (the dyes reduce faster than does acetone)
isopropanol, and the like. Generally, from 10 to 100 parts by
volume of solvent per part by weight of dye is used depending on
the solubility of the particular dye. It is often advantageous to
carry out the reduction in a mixture of water and a
water-immiscible solvent such as, for example, benzene, toluene,
methylene chloride or chloroform because the amine is generally
more soluble in the water-immiscible solvent.
The reduction is complete when color has been discharged from the
dye solution. This generally required from a minute or so to 3 or
more hours depending on the amount and solubility of dye being
reduced as well as on the solubility of the reducing agent and
whether it is liquid or solid. Although quantities of several grams
of dye in water may be reduced in a few minutes by aqueous
solutions of sodium borohydride, quantities of 10 kg or more of dye
may require 3 or more hours with the same reducing agent. Because
the reaction is exothermic, it is advantageous to cool the
reaction.
In addition to sodium borohydride, mentioned above as a reducing
agnet, suitable reducing agents include tetramethyl ammonium
borohydride, sodium hydride, sodium amalgam, aluminum hydride,
lithium aluminum hydride, sodium in alcohol, stannous chloride in
alcohol, zinc and alcoholic hydrochloric acid, amalgamated tin and
hydrochloric acid (care must be taken to exclude oxygen during the
reaction and then to neutralize the acid with base immediately
following the reaction). Some of these must be used under anhydrous
conditions. Electrochemical reduction is also a suitable
procedure.
Following the reduction reaction, the solution of crude substituted
heterocyclic amine, if in a nonaqueous solvent, is conveniently
diluted with water and extracted with several portions of a water
insoluble solvent such as benzene, toluene, dipropylether,
chloroform, methylene chloride, or the like. Methylene chloride is
found to be especially convenient. The crude amine is recovered
from the combined extracts and purified by recrystallization or by
liquid chromatography.
The substituted heterocyclic amines of the invention find use in
nonsilver photosensitive compositions and in elements or
constructions utilizing these compositions which print out an image
directly on exposure to suitable radiation. Such compositions
generally comprise at least one amine of the invention, an acid
progenitor or anionogen in a suitable binder. An anionogen is a
compound which is stable when exposed to normal room light, is
soluble in the binder system, and provides an anion when exposed to
a source of energy such as an electron beam. In a preferred
composition, the binder is also the anionogen such as a polymer
containing halogen. The composition may also contain additional
components such as, for example, sensitizing compounds or dyes,
fillers, plasticizers, or other modifiers all coated on a
supporting film such as polyethylene terephthatate, or in a
self-supporting film.
In the absence of sensitizing compound or dye, the compositions,
including the heterocyclic amines of the invention, are insensitive
to visible radiation, i.e., those radiations having a wavelength
greater than about 4000A. Such compositions, contrary to prior art
compositions are stable to storage, even in normal light,
essentially indefinitely. However, they are somewhat sensitive to,
and hence exposed by ultraviolet light, i.e., light having a
wavelength substantially less than about 4000A as a result of
formation of acid or much more readily by harder radiations such as
are afforded by electron beams, X-rays, and other high energy
radiation in the presence of anionogens. Many of the compositions
are also sensitive to heat.
The dye progenitor compounds herein described by which will be
understood the dihydroheterocyclic amines of the invention find
particular utility in the preparation of normally stable image
recording sheets on which images may be recorded directly by
exposure to a suitably modulated electron beam; and in one aspect
the invention therefore relates to the preparation and use of such
sheet materials.
Sheet materials capable of being directly imaged by exposure to the
electron beam have been previously described. The sheets of U.S.
Pat. No. 3,370,981 are initially colored, being converted to a
different color by the action of the beam. They do not provide a
colorless background and accordingly cannot be combined in
multiple-color packs to provide true color reproduction. U.S. Pat.
No. 3,425,867 uses colorless materials but the colored product
obtained on treatment is unstable and the color soon fades.
