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Publication numberUS3916069 A
Publication typeGrant
Publication dateOct 28, 1975
Filing dateApr 2, 1973
Priority dateApr 2, 1973
Also published asCA1035366A, CA1035366A1, DE2415751A1
Publication numberUS 3916069 A, US 3916069A, US-A-3916069, US3916069 A, US3916069A
InventorsTiers George V D, Wiese Jr Joseph A
Original AssigneeMinnesota Mining & Mfg
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Reduced styryl/cyanine dye
US 3916069 A
Abstract  available in
Previous page
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 1191 Tiers et a].

14 1 Oct. 28, 1975 1 REDiJCED STYRYL/CYANINE DYE [75] Inventors: George V. D. Tiers; Joseph A.

Wiese, Jr., both of St. Paul, Minn.

[73] Assignee: Minnesota Mining and Manufacturing Company, St. Paul, Minn.

[22] Filed: Apr. 2, 1973 [21] App]. No.: 347,193

[52] US. Cl. 428/411; 96/1.6; 96/129; 7 250/475; 260/240.9 [51] Int. Cl. B41M 5/00; B41M 5/20 [58] Field of Search 96/l.6, 129; 260/2409;

OTHER PUBLICATIONS Chemical Berichte, Vol. 65, pages 1737-1742 (1932).

Primary ExaminerThomas .1. Herbert, Jr. Attorney, Agent, or FirmA1exander, Sell, Steldt & DeLa1-1unt [5 7 ABSTRACT Dihydroheterocyclic amines having a N-hydrocarbyl substitution and a 2-(or 4-) (omega-(nuclearly substi- [56] Refere Cit d tuted cyclic)) vinylenyl substitution are described.

UNITED STATES PATENTS These compounds are oxidized in an acidic environ- 3,370,9s1 2/1968 Ney et a1. 117/230 mm to produce Sty'y] and cyanme dyes 3,567,439 3/1971 Daniel et a1. 96/1.6 7 Claims, 150 Drawing Figures (h=(/{-(// f IV 3 US. Patent Oct.28,1975 Sheet10f8 3,916,069

U.S. Patent Oct.28, 1975 Sheet4of8 3,916,069

US. Patent Oct. 28, 1975 FIG. IO!

hg C (H77 \dli? H3 FIG. I07



U.S. Patent Oct. 28, 1975 Sheet 8 of 8 3,916,069

REDUCED STYRYL/CYANINE DYE 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'yie'ld 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 US. 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-phenylmethane or diphenylmethane dyes. These elements produce colorations limited mainly to the blue to green range of the visible spectrum. In US. 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-hydroca'rbyl 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, cycl'oalkyl, phenyl and benzyl and including not more than about 60 atomic weight units of the atom elements, 0, N, F, C1 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,

2 thiophene and that reducedv forms will in general be named appropriately.-

,ln radiation sensitive elements containing anionogens,these color progenitors are storage stable for all practical purposeslindefinitely (i.e., the element does not develop color in areas that have not been exposed tosuitable radiation). More specifically, the amines of the invention are essentiallycolorless N-hydrocarbylsubstituted-2-(or 4-) (omega-(nuclearly substituted cyclic)vinylenyl) dihydroheterocyclic amines. These many frequently be referred to herein as substituted heterocyclic amines or asvinylenyl-substituted hetero- ,cyclic 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 [2 wherein Q is a divalent radical of 1 to 4 atoms which joins N to C when m l or 1, or joins N to C when m l and, except for auxochromic substituents and hydrogen, consisting essentially of the nonmetallic atoms necessary to complete a5 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;

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 lto 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 or C are attached to H except that not more than one may be attached to 3 ployed. 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.

v 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 l to 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;

Structure II Structure III In Structures II and Ill, n is an integer from 1 3 and n" is O 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.

In Structure IV, R is hydrocarbyl and preferably primary alkyl of l 6 carbon atoms, Q is CRR, S, 0, Se, or NR in which each R 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 benzoor naphthosubstituent 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.

