CA1158912A - Tellurium imaging composition including a n-amido substituted pyrazo containing masked reducing agent - Google Patents

Abstract

ABSTRACT

This application relates to an imaging composition employing a tellurium compound sensitive to activating radiation. Such imaging compositions have been disclosed in a number of earlier patents, such as U.S. Patents 4,142,896, 4,066,460 and 4,106,939. This application dis-closes improvements in masked reducing agents for such com-positions. The improved masked reducing agents are compounds of the formulae ; or wherein Y is hydrogen or , said compound containing at least one

Description

\ l 8 ~1 2 ; This application relates to an improved imaging composition system employing tellurium compounds senstive to activating energy.

_he Pr.ior Art Background Various methods are known Eor producing images or duplicates oE images. The imaging materials used are, in certain cases, particular inorganic compounds and, in other cases, particular organic compounds. Some of these heretofore known methods emplo~ mi~tures of inorganic com-pounds such as silver halide with one or more particularty~es of organic compounds as sensitizers.
A new photographic process using tellurium com-pounds to provide the image is disclosed in U.S. Patent 4,142,896. In accordance with Patent No. 4,142,896, an emulsion is formed using certain reducible tellurium com-pounds in combination with a reductant precursor in a binder suitable for forming a film-like coating on a substrate.
The film prepared therefrom is exposed imagewise to :!

.~

m~ ) iJ

activatin~ energy and may be thereafter developed as is known in the art hereinafter described. Heat development is preferred.
Some tellurium compounds described for use in the photographic process of Patent No. 4,1~2,896 may be repre-sented, for example, by the formula:

Rx-Te-Xy in which R is an organic radical containing at least one carbonyl group, X is halogen, preferably cnlorine, and X
is 1, 2 or 3, and x + y -- 4. The organic radical R may be either two indepQndent radicals or may be joined to-gether to form a cyclic compound. Another ~roup of com-pounds mentioned in U.S. Patent 4,142,896 are or~anic telluriwn compounds which may be considered or characterized as telluri~n tetrahalide adducts of ethyleneic or acetyleneic hydrocarbons. Some of such compounds can be represented by the formulae:
., X
X-R-Te-Rl-X
X

and (X-R~n-Te-X

wherein R and Rl are each the residue of an ethyleneic hydrocarbon, and X is a halogen, preferably chlorine.
Another broad category of photosensitive tellurium compounds which have been found useul are halogenated 23~51 t.. ~, ..

1 1~8gl2 ~cllurium compounds, such as cOmpounds of thc formula TeclnBrm wh~re n is an inte~er from 2 to 4, and n ~ m - 4. The use o~ such halogenated tellurium compounds in imaging pro-cesses is disclosed in U.S. Patent No. 4,066,460 to Chang et al.
Still another category of useful tellurium com-pounds are described in U.S. Patent No. 4,106,939O These compounds are tellurium tetrahalide adducts of aromatic amines in which the nitrogen attached directly or indirectly to the aromatic ring i.s substituted by alkyls of 1-4 carbon atoms, the adduct being free of diazo groups.
The tellurium compounds such as the foregoing may be employed in conjunction with a reductant precursor which serves as a sensitizer. The reductant precursor lS
a compound which, under the influence of activating energy, will absorb radiation energy and abstract labile hydrogen from an appropriate hydrogen donor to become a strong re-ducing agent. The strong reducing agent reduces the :~ 20 tellurium compound, which results in a change in optical density suitable for recording information. In generaI
terms, the foregoing reaction may be represented by the following mechanism:
hv pQ ~ pQ ~ 3pQ

3PQ ~ 2RH ~ PQH2 -~ R-R

(Rl)2-Te-X ~ 2PQ-H2 ~ 2PQ ~ 2RlH ~ Te ~ 2HX

23~57 1 P58~12 wherein PQ is the reductant preCursor sensitizing agen-t;
~ Q is the first excited singlet state thereof; 3PQ is the ~riplct state thereof; RII is the hyarogen donor; PQ El2 is the reductant precursor in its reduced state; and (Rl)2-Te-X2 is the reducible tellurium image-forming compound.
In this connection, it should be noted that the hydrogen donor need not be specifically provided, although a variety of alcohols can be used if desired. In the ab-sence of a specially provided hydrogen donor, the labile hydrogen can sometimes be abstracted from the organic resins used as binders. In other cases, the sensitizer can be its own hydrogen donor, and *his is known to be the case with at least one preferred sensitizer, namely, isoproxynaphtho-quinone.
A modification of the tellurium photographic pro-cess is described in Belgian Patent No. 854,193, where certain diols of the formula Rlo-CHOE~-Z-CHOH-Rll may be employed as the hydrogen donor for use in conjunc-tion with the photosensitizer described above. In the fore-going formula, Rlo and Rll represent hydrogen and various organic substituents. Z may be a direct carbon-carbon linkage between the two hydroxy-subs-tituted carbon atoms, or may be any of various linkins groups. Reference is made to Belgian Patent No. 854/193 for a fuller description of the diols referred to. In the Belgian patent, these diols are said to serve as hydrogen donors. Subse~uent re-search has suggested that this is not completely accurate.