In forming and using the recording sheets of the present invention,
a transparent, translucent, or opaque substrate is coated with a
polymeric binder containing an electron beam sensitive colorless
dye progenitor. An electron beam impinging on such a sheet produces
a permanent image immediately and does not require fixing. Positive
or negative images of a copy and full color copies can be made.
Color correction is easy and enhancement of any given color is
possible. Additional images may be added to a previously imaged
sheet.
The electrical characteristics of the substrate are of considerable
importance in the preparation of the recording sheets. If the
dielectric constant is high enough (e.g. above about 5.0), no
conductive coating is required. If the dielectric constant is lower
(e.g. below about 5.0), then a conductive coating is required. If
the substrate has a dielectric constant below about 5.0, then a
conductive coating must be laid down on the substrate so that the
resistivity will be less than 10.sup.8 ohm-cm.
By interaction with an electron beam, the progenitors yield
cationic dyes which are intensely colored and transparent. A source
of anion, which is referred to as an anionogen, must be available
in order to allow formation of the colored form. The anionogenic
function can come from the dye molecule, from the binder or from an
additive in the binder-dye progenitor system.
The anionogen is a required component, and may come from the dye
progenitor or precursor molecule, the binder, or an additive.
For example, the dye progenitor of FIG. 88 itself serves as an
anionogen by virtue of the ring-substituted halogen atom. The
compound is colorless and may be incorporated into a neutral binder
(e.g. ethylcellulose, polyvinyl acetate, styrene-acrylonitrile
copolymer). Upon exposure to an electron beam, a magenta image is
produced immediately in the areas struck by the electron beam at
about 10.sup.13 to 10.sup.14 electrons/cm.sup.2.
The anionogen must be a compound which is stable to normal room
light, soluble in the binder system, and able to provide an anion
upon interaction with the electron beam. Halogen-containing
compounds which provide a halide ion by interaction with the
electron beam are useful. They include
polyvinyl chloride
p-diiodobenzene
4,4'-dibromobiphenyl
1,2,4,5-tetrabromobenzene
4,4'-dibromodiphenyl ether
1,3,6,8-tetrachloropyrene
hexachloro diphenyl oxide
bromotrifluoroethylene fluid
chlorinated biphenyl
tetrabromomethyl methane
p-phenoxybenzenesulfonylfluoride
Full color positive or negative copies of colored transparencies or
hard copy can be prepared using the sheet material of this
invention. The material to be copied is mounted in a convenient
position and a video camera is focused on the material. The image
viewed by the video camera may be monitored by a color TV monitor
and the signal from the camera is fed into the electron beam
recorder. For full color copies, color filters are sequentially
placed before the video camera to provide color separation and the
sheet material containing appropriate dye progenitor is used
sequentially in the electron beam recorder. Finally, the three
exposed sheets are laminated in register to form the full color
transparency.
The invention is further illustrated by the following non-limiting
examples in which all parts are by weight and temperatures in
degrees centigrade unless otherwise indicated.
EXAMPLE 1
The substituted heterocyclic amine of FIG. 87,
2(4-dimethylaminostyryl)-1,3,3-trimethylindolenine, is prepared by
the dropwise addition of a solution of 1 part of sodium borohydride
in 10 parts of water to a stirring mixture of 30 parts of methylene
chloride and 40 parts of an aqueous solution containing 2 parts of
the styryl dye, 2(4-dimethylamino-styryl)-1,3,3-trimethylindolinium
chloride. The addition of borohydride solution is continued until
the color is fully discharged from the dye solution. The stirring
is stopped, the phases separated, and the lower nonaqueous phase
washed several times with several parts of water. The washed phase
is then dried over anhydrous sodium sulfate (about 2 parts) and the
methylene chloride distilled off. The residue obtained is
recrystallized from methanol and yields the desired amine having a
melting point of 124.5.degree. - 126.degree. C. Data from high
resolution mass spectrography establishing the molecular formula of
the purified substituted heterocyclic amine as C.sub.21 H.sub.26
N.sub.2.