-Wi or Structure V 4 Z is H, Cl, F, alkyl of l 6 carbon atoms, OR or Z" is H, Cl, F, alkyl of l 6 carbon atoms or 0R Z and adjacent Z" taken together can be benzo or naphtho with or without auxochromic substituents;

R is alkyl of 1 6 carbon atoms;

R is methyl or ethyl;

R and R 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:

2, IQ}, 2 I.

l R R wherein R, Q and the two Zs 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 in clude those shown in FIGS. 1 to 29 inclusive, wherein the names of the respective structures are:

FIG. Name 1 l ,3 ,3-trimethyl-2,3-dihydro-2-indolyl 2 l ,3 ,3-triethyl-2,3-dihydro-2-indolyl 3 S-ethoxyl ,3,3-trimethyl-2,3-dihydro-2-indolyl 4 l-methyl-3 ,3-dibenzyl-2,3-dihydro-2-indolyl 5 S-c hlorol ,3 ,3-trimethyl-2.3-dihydro-2-indolyl 6 S-phenyll ,3,3-trimethyl-2,3-dihydro-2-indolyl 7 5-diethylaminol ,3,3 -trimethyl-2,3-dihydro-2-indolyl 8 S-benzene sulfonyll ,3,3-trimethyl-2,3-dihydro- 2-indolyl 9 S-ethoxycarbonyll ,3 ,3-trimethyl-2,3-dihydro-2- indolyl l0 S-dimethylamino carbonyll ,3,3-trimethyl-2,3-

dihydro-Z-indolyl l l 5-cyanol ,3 ,3-trimethyl-2,3-dihydro-2-indolyl l 2 N-butyll ,Z-dihydro- Z-quinolyl l 3 6-bromol-phenyll 2-dihydro-2-quinolyl l4 6-ethoxyl-ethyll ,2- dihydro-Z-quinolyl l 5 1 -ethyl-l ,2-dihydro-2-( 5 ,6-benzo )-quinolyl l 6 3-ethyl-2,3-dihydro-2-benzoxazolyl l 7 6-methoxy-3-ethyl-2, 3-dihydro-2-benzoxazolyl l 8 3-methyl-2,3-dihydro -2-benzothiazolyl I 9 6-chloro-3-n-propyl-2,3-dihydro-2-benzothiazolyl 20 6-phenoxy-3-ethyl-2, 3-dihydro-2-benzothiazolyl 2 l 6-methyl-3-phenyl-2, 3-dihydro-2-benzothiazolyl 22 6-dimethylaminosulfonyl-3-ethyl-2,3-dihydro-2- benzothiazolyl 23 3-butyl-2,3-dihydro2 [2,1 ,d]-naphththothiazolyl 24 3 ,5 ,6-trimethyl-2,3-dihydro-2-benzothiazolyl 25 3-cyclohexyl-2,3-dih ydro-2-benzothiazolyl 26 l ,3-dimethyll ,2-dihydro-2-benzimidazolyl 27 S-methoxy- I ,3-diethyll ,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:

Examples of suitable nuclei A, Structure V heterocyclic radicals include those shown in FIGS. to 58 inclusive wherein the names associated with the respective structures are:

FIG, Name 30 2-pyridyl 3 l 4-quinolyl 32 Z-bcnzothienyl 33 l-methyl-2-benzimidazolyl 34 2-benzoxazolyl 35 -furyl 36 3-thienyl 37 2-thienyl 38 l-ethyl-3-pyrryl 39 l-methyl-Z-pyrryl 40 l-methyl-3-indolyl 4l lO-melhyI-7-phenothiazinyl 42 4-diethylamino-phenyl 43 4-dimethylamino-a-naphthyl 44 2-dimethylamino-5-methyl-phenyl 45 4-rnorpholinyl-phenyl 46 p-anisyl 47 p-hydroxyphenyl 48 o-butoxyphenyl 49 p-phenoxy-phenyl 50 biphenylyl 5 l phenyl 52 a-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 4 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 Z-methylprop- 1 -en- 1 -yl-3-ylidene 62 Z-phenylprop- 1 -en- 1 -yl-3-ylidene 63 1,3-(2' ,2'-dimethylpropan0 )-pental ,3-dienl-yl- 5-ylidene 64 pental ,3-dienl -yl-5 -ylidene 65 hepta- 1 ,3,5-trienl-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.