~ ~158~
In fact, a major portion of the diol appears to form a complex with the tellurium compound.
This finding has led to the discovery of diols oE
the general formula R-0-C~I~C~IO~I-C~I10ll which have improved characteristics when used in -tellurium-based photographic films.
The radical R may be a simple aliphatic group (for example, alkyl or alkenyl). Alternatively, the radical R
may contain a carbonyl group ~for example, an acyl radical)~
Preferably, however, the radical R is aromatic. Best results are obtained where the aromatic ring is separated from the ether oxygen by one methylene grouping~ A more complete description of these diols is contained in U.S.
Patent No. 4,281,058~
Still another modification in the use of tellurium compounds as photosensitive agents involves what is known as a "masked reducing agent". A number of compounds are known, such as phenidone, which will reduce organo-tellurium compounds~ The reducing capacity of such compoundsmay be "masked" - i~e~, inhibited - by appropriate substitution. In such cases, if the substituent is one which can be cleaved by the reaction products liberated upon the photoreduction of the tellurium compound, the masked reducing agent can be used to amplify the photo-response through the mechanism:

dm:~ N~ - 5 ~, .

23~57 ,,~ ;

Ligh~ ~ sensitizer ~ Pilo~oactive ~ + Te Comp.
reducing agt. ~ ~ Tellurium Dcmaslcecl re- J +
ducing agt. ~ ~ ~y-products mask~d reducing agent Since the tellurium compounds commonl~ used release hydrogen halides (particularly hydrogen chloride) as by-products of the reduction reaction, and the reducing agents, such as phenidone, are amino compounds, the masking agents most effectively employed are compounds which will convert the amino nitrogen into an amide. A typical masked reducing agent thus is the compound:
.

~ C - NHC -( ~

- A more complete description of the masked reducing agent may be fou~d in Belgian Patent No. 863,052, and reference thereto is made for an additional description thereof.
In practice, the foregoing ingredients, l.e., a tellurium derlvative, a reductant precursor, and the op-tional ingredients such as the glycol and a masked reduc-ing agent, are combined in a suitable matrix to form an emulsion which is supported by an appropriate carrier. A
latent imaye is formed by exposure to an appropriate ~u~ /

8~12 imaging energy (for example, a light image). The latent image is thereafter developed by heating the exposed film as described in Patent No. 4,142,896.
Alternately, the latent image may be induced by using an electron beam or an electric current as the activating energy. Since electrons so introduced into the film are capable o acting directly on the tellurium compound when such activating energy is used, the rèduc-tant precursor can be omitted from the composition.
Other forms of activating energy will be recog-nized by those skilled in the art, and can also be applied under appropriate conditions.

~158~3~2 ~ Invcntion _ _ _ _ The present invention concerns an improvement in ~h~ al~ove-describcd organo-tellurium system for photo-Ycnsitive emulsi.ons. ~lore specifically, we have found new masked reducincJ agents of the general formulae:

Rl-NZ-NZ2 R2 o R4~ ; or / N~ \

R3 Y y o o wherein Y lS hydrogen or CNEIR , said compound containing at least one ~-NH-R5 group. In the foregoing formulae, Rl may be alkyl, alkanoyl, alkoxycarbonyl, phenyl, benzyl, benzoyl, nitrophenyl, benzylcarbonyl, diphenylmethyl, di-phenylethyl, or di.phenylpropylcarbonyl, or aminocarbonyl.
R2, R3 and R4 each, and independently~ may be hydrogen, alkyl or phenyl and amino. R5 may be phenyl, nitrophenyl, halophenyl, alkyl, mono-, cli- or tri-haloacetyl, benzoyl, alkylphenyl, or alkyl-p-i~ocyanophenyl. The masking group may be substituted at either one or both of the amino nitrogen sites of the reducincJ agent. The alkyl c~roups referrcd to above may contai.n up to seven carbon atoms.

23~57 ~t~58~12 Thcse compounds are conveniently accessible through rc.lc~ion of tile parent hydrazine or pyrazolidine with an i!:ocy;ln~tc of the formula R5-N=C=o Representative compounds of the foregoing are the following:

O O
_ C-N-N-C-N
H H H

O O
- C-N-N-C~ ~ NO2 H H H

0 0 \ O O
~ 15 ~ C-N-N-C-N- ~ -N-C-N-N-C ~

- o o o.
- ~ C-N-N-C-N-C-CC13 H H

l l H H H

~q ' 23~5-i :

l ~58~12 o o <( ~ -C-~-N-C-N ~ Cl . I ~I H

02N ~ _ N-N-C-N-H H H

02N - ~ N-N-C-N ~ - Cl H H

. CH3-C-O-C-N-N-~-N

.

CH O O O
1 3 ~
Crl3_c_o-c-N-N-c-N-c-ccl3 C~l3 Ol O O
C~13-C-O-C-N-N-C-N-C-CH3 H H El _ID

1 ~58~2 CH -C-O- C-N -N-C-N ~ C l CE13 El El El O O
CH3-O~C-N-N-C-N--(~
H H H

O O O
Il 11 11 H H H

o o 'o H H H

OO

E-I H H --Cl CH3 H El H

~11 -11~8~

o o Cll 3 -C-N-N-C-N--o o CH3-C-N_N_~_N ~ - Cl O O O
Cl ~ - N-C-N-N-C-N-N-C-N ~ - Cl o N-N-C-N
H H

..