EXAMPLE 2 (FIG. 88)
The substituted heterocyclic amine of FIG. 88
2(2-chloro-4-dimethylaminostyryl)-1,3,3-trimethylindolenine is
prepared by following the procedure of Example 1 with the
substitution of the styryl dye
2(2-chloro-4-dimethylaminostyryl)-1,3,3-trimethylindolinium
chloride for that used above. The desired amine is obtained with a
melting point of 153.5.degree. - 155.5.degree. C., molecular
formula by high resolution mass spectrography: C.sub.21 H.sub.25
N.sub.2 Cl.
EXAMPLE 3 (FIG. 90)
The heterocyclic amine of FIG. 90
(2-(4-morpholinostyryl)-1,3,3-trimethylindoline) is obtained by
replacing the styryl dye used in the procedure of Example 1 with
the styryl dye, 2(4-morpholinostyryl)-1,3,3-trimethylindolinium
chloride. The desired amine is obtained as a partially purified
material having a melting point of 121.degree.-131.degree. C. and
an empirical formual of C.sub.23 H.sub.26 ON.sub.2.
EXAMPLE 4 (FIG. 108)
The substituted heterocyclic amine of FIG. 108
(2-(4,4-bis(4-dimethylaminophenyl)butadienyl)-1,3,3-trimethylindoline
is prepared by dropwise addition of a solution of 1.1 parts of
sodium borohydride in 13 parts of water to a stirring mixture of
4.86 parts (0.01 moles) of the styryl dye,
2(4,4-bis(4-dimethylaminophenyl)butadienyl)-1,3,3-trimethylindolinium
chloride in 100 parts of water and 37 parts of methylene chloride.
After 4.6 parts of the sodium borohydride solution has been added
the blue color of the styryl dye is fully discharged. The methylene
chloride layer is separated, dried over sodium sulfate and the
methylene chloride distilled off in a rotory evaporator. The dark
brown residue is milled in 95 percent ethanol containing about 0.1
parts of sodium borohydride and then filtered. After vacuum drying,
the tan colored insoluble portion weighs 3.25, sinters at
172.degree. C. and melts at 182.degree. - 183.degree. C. The
molecular formula of the purified substituted heterocyclic amine is
found to be C.sub.31 H.sub.37 N.sub.3.
EXAMPLE 5
In a suitable container equipped with an air condenser and a drying
tube to exclude atmospheric moisture and heated by a steam bath are
replaced 50 part glacial acetic acid, 2 parts of concentrated
hydrochloric acid, 7.07 parts of
3,3-bis(4-dimethylaminophenyl)acrolein (0.024 moles) and 4.16 parts
of 1,3,3-trimethyl-2-methylene-indoline (0.024 moles). The mixture
is heated for 18 hours during which time it takes on a deep blue
coloration. The solution is concentrated to about one-half its
initial volume, diluted to 600 parts by volume with water and
salted out with a mixture of sodium chloride and sodium acetate.
After filtering and drying, the solid is extracted with chloroform
in a Soxhlet extractor to remove salt and the chloroform
concentrate evaporated to yield 11.7 parts of green-grey
microcrystals of
2-(4,4-bis-(4-dimethylaminophenyl)butadienyl)-1,3,3-trimethylindolinium
chloride.
The above indolinium chloride is used in place of the styryl dye of
Example 1 to give the heterocyclic amine of FIG. 107.
EXAMPLE 6
By replacing the styryl dye used in the procedure of Example 1 with
2(5(1,3,3-trimethylindol
ylidene)-penta-1,3-dienyl-1)-1,3,3-trimethylindolinium chloride,
the dihydroheterocyclic amine of FIG. 125 (2[5(1,3,3-trimethylindol
ylidene)penta-1,3-dienyl-1]-1,3,3-trimethylindoline) is prepared.
The molecular formula is established as C.sub.27 H.sub.32 N.sub.2
by high resolution mass spectroscopy.