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-(di'methylamino)styryl l ,3,3-trimethylindoline 88 2-( 2-chloro-4-dimethylaminostyryl l ,3,3-trimethylindoline 89 2-( 4-diethylaminostyryl )-l ,3 ,3-trimethylindoline 90 2-(4-morpholinostyryl l ,3 ,3-trimethylindoline 9 l 2-(3,4-dimethoxy styryl l ,3,3-trimethylindoline 92 (2-(4-( ethylbenzylamino)styryl l ,3 ,3-trimethylindoline 93 2-(3,5-di-t-butyl-4-hydroxystyryl)-1,3 ,3vtrimethylindoline 94 2-( 2,3-benzostyryl l ,3 ,3-trimethylindoline 95 2-( 2-dimethylamino-S-methyl-styryl l 3,3-

trimethylindoline 96 2-( 4-( phenylmethylamino )styryl l ,3,3-trimethylindoline 97 2-( 4-bis( 2-chloroethyl )amino styryl l ,3 ,3-

trimethylindoline 98 2-( 4-hexyloxystyryl l ,3,3 -trimethylindoline 99 2-( 2-ethoxy-4-diethylaminostyryl l ,3 ,3-trimethylindoline I00 2-(4-dibenzylaminostyryl l ,3,3-trimethylindoline l0l 2-( 2-methyl-4-( benzylethylamino)styryl l ,3 .3-

trimethylindoline 102 2-( 2-( 9-ethyl-3-carbazolyl )ethenyl l ,3 .3-trimethylindoline /|LZv and wherein Q, R, Z, Z, Z" are as defined above and Y is NR R wherein R and R 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-( l-ethyl-3,3-dimethylindolylidene-2)prop-1-enyl-l l -ethyl-3 ,3-dimethylindoline 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 arid Related Compounds, Hamer, lnterscience 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.,

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 ll 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 are as defined before; p is O to 3; and R 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 to 50 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 to 30 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. ln 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 sufiicient 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 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. 1

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 US. 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. US. 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 l0 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 to 10 electrons/cm? 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 ex- 13 posed 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 l ,3 ,3 -trimethylindolenine, is prepared by the dropwise addition of a solution of 1 part of sodium borohydride in 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)-l,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 124.5 126 C. Data from high resolution mass spectrography establishing the molecular formula of the purified substituted heterocyclic amine as C I-I N 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)- l ,3 ,3-trimethylindolinium chloride for that used above. The desired amine is obtained with a melting point of 153.5 l55.5 C., molecular formula by high resolution mass spectrography: C l-l N Cl.