O O
~ -N-N-C-N-C-CC13 H H H

~ - N-N-C-N ~(3~ cl H H H

1 1$8912 o H H H

O O
S CH3-N-N-~-N-~-- H H ~1 C~3~ -C-N ~ - Cl H H H

' 1 0 ' l l ~; (~CH2-c~N-N-c-N--~) H H H

: ~

H2-c-N-N-c-N - ~ - Cl -' ~

o -(~ CH2-N-N-C-N--(~
: H H H ~

23~357 ~`
9 ~ 2 C~l2-N-N-C-N~ Cl c6H~ Do ~1 N---~>

.

C6~15 ~0 ~1 C N - C ~>

O = C - N - C

, .

/f o H

2 0 )~N - 1 - N ~>

C 6~1 5 1 - N--~) _ /~

u~ /

15~
o o ~ c ~ N

r~ ~1 0 yO

C~13 ~,~ N--<~

C H 3 C - N--~>
o D O H

/~ - C - N--(~

O, 25 ~ ~~C
C - N <~>
O H

2~357 ~ - C - N--Nl o L ~ ~

o (~ C - N - C - cC13 C 6H5 -N - C ~ N ~ o L ~ C 1-~

]t~

I 15~2 -\`Detailed Descrlption of Emulsions ~ccordlng to the Present Inveiltion __ An emulsion formulated in accordance wlth the present inventlon contalns a tellurlum compound, a reductant precursor, and an appropriate binder, and a carrier on whlch a photosensitive fllm can be formed, and a masked reducing agent of the above descri.ption. Optionally, a diol is provided, prefeLAably a glyceryl compound of U.S. Patent No. ~,281,058.
The image-forming tellurium. A number of image-forming tellurium compounds are described in the prior art and such compounds are generally useful in the present invention. In general, the present invention comtemplates using these and other tellurium compounds which undergo analogous reduction reactions in the presence of a reductant precursor as hereinafter described.
It has been found that many tellurium compounds possess certain properties which adapt them especially for use in imaging processes. In general, these are compounds from which, as a result of the imagir.g and developing steps generally referred to above, elemental tellurium is deposited from the tellurium compounds. Tellurium is chain-forming in character, and it is generally deposited from the tellurium compounds useful for photographic purposes (preferably including thin needles), the compounds being capable of rapid nucleation and growth as crystallites, which crystallites grow as chains and largely or mainly as needles. Such chains or needles are opaque and are characterized by excellent light scattering properties to produce good optical density observod after thermal or other development.

dm~ 17 -~ .

~J~JJ /
"
1 ~8~1~

~fects which may involve oxide formation are sub-~tan~ially restricted to surface e~ects as distinguished ~om cffects which cause deyradation through the bodies of thc needles or chains.
Preferably, the tellurium imaging compound is an organo-tellurium compound such as disclosed in U.S. Patent No. 4,1~2,~96 o~ Chang ~t al. These compounds are organic tellurium compounds which inherently possess sensitizer properties (and/or may be mixed with a separate sensitizer) in which the tellurium is linked directly to at least one carbon atom or the organic radical of the organo-tellurium material, the organic tellurium compound being of one struc-ture and having a detectable characteristic which is capable of undergoing a change in response to the application of imaging energy in the form of particle or wave radiation to produce a material of different structure having another detectable characteristic. The material having a different structure and different detectable characteristics resulting from the imaging step is sometimes referred to as the "image-forming compound".
A particularly advantageous subgroup o~ the imag~
ing organo-tellurium compounds utilized in the practice of the present invention comprises organic compounds which contain an organo radical and halogen attached directly to the tellurium atom, there being at least one carbonyl group in the organo radical. Certain of them are addu~ts o~
tellurium halides, notably tellurium tetrachloride, with organic compounds, notably ketones or similar chromophores, containiny at least one carbonyl ~roup in the organic com-pound. They may, thus, be considered or characterized as 23~5l ~ 1~8~2 organo-tcllurium compounds or adducts containing halogen, namcly, chlorine, bromine, iodine, and fluorine, attached directly to the tellurium atom. Most of this particular class or c~roup of said imaging compounds have two carbonyl-containin~ organo radicals. Those which are especially use-ful in the practice of the present invention have chlorine as the halogen but, in certain cases, although generally less satisfactory, other halogens can be present. The imag-ing compounds should be selected to be soluble or homogeneously dispersible in any particular matrix material which may be utilized, as is described herea~ter. Many of this group of imaging organo-tellurium compounds may be represented by the formula Rx-Te-Ha ly where R is an organo radical containing at least one carbonyl group, Hal is halogen r especially chlorine, x is 1, 2 or 3, and .!
x ~ y = 4, subject to the proviso that Te is linked directly to carbon in an organo radical. Preferably, x is 2 or 3.
Others can be represented by the formula R2-Te-Hal4 where R is a carbonyl-co,;taining organic radical, and ~al is halogen.
The R radical can be aliphatic, cycloaliphatic or aromatic (mononuclear or dinuclear) or a combination thereof and may contain one or more hetero atoms in the chain or rings. It may be unsubstituted or substituted by various organic or inorganic radicals, which may assist in or at least do not interfere with the desired imaging effect, illustrative of such radicals being Cl-C6 alkyl, G _~ ~.) J I
" .
~ 158~12 correspondlng oxyalkyl radicals, acetyl, nitro, C--N, Cl, llr, 1`, etc. Generally speaking, the aforesaid organo-~ollurium imaCJinC3 compounds which contain a trihalide ~rou~ a5 ~ for instance, acetophenone tellurium trichloride, tcnd to have relatively low melting points (~70-80~C.), and are more hygxoscopic and less stable than those generally similax compounds containing two halogen atoms and, there-fore, such trihalides are less desirable for use in the practice oE the present invention.
A more limited class of this particular subgroup of imaging organo-tellurium compounds may be represented by the formula (Ar-CO-CEI2) 2Te-Hal2 where Ar is an aromatic hydrocarbon radical, which may be lS substituted or unsubstituted, as indicated above, and Hal is halogen, especially chlorine. This subgroup of com-pounds, particularly where Hal is chlorine, represents especially advantageous embodiments of the invention, with respect to the imaging organo-tellurium compounds which are used in the practice of the present invention.
Another subgroup of imaging oryano-tellurium com-pounds, useful in the practice of and co.ntemplated by the présent invention, ~7hich do not contain a carbonyl group in an organo radical but in which tellurium is linked di-rectly to carbon are compounds which may be considered orcharacterized as tellurium tetrahalide adducts of ethylenic or of acetylenic hydrocarbons. These compounds are generally conveniently produced by reacting 1 to 2 moles, particularly 23~57 115~912 2 n~oles, of th~ ethyl~neic or acetyleneic hydrocarbon with l mole o~ tellurium tetrahalide, especially preferred for ~uch use being TcCl~ Certain of such compounds can be re~resented by the formulae:

Hal Hal R9 - Te R8 Hal ; and I

~Ial (Hal R9)x - Te Haly where R8 and R9 are each the residue of an ethyleneic hydro-carbon, for instance, an alkene or a cycloalkene, ~Ial is chlorine, bromine or iodine, especially chlorine, x is 1 to 3, and x + y = 1.
Illustrative of the ethyleneic and acetyleneic hydrocarbons which can be adducted with tellurium tetra-halides to produce such imaging organo-tellurium compounds are propylene; butene-l; isobutylene; butene-2; 2,3-dimethyl-2-butene; 3,3-dimethyl-l-butene; 2,4-dimethyl-1-pentene;
4 ! 4-dimethyl-1-pentene; 2,5-dimethyi-3-hexene; dipentene;
l,l-diphenylethylene; l-heptene; l-hexene; 2~methyl-1-hexene; 3-methyl-1-hexene; 4-methyl-l-hexene; 2-ethyl-1-hexene; 2-isopropyl-1-hexene; 2-methyl-l-pentene; 2-methyl-2-pentene; 2-ethyl-2-pentene; 3-methyl-l-pentene; piperylene;
vinylcyclohexene; vinylcyclopentene; 2-vinylnaphthalene;
1,2,4-trivinylcyclohexene; 4-methyl-l-cyclohexene; 3-methyl-l-cyclohexene; l-methyl-l-cyclohexene; l-methyl-l-cyclopentene;
cycloheptene; cyclopentene; cyclohexene; 4,4-dirnethyl-l-cyclohexene; 2-methylbutene-l, 3-methylbutene-1; and l-octene; lower alkyl and lower alkoxy derivatives of ~ 1 15~12 various of the alkenes such as cyclohexene; l-pentyne;
2-pentyne; l-hexyne; and 3-methyl-1-butyne.
The preparation of the aforementioned organlc tellurium compounds as well as many examples thereof are more fully set forth in U.S. Patent 4,142,696.
As ind.~cated above, tetrahalides of tellurium in which the halide is at least one member selected from the group consisting of chlorine and bromine are also useful as the image-forming material in the present invention. Such telIuri.um halides are fully described in U.S. Patent No. 4,066,460~ Certain of these imaging materials can be represented by the formula TeCl Br n m where n is an integer from 1 to 4 and m + n = 4. Typical tellurium tetrahalides which may be used are ~eCl4;
TeCl2Br2; and TeClBr3. TeCl4 is especially useful.
Reference is made to U.S. Patent 4,066,460 for a fuller description of these tellurium tetrahalides and their use as image-forming compounds.
Still another group of image-forming compounds are certain compounds derived from tellurium tetrahalides which are described in U.S. Patent 4,106,939 to Chang et al.
These involved compounds are adducts of tellurium tetra-halide with aromatic amines exemplified by the te].lurium tetrachloride adduct of dimethylaniline, which adduct is free of diazo groups. Mor.e specifically, these tellurium dm~ 22 -~ 158~2 t:etrahalLde adduets are forrned by combining a t.ellurium tetrahalicle with an aromatle amine in which Nitrogen attaehed clirectly or indireetly to the aromatie radieal is substituted by alkyls eontainlng from 1 to 'l earbon atomsr the imaging organo-tellurium material being free from dia~o groups.
These aromatic amine adducts of the tellurium tetrahalides are fully described in U.S. Patent ~,106,939 to Chang et al.
The active tellurium compounds may, if desired, be formed in situ, for example, by using a tellurium oxide or a tellurium salt in combination wi~h a suitable organic compound. Sometimes the _ situ formation is promoted by_ the presence of an acid. For example, tellurium oxide or alkali metal tellurates may be combined with one of the glyeols described below to form a tellurium-organie eompound eomplex which is aetive. It is believed that the reaetion is analogous to the reaction between organic tellurium eompounds sueh as deseribed above and a diol.
Preliminary information suggests that the reaetion is favored by an- acidic medium. Small amounts of an acid sueh as anhydrous hydrogen ehloride may be added.
Alternatively, halogen-eontaining tellurium compounds will provide the requisite acidity.
The reductant precursor: In addition to the tellurium image-forming compound, the imaging systems of the present invention may include a reductant preeursor, dm~ 23 -~3~57 1 ~8~2 or sensitizer, which, as described above, is a compound that, under th~ influcnce of activating energy, has the propert~ of extractin~ labile hydrogen from a hydrogen donor to become a reducin~ agent with respect to the image-forming tellurium compound. The activated reducing agent then re-duces the tellurium compound to produce the desired image.
The hydrogen donor may be an external source of hydrogen such as an alcohol specifically provided for the purpose.
However, the hydrogen donor may equally well be an appro-priate group which is a part of the molecular structure ofthe reductant precursor.
Preferred reductant precursors useful in the pre-sent invention are quin-ones, particularly 2-isopropoxynaptho-quinone; 9,10-phenanthenequinone; and 2-t-butylanthraquinone.
Benzophenone, althouyh not a quinone, is also useful as a reductant precursor, as are a number of the simpler ketonesO
A factor of importance in the selection of reduc-tant precursors is the spectral range to which the reductant pxecursors respond. For that reason,, the simple ketones 2~ are not generally useful for recording visible light since their spectral sensitivity is in the ~ar ultraviolet region.
Other reductant precursors and their approximate spectral sensitivity ranges are as follows:

23~57 ~ ~58gl2 Spcctral sensitivity ~eductant ~recursor_ range (nm) 9,10-phcnallthrenecluinone~200 - 400 -U.V. Visible S l,1'-dibenzoylferrocene400 - 600 l-phenyl-1,2-propanedione400 - 500 2-hydroxy-1,4-naphthoquinone400 - 500 Benzil ~o~ _ 450 Furil 400 - 480 Diacetylferrocene 400 - 450 Acetylferrocene 400 - 450 1,4-bis(phenyl glyoxal) benzene 400 - S00 o-naphthoquinoneUp to about 560 4,5-pyrinequinoneUp to about 530 4,5,9,10-pyrinequinoneUp to about 550 The following are illustrative reductant precursors which are sensitive in the range of up to about 400 nm and, therefore, are useful only in the ultraviolet range:
Benzophenone; acetopher.one; 1 t 5-diphenyl-1,3,5-pentane-trione; ninhydrin; 4,4'-dibromobenzophenone; and 1,8-dichloroanthraquinone Various other reductant precursors can be utilized, particularly those of th~ type of substituted or unsubsti-tuted polynuclear quinones, of which class some have been mentioned above, and others of which are 1,2-benxanthraquinone;
~-methylanthraquinone; l-chloroanthraquinone; 7,8,9,10-tetra-hydronaphthacenequinone; 9,10-anthraquinone; and 1,4-dimethyl-anthraquinone. It will be understood that not all reductant precursors will be effective or equally effective, with each given imaging material, even taking into account the ~3~57 :, 1 15B~l~

utilization of imagin~ energy in the sensitivity range of thc rcductant precursor employed and that suitable selec-t:ions of combina~ions of particular imaging materials and p~r~icular reductant precursors will be required to be made for achieving desirable or optimum results. Such selections, however, can be made relatively readily.
In general, in connection with the foregoing matters, it may be noted that reductant precursors have ~* states, both singlet and triplet, of lower energies than ~,~* states and, at least in most cases, compounds which have their ~,~* states of lowest energy will not be photosensitively effective, although, in certain limited cases, compounds ~hich ~ulfill the test of having lower energy n ~ ~* than ~ ~ ~* transitions do ~ot function as reductant precursors.
~owever, the above consideration is, in the main, an effec-tive one for determining in advance whether a given com-pound will function as a reductant precursor ~or use in the practice of the present invention. In any event, a simple preliminary empirical test in any given instance can readily be carried out if necessary by preparing a test emulsion using the desired lrnaging compound ar.d reductant precursor.
In some cases an external sensitizer is not needed.
For~example, at wavelengths in the region of 250--300 nm most organotellurium compounds are directly photolyzed;
and, certain other tellurium compounds, notably the halides, are sensitive to the blue portions o~ the visible spectrum.
When imaging is to be accomplished by electrons, no addi-tional sensitizcr i5 needed, since the electron e~fects direct decomposition of the imaging material.

,~, 23~S7 .
l 1589~2 The Diol: In accordance with the present inven-~ion, ~h~rc may also be included a diol which reacts with thc ~ellurium compound to form an active intermediate com-pl~x. While the chemistry of the complex is not well under-stood, we believe that, in general, the complex requires approximately 2 moles of diol for each mole of tellurium.
Preferably, the diol, wh~n present, is used in excess of the minimum amount to form a complex since the diol will also function as a sourcè of labile hydroyen to provide the source of hydrogen required in the reaction of the reductant precursor.
While the present invention involving the use of novel masked reducing agents can be practiced without the inclusion of a diol, the presence of a diol is much pre-ferred. We have found that the presence of a diol serves to markedly reduce the optical density of unexposed areas (i.e., thus increasing the contrast between the~exposed and unexposed areas) particularly when a masked reduciny agent is present. Thus, while masked reducing agents can be used in the absence of a diol, tellurium film composi-tions containing masked reducing agents tend to have a rela-tively high optical density in the unexposed areas because the reducing capacity of the masked reducing agent is not fully inhibited by the masking group.
One group of diols which may be used in formulat-ing imaging compositions are diols of the formula -~7-. 23~57 ~ ~L589~