EXAMPLE 7
The substituted heterocyclic amines shown in FIGS. 87 - 137 are
prepared by the dropwise addition of a solution of 1 part of sodium
borohydride in 20 parts of ethanol to a solution of 1 part of the
corresponding methine dye in 100 parts of methanol. The addition of
borohydride solution is continued until the color is discharged
from the dye solution. The methanol is evaporated from the reaction
mixture and the residue taken up in about 20 parts methylene
chloride. The supernatant solution is decanted from the insoluble
residue formed on standing and is evaporated. The essentially
colorless substituted heterocyclic amine obtained as a residue by
evaporation of the methylene chloride is added to 100 parts of a 10
percent weight per weight solution of a copolymer of 87 percent
vinyl chloride-13 percent vinyl acetate (Bakelite VYHH) in 75/25
methyl ethyl ketone/toluene by weight to form a coating
composition. The coating composition is coated at a wet thickness
of 3 mils (75 microns) onto a transparent electrically conductive
polyester film and dried. Samples of the coated sheet are exposed
to a conventional electron beam at 20 kilovolts and 3 microamperes.
Color of the developed image, and sensitivity, are given in Table
1.
Table 1 ______________________________________ Compound of FIG.
Color Sensitivity.sup.(a) ______________________________________ 87
Magenta A 88 Magenta A 89 Magenta A 90 Red-magenta A 91 Yellow C 92
Magenta A 93 Orange B 94 Amber C 95 Yellow D 96 Magenta A 97
Scarlet A 98 Yellow C 99 Magenta A 100 Magenta A 101 Magenta A 102
Red-orange A 103 Orange A 104 Orange A 105 Yellow B 106 Yellow A
107 Blue B 108 Blue A 109 Orange-yellow A 110 Purple A 111 Blue A
112 Magenta A 113 Blue A 114 Blue A 115 Blue A 116 Yellow D 117
Magenta B 118 Blue B 119 Magenta C 120 Blue B 121 Magenta C 122
Magenta C 123 Blue B 124 Red A 125 Cyan A 126 Blue-cyan A 127
Magenta C 128 Blue C 129 Blue B 130 Blue B 131 Pink B 132 Blue D
133 Blue B 134 Magenta C 135 Magenta B 136 Magenta A 137 Blue C
______________________________________ .sup.(A) Sensitivity A =
Good B = Medium C = Low D = Insensitive
Those skilled in the art will readily perceive that numerous other
dihydroheterocyclic amines of the invention can be obtained by the
procedures herein disclosed and that they can be used similarly in
radiation-sensitive compositions.
EXAMPLE 8
Transparent polyester film (2.5 mil or 0.0625 mm) was vapor coated
with chromium to yield a sheet material with a resistivity of
10.sup.4 ohms per square and a visible light transmission of 50
percent. The conductive surface of the sheet was knife coated at a
wet thickness of 3 mils or 0.075 mm. with a solution of 50 mgm. of
the dihydroheterocyclic amine compound of FIG. 108 and 0.5 gm.
copolymer of 87 percent vinyl chloride -- 13 percent vinyl acetate
("Vinylite VYHH") dissolved in 3.4 gm. methylethylketone and 1.1
gm. toluene.
The dihydroheterocyclic amine was dissolved in the polymer solution
to form a clear colorless solution. After coating, the sheet was
dried at room temperature to form a colorless transparent sheet
which was stable in room light.
The sheet was exposed to a conventional electron beam using 20kV,
3.mu.A. The film, upon exposure to the electron beam, immediately
developed a transparent blue color. After removing the film from
the electron beam assembly, the exposed portion of the film
maintained its blue transparent color and the background remained
clear, colorless, and transparent. Unexposed film was stored in
room light for an extended period of time without deleterious
effect. The exposed film was also uniformly stable. Another portion
of the prepared film was tested using an electron beam of 20kV, one
square inch raster at from 10.sup.11 to 10.sup.14
electrons/cm.sup.2. Variations in the optical density were achieved
from visible marking at 10.sup.11 electrons/cm.sup.2 to dense blue
transparent image at 10.sup.14 electrons/cm.sup.2. The unexposed
film was stored in the laboratory under normal light conditions for
about one-half year. This film was then exposed in the electron
beam arrangement and the color developed immediately. A comparison
with film which had been exposed to the electron beam one year
before and allowed to remain in the laboratory under normal
lighting showed no discernible difference.