The heterocyclic amine of FIG. 90 (2-(4-morpholinostyryl)-l,3,3-trimethylindoline) is obtained by replacing the styryl dye used in the procedure of Example 1 with the styryl dye, 2(4-morpholinostyryl)-l,3,3- trimethylindolinium chloride. The desired amine is obtained as a partially purified material having a melting point of 12 ll3l C. and an empirical formual of za zs z- EXAMPLE 4 (FIG. 108) The substituted heterocyclic amine of FIG. 108 (2- (4,4-bis(4-dimethylaminophenyl)butadienyl) l ,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 I weighs 3.25, sinters at 172 C. and melts at 182 183 14 C. The molecular formula of the purified substituted heterocyclic amine is found to be C l-I N 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-Z-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 ll.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(l,3,3-trimethylindol ylidene)-penta-1,3-dienyl- 1 )-l ,3 ,3-trimethylindolinium chloride, the dihydroheterocyclic amine of FIG. 125 (2[5( 1,3,3- trimethylindol ylidene )pental ,3-dienyl-l ]-l,3,3- trimethylindoline) is prepared. The molecular formula is established as C I-I N 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 evapo rated 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- 1 3 percent vinyl acetate (Bakelite VYI-II-l) in /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 l-continued Compound of HG. Color Sensitivity 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 Redorange A 103 Orange A 104 Orange A 105 Yellow B 106 Yellow A 107 Blue B 108 Blue A 109 Orange-yellow A 1 Purple A 1 l 1 Blue A 1 l2 Magenta A 1 13 Blue A 1 14 Blue A 1 Blue A 1 16 Yellow D 1 l7 Magenta B 1 18 Blue B 1 l9 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 ""Sensitivity A Good B Medium C Low D lnsensitivc Those skilled in the art will readily perceive that numerous other dihydroheterocyclic amines of the invention can be obtained by the procedures herein dis closed and that they can be used similarly in radiationsensitive 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 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. 1108 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 kV, 3 ,uA. 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 to 10 electrons/cm? Variations in the optical density were achieved from visible marking at 10 electrons/cm to dense blue transparent image at 10 electrons/cm? 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 re quired to produce an optical density of 1 being indicated for convenience.

Compound (FlG.) Color Exposure 91 Yellow 10 Yellow 10 1 1 1 Blue 1O Cyan 10" EXAMPLE 9 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 3uA 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. VYHl-l applied as 10% solution in 3/1 mixture of methylethylketone and toluene.

17 B. 10 percent solution of polyvinyl acetate (Gelva V-100 from Shawinigan Products) in methylethylketOl'ie.

C. 3 percent solution of ethylcellulose in toluene (Ethocel N-200 from Dow Chemical (30.);

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 elec tron beam recording sheets.

EXAMPLE 1 l A clear colorless solution of 50.0 mgm. of the dihydroheterocyclic amine of FIG. 88 and 5.0 gm. VYl-IH solution (10 percent by weight VYI-II-I 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 electrons/cm and at 10 electrons/cm 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, 3uA. The film, upon exposure to the electron beam, immediately developed a sharp transparent purple image. The image was easily defined at 10 electrons/cm? An optical density of one was obtained by an exposure of X electrons/cm? 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 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 EXAMPLE 14 Three separate transparent recording sheets (A, B and C) are prepared in accordance with the procedures described in Example 8, but using'thespecific 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 mp.) is placed in front of the camera lens and the resulting signal is fed into a 3M Electron Beam'Reco'rder 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 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 mp. 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 8 /2 X 11 inches color picture. The transparency was projected to about a 4 X 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 grns of a 10 percent solution of VYI-II-I 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 Michlers Hydrol, bis(p-dimethylaminophenyl)-carbinol, in 5.0 gms of a 10 percent solution of VYI-II-I 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 US. Pat. No. 3,542,775) in 5.0 gms of a 10 percent solution of VYI-ll-I in methylethylketone. The resulting sheet yields a yellow image upon exposure to an electron beam.

The three sheets are exposed as described in Example l3 and the resulting positive transparency yields a very sharp, faithful projection of the original.

What is claimed is:

l. 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 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)- l ,3 ,3-trimethylindoline.

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U.S. Classification430/338, 548/440, 546/176, 430/343, 548/150, 548/468, 548/152, 546/165, 430/344, 548/455, 546/329, 548/217, 544/143, 546/277.4, 548/159, 548/255, 548/490, 548/511, 548/509, 548/156
International ClassificationG03C1/72, G03C1/675, G03C1/73, G03G15/05
Cooperative ClassificationG03C1/732, G03C1/733, G03C1/675
European ClassificationG03C1/73P, G03C1/73L, G03C1/675