H H
}? l ~
0~ 011 wherein each of R10 and Rll independently represents hydrogen, a hydrocarbon group, including straight chain, branched chain and cyclic hydrocarbon groups, hydroxyalkyl groups, alkoxycarbonyl groups, cycloalkyl groups or aryl groups;
and Z represents an arylene group (for example, phenylene), the group (-C~C-), the group (-CR12=CR13)n, wherein n repre-sents a whole number, for example, 1 or 2, and each of R12and R13 represents hydrogen or an alkyl group or taken from part of a carbocyclic or heterocyclic ring. Z also may be omitted - that is, the two hydroxy-substituted carbons are joined directly to each other. The following table illustrates a number of diols which may be used:

Boiling Point (BP) No. of the C or Melting Compound R10 z Rll Point (MP) C
_ 2 ~ ~ H MP 67

3 H3C- - H BP 189

4 H3C ~ -CH3 BP 183 H -C=C- H MP 52-54 6 H ~ H MP 112 7 HO(CH2)4- - H BP 178/5 mm Hg 8 c2H5oc- - C2~5-I- BP 280 O O

-2~-A fuller description of the forcgoing diols may be found ln Be]glan Patent 85~l,193.
Preferab].y, however, the diol ls of a more complex type than disclosed in the abovc-mentioned Belyian patent application. These more complex diols are the subject ma~ter of U.S. Patent No. 4,281,058.
The preferrcd diols, as described in the afore-mentioned U.S. Patent No. 4,281,058 are compounds of the formula R7-o-CH2-CHo~-cH2oH
In the foregoing compound, R7 may be alkyl, acyl, thiazoli~yl, alkenyl, phenyl, alkylphenyl, alkenylphenyl, hydroxyalkyl-phenyl, benzyl, alkylbenzyl, alkoxybenzyl, hydroxylalkyl-benzyl, and halobenzyl and similar radicals.
The "thio" analogs of the foregoing compounds can be used (i~e., compounds in which the radical R7 is joined to the glycerol residue by a thio linkage in place of the oxy linkage.
Preferred compounds of the foregoing structure are those in which the radical R7 is benzyl or a substituted benzyl. The use of the diols of the foregoing structure has been found to be preferred since they are more effective in reducing the optical density of the unexposed areas than are the diols described in 8elgian Patent 854,193.
Ancillary Ingredients: In addition of the foregoing principal ingredients of the present formulation, ancillary ingredients may be included for various purposes.

.

dm:~ 29 -~ .
~

;

Thus, for example, it has been found that certain materials cnhance the shelf life of unexposed virgin dry film com-positions of the present invention, and in certain instances, thcy also enhance the sensitivity of said film compositions.
S Illustrative cmbodiments of such aclditional or supplemental materials, which contain ether or polyether linkages in the molecules thereoE, are such materials or polymers as poly-ethylene-20 sorbitan monolaurate; polyethylene-20 sorbitan ~ monooleate; Polyox-10; Polyox-80; Polyox-750; polyethylene glycol-~00 distearate; polyethylene glycol~600 dis~earate;
poly (1,3-dioxolane); poly (-tetrahydrofuran); poly (1,3-dioxepane); poly (1,3-dioxane); polyacetaldehydes; polyoxy-methylenes; fatty acid esters of polyoxymethylenes; poly (cyclohexane methylene oxide); poly (4-methyl-1,3-dioxane);
polyoxetanes; polyphenylene oxides; poly [3,3-bis (halo-methyl) oxoc~clobutane]; poly (oxypropylene) glycol epoxy resins; and copolymers o propylene oxides and styrene o~ides. Such materials can be incorporated in the imaging film compositions in varying amounts, generally from 5 to 20% by weight of the solid imaging film compositions. In certain cases then enhance or prolong the shelf life or storage life, under given storage conditions, as much as 50% or even very substantially more timewise, and, as indi-cated, they also, in various cases, effectively increase film sensitivity.
~ gain, the inclusion in the imaging films of re-ducing sugars has been found, generally speaking, to bring about an enhancement in density of the image area (O.D. image-O.D. background), when the film is imaged as disclosed above f ~ Je ~,~