Other color progenitor dihydroheterocyclic amines were substituted
for that of FIG. 108 used above to produce equally effective
electron beam recording sheets which produced images of other
colors. Typical examples are as tabulated, the exposure in
electrons/cm.sup.2 required to produce an optical density of 1
being indicated for convenience.
______________________________________ Compound (FIG.) Color
Exposure ______________________________________ 91 Yellow 10.sup.14
105 Yellow 10.sup.14 111 Blue 10.sup.14 125 Cyan 10.sup.14
______________________________________
EXAMPLE 9
In order to provide increased surface conductivity, a polyester
film carrier was first coated with a dilute solution of
polydimethyl dialkyl ammonium chloride ("Calgon 261"), and dried.
The film was then further coated with the solution of binder and
color precursor as in Example 8. The sheet had a resistivity of
10.sup.4 ohms/square and a light transmissivity approximately 97
percent of that of the uncoated polyester film. Under an electron
beam exposure of 10.sup.14 electrons/cm.sup.2 the sheet produced a
blue transparent image.
EXAMPLE 10
The film base of Example 8 was coated with a solution of 0.5 g of
styrene-acrylonitrile copolymer ("Tyril 880") and 50 mgm. of the
dihydroheterocyclic amine of FIG. 88 in 4.5 g. of methyl isobutyl
ketone. Exposure of the dried colorless sheet to the electron beam
at 20kV and 3.mu.A produced a transparent magenta image.
After removing the film from the electron beam assembly, the
exposed portion maintained its magenta transparent color and the
background remained clear, colorless, and transparent even though
it was left on an intensely lighted (600 watt) overhead projector
for over 4 hours.
Similar results were obtained when the binder was replaced
with:
A. VYHH applied as 10% solution in 3/1 mixture of methylethylketone
and toluene.
B. 10 percent solution of polyvinyl acetate (Gelva V-100 from
Shawinigan Products) in methylethylketone.
C. 3 percent solution of ethylcellulose in toluene (Ethocel N-200
from Dow Chemical Co.).
D. 10 percent solution of a chlorinated polyethylene containing 48
percent chlorine (QX 2243.25 from Dow Chemical) in
methylethylketone.
Other materials which liberate anions on exposure to an electron
beam and which serve as anionogens suitable for the purposes of the
invention, such as those listed above, are also employed in making
useful electron beam recording sheets.
EXAMPLE 11
A clear colorless solution of 50.0 mgm. of the dihydroheterocyclic
amine of FIG. 88 and 5.0 gm. VYHH solution (10 percent by weight
VYHH in methylethylketone-toluene solvent; 3 parts
methylethylketone, 1 part toluene) was knife coated on a sheet of
polyvinylidene fluoride (3 mil or 0.075 mm) to a wet thickness of
three mils (0.075 mm) and then dried at room temperature to form a
light-stable colorless transparent sheet.
Exposure of the sheet material to a conventional electron beam
yields a transparent, sharp magenta image. The magenta image is
clearly visible at 10.sup.12 electrons/cm.sup.2 and at 10.sup.14
electrons/cm.sup.2 the optical density equals one.
EXAMPLE 12
Polyester (2.5 mil or 0.0625 mm) was vapor coated with chromium to
yield a sheet material with a resistivity of 10 ohms-cm and a
visible light transmission of 50 percent. A clear colorless
solution of 50 mgm each of the dihydroheterocyclic amines of FIGS.
87 and 108 and 5.0 g. of a solution of 10 percent VYHH in 3:1
methylethylketone-toluene solvent was knife coated on the
conductive surface of the substrate at a wet thickness of 3 mils
(0.075 mm) and dried at room temperature to form a colorless
transparent sheet which was stable to room light.