.~

and then developed, for instance, at about 120-150C.
and for of the order o~ about 15 seconds, especially where the iMac3in~ film is fresllly prepared or not older than about a day after initial preparation. Such films, when exposed S to imaging energy and then developed resulted in the pro-duction of a positive image (i.e., the optical density is greater in the non-exposed areas than in the exE~sed areas) in contrast to the negative working system which exists in the usual practice of the present invention. The inclusion of xeducing sugars in the imaging compositions also enables development of the image, after exposure to imaging energy, to take place at lower temperatures, even at room tempera-tures, in a period of several hours, for instance, commonly in 10, 12 or 15 hours. The reducing sugars which can be employed are many, illustrative of which are dextrose, glucose, arabinose, erythrose, fructose, galactose, fucose, mannose and ribose. Especially effective are dextrose, arabinose, galactose, fucose and ribose. The reducing sugars can be used in variable amounts, but generally in equivalent amounts, or somewhat smaller or greater, in re-lation to the amount of imaging organo-tellurium materials in the imaging compositions~
It may be desirable in many cases to include a small amount of a silicone oil or similar material as is well known to aid in coating of smooth continuous films.
The matrix material: A film composition in accor-dance with the present invention is completed by dissolving the ingredients and op-tional ingredients described above in a suitable matrix. The matrix should be as concentrated as is practicable in the active ingredients, i.e., the least 1 15~12 amount o~ matrix is preferably used. The amount of matrix should be sufficien~ as to just retain the various active in~r~dicnts in a soli.d solution. ~n additional quantity of matrix may be used, however, that obviously tends to dilute the concentration of active incJredients, thereby slowing down the photo-response of the film composition. The selection of matrix materials, of course, must be related to the active ingredi.ents used so as to provide the maximum solubility ~or any particular composition.
The matrix materials, into which the imaging organo~
tellurium materials, and the separa e sensitizers when em-ployed, are incorporated to produce the imaging Eilm or coating, are solids at room temperature, and they can be selected from a relatively large num~er of materials. They should desirably be at least in part of amorphous character and it is especially desirable that they be glassy, polar amorphous materials having a glass transition temperature, which desirably should not exceed about 200C. and may be as low as about 50C., and, better still, should be within the range of about 80-120C. They are generally polymeric materials. Illustrative thereof are..cyanoethylated starches, celluloses and amyloses having a degree of substitution of cyanoethylation of > 2; polyvinyl-benzophenone; polyvinyl-B idene chloride; polyethylene terephthalate ("MYL~ ~); cellu-lose esters and ethers such as cellulose acetate, cellulose propionate, cellulose butyrate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinylcarbazole;
polyvinyl chloride; polyvinyl methyl ketone; polyvinyl alcohol; polyvinylpyrrolidone; polyvinyl methyl ether;
polyacrylic and polymethacrylic alkyl esters such as 7~ O JQ ~ 4~

-3?-~3~7 I 1~8~2 polymet}lyl methacrylate and polyethyl methacryla-te; co-polymer of polyvinyl methyl ether and maleic anhydride;
various c3rades of polyvinyl formal resins such as so-called ~ 5, 6/95 E, 15/95S, 15/95E, B-79, B-98, and the like, S sold under the trademark "FORMVAR" - (Monsanto Company).
Of especial utility is polyvinyl formal 15/95% which is a white, ~ree flowing ~owder having a molecular weight in the range of 24,000-~0,000 and a formal content expressed as percent polyvinyl formal of approximately 82%, possess-ing high thermal stability, excellent mechanical durability,and resistance to such materials as aliphatic hydrocarbons, and mineral, animal and vegetable oils. These polymeric materials or resins and their preparation are well known to the art. In addition to their functioning as carriers for and holding together in a unitary composition the imaging organo-tellurium materials, sensitizers and any other ingredients which may be incorporated into the imaging film or coating or layer and their functioning as dry or essentially dry film-forming materials to provide thin films and providing mechanical durability in the finished imaged film, at least many of them appear also to play a chemical or physical role in the imaging process by provid-ing, importantly, a source of readily easily abstractable hydrogen and, thus, appear to play a significant role in the latent image formation mechanism, as discussed hereafter.
In certain instances, it may be desirable to decrease the viscosity of the matrix, which can be done, by way of illus-tration, by the addition of certain plasticizers, for in-stance, dibutylph~halate or diphenylphthalate, which addi-tions tend to result in the production of images desirably ~3~-~3~57 I 15~2 of higller opt:ical densities but which, however, also tend to ~lavc the disadvantacJe of increasing background fogging.
It may be noted that matrix materials o the type which contain basic groups may comple~ with the imaging ot-~ano-tellurium materials and, therefore, to the extent that such complexing may occur, the use of such matrix materials should be avoided.
Formulation of Film Compositions: In the produc-.
tion of the films or thin layers of the imaging material compositions, which are generally prepared in the form ofsolutions or homogeneous dispersions and coated or laid down on a substrate, it is especially desirable to dissolve or homogeneously disperse the ingredients in an organic solvent. Illustrative of suitable solvents are methyl ethyl ketone (MEK), dimethylformamide (DMF), chloroform, tetra-hydrofuran (THF), dimethylacetamide (DMA), dioxane, dichloro-methane and ethylene dichloride, or compatible mixtures of such organic solvents or with other organic sol~ents. After the solution or homogeneous dispersion is filmed on a sub-strate in any suitable manner, the major proportions of suchorganic solvent or solvents are evaparated of~, preferably at a relatively low temperature and, sometimes desirably, under subatmospheric pressures or in vacuo, until the film or coating is substantially dry to the touch, such dry~to-the-touch coating being especially desirable for handling and processing purposes. Although such films or coatings may be, generally speaking, dry to the touch, it should be understood that this does not mean that the film is free from organic solvent. Indeed, it has been found that it is frequently very desirable that the finished films or 't A~