The resulting sheet was exposed to a conventional electron beam
using 20kV, 3.mu.A. The film, upon exposure to the electron beam,
immediately developed a sharp transparent purple image. The image
was easily defined at 10.sup.11 electrons/cm.sup.2 . An optical
density of one was obtained by an exposure of 5 .times. 10.sup.13
electrons/cm.sup.2. The imaged sheet was stored under normal room
light for one week and then re-exposed to the electron beam on an
area of the film which previously has not been struck by the beam.
The transparent purple image developed and the optical density of
image was essentially the same as the originally developed
areas.
EXAMPLE 13
Bond paper (No. 10) was knife coated with a solution of Calgon 261
(4 parts Calgon 261 to 6 parts H.sub.2 O) to a wet thickness of 3
mils (0.075 mm). The resulting sheet was allowed to dry, but while
it was still tacky it was knife coated with the dye
progenitor-binder formulation of Example 11 above. The coated sheet
was dried at room temperature to form a light-stable colorless
sheet.
Exposure of the sheet to conventional electron beam yields a sharp
magenta image at 10.sup.12 electrons/cm.sup.2.
EXAMPLE 14
Three separate transparent recording sheets (A, B and C) are
prepared in accordance with the procedures described in Example 8,
but using the specific dihydroheterocyclic amines of FIGS. 125, 88
and 98 respectively.
A full color picture was mounted horizontally in a rigid frame and
a television camera (Concord Separate Mesh Vidicon- Model CTC-30)
was focused on the picture. Focusing and centering is observed on a
TV monitor. A red filter (peak transmission at 630 m.mu.) is placed
in front of the camera lens and the resulting signal is fed into a
3M Electron Beam Recorder Model 100. Sheet A is used to record the
resulting red separation and gives a cyan image. The process is
repeated using a green filter which peaks at 525 m.mu. and the
green separation is recorded on Sheet B to give a magenta image.
The process is again repeated using a blue filter which peaks at
450 m.mu. and the blue separation is recorded on Sheet C to give a
yellow image. The resulting three images are laminated in register,
with the yellow image on the bottom, then the cyan and finally the
magenta image on the top. The composite is then a full color 16 mm
positive transparency of the original 81/2 .times. 11 inches color
picture. The transparency was projected to about a 4 .times. 5 foot
size to give a sharp, clear, faithful color reproduction of the
original picture.
EXAMPLE 15
Three sheets of polyester were coated with Calgon 261 as described
in Example 9. The resulting conductive sheets were coated with dye
progenitor-binder systems and exposed to the modulated electron
beam as described in Example 13. The three exposed color
separations were laminated in register and the resulting positive
transparency was projected to give a superior, sharp, brightly
colored copy of the original.
EXAMPLE 16
Three sheets of polyester were coated with Calgon 261 as described
in Example 9. The first sheet was coated with a mixture of 50.0 mgm
of the dihydroheterocyclic amine of FIG. 88 in 5.0 gms of a 10
percent solution of VYHH in methylethylketone to a wet thickness of
3.0 mils. The resulting sheet yields a magenta image upon exposure
to an electron beam.
The second sheet was coated with a mixture of 50.0 mgm of Michler's
Hydrol, bis(p-dimethylaminophenyl)-carbinol, in 5.0 gms of a 10
percent solution of VYHH in methylethylketone to a wet thickness of
3.0 mils. The resulting sheet yields a cyan image upon exposure to
an electron beam.
The third sheet was coated with 50.0 mgm of
2-(2-(4-carbamidoxyphenyl)ethenyl)-3,3-dimethylindolenine
(described in U.S. Pat. No. 3,542,775) in 5.0 gms of a 10 percent
solution of VYHH in methylethylketone. The resulting sheet yields a
yellow image upon exposure to an electron beam.
The three sheets are exposed as described in Example 13 and the
resulting positive transparency yields a very sharp, faithful
projection of the original.
* * * * *