coatin(3s, prior to exposure to imaging energy, contain a small pcrcentage, co~nonly of the general order o about 2 to 3%, by wei~ht of the film or coating, or organic sol-vent, or instance, dimethylformamide (DMF) since its pre-s~nce appears to play a favorable role in the sensitivityo~ the system in relation to the latent image formation and/or ultimate image obtained after the development step.
The elimination o all or essentially all of the DMF, or other organic solvent or solvents, Erom the virgin film prior to the imaging and development frequently leads to a decrease in sensitivity. In any event, in any given in-stance where drying of the virgin imaging film has been carried out to a point where essentially no organic solvent is present, and whereby sensltivity is unduly reduced~
sensitivity can be increased or restored by adding a small amount of organic solvent to the film prior to exposing it to imaging energy.
The imaging ~ilm or coating thickness are variable but will usually fall within the range of about 1 to about 35 ~m with ab~ut S to 15 ~m generally being a good average.
In thickness in terms of millimeters (mm), such may vary from about 0.0005 to about 0.05 mm, or much greater, such as ~rom 0.05 to 5 mm, the selected thickness beir~ dependent upon the particular use to which the imaging film is to be `
put.
The production of the imaging organo-tellurium materials, and the coating, handling and processing opera~
tions, to the extent which ma~ be required, are carried out under appropriate light condi~ions, as those skilled in the 23~7 ~ 15~2 art will readily understand. For instance, the formula-tion of the coating compositions and the coating and drying operations are conveniently carried out under amberlite filtered licJht (weak transmission at 550 nm). The dry film priox to imaging, is desirably stored in the dark.
In certain cases, avoidance of contact of certain of the ingredients with certain metals may be in order where un-desired reactions, such as reductions, may occur. In general, the vessels or containers, stirrers, etc., utilized should be made of glass or other vitreous materials or other materials inert to the coating ingredients to insure against contamination or possible undesired reactions. It is ad-vantageous, in general, to prepare the imaging composi-tions shortly prior to coating them on the selected sub-strate. Under suitable storage conditions, which generallyare conditions of darkness and reasonable avoi~ance of air or oxidizing atmospheres and humidity conditions, the stability of the imaging compositions is good.
In the imaging compositions, the proportions of the matrix, the imaging organo-tellurium materlal and the reductant precursor are variable. In those special cases where the imaging organo-tellurium material utilized is one which also inherently or concomitantly possesses de-sired sensitizing propert~es, as noted above/ a separate reductant precursor is not necessary. It may, however, even in such cases, be desirable to employ a separate or added reductant precuxsor which may be of entirely dif-ferent sensitizing properties from that inherently possessed -by the particular imaging organo-tellurium material utilized.

2:3~57 In an~ event, ~enerally spea~ing, excluding the organic solvent or solvents, where employed as described below, at least in most cases the matrix material, which is a normally solid material, that is, solid at room temperature, will be S employed in amounts in excess of any one of the other materi.als and will also usually be present in major amount, that is more than 50% and broadly in the range l-~ to 90%
by weight, of the total materia]s present in the imaging composition. The imaging organo-tellurium material, generally also a normally solid material, will ordinarily constitute from about 1 to above 20 parts per 100 parts of matrix, usually about 5 10 parts per 100 parts of matrix.
The reductant precursor, where it is a separate ingredient, which is usually a solid, will usually be employed in lesser proportions, commonly of the order of about 5 to 20%, usually about 6 to 15%, by weight, of the imaging composi-tion, although, in certain cases the proportions thereof can be substantially higher, approximately or even exceed-ing somewhat the proportions of the imaging organo-tellurium material. With further regard to the proportions of the aforesaid ingredients, it may be stated that the area den-sity of the reductant precursor is desirably selected so that about 70-95% of the photons falllng on the film in the region of the absorption bands of the reductant precursor are absorbed. Considerably higher concentrations of reduc-tant precursor would leave the dark side of the film unexposed and no advantage would thus be served. In general, for optimal results in many cases, the mole -3l-23~57 ~ 158~2 concentration of the imaging organo-tellurium material shollld be reasonably close to or roughly approximate to that of the reductant precursor. The concentration oE the polymer matrix material should be sufficient to produce an essentially amorphous film without bringing about precipi-tation of the imaging organo-tellurium material, the sen-sitizer and other supplemental ingredients when utilized.
Excess polymer matrix material also tends to decrease the sensitivity o the film.
As has already been indicated, the amount of diol should be present in a concentration sufficient to provide at least 2 moles o diol for each mole of tellurium com-pound, and preferably to provide up to a ratio of 6:1 moles. As indicated above, our work has suggested that a complex is formed between the diol and the tellurium com-pound in a molar ratio of ?:1, and that excess diol above that is useful to provide a source of labile hydrogen for reaction with the reductant precursor. Larger amounts of the diol may be used if desired. To some extent, improved results are obtained when these larger amounts of diol are used; however, there is a point of di,minishing returns above which increasing the amount of diol will not provide commensurate improvement in photoresponse of the finished film.
The masked reducing agent of the present inven-tion may be present in amounts o 1% up to 200~ by weight of the tellurium compounds. Measurably improved sensi-tivity can be found in accordance with the present invention with even very small amounts of masked reducing agent -3g-` - ~ 1 5 ~ 2 and wlthin limLtations the degree of lmprovement ls in proportlon to the amount of masked reducing agent which ls lncorporated in the film. Aqaln, however, a la~ oE
dimlnlshing ret~rns ls observed, and whlle large amounts of the masked reducing agent wlll be incorporated - in the order of 2 to 4 times the amount oE tellurium compound -beyond these large amounts the increase in photoresponse obtained is not commensurate with the increased amount of masked reducing agent incorporated.
~The film-forming compositions as described above will be applied to any suitable substrate. Glass, porcelain, paper and various plastic substrates have been ound suitable. For the purposes of forming film-like materials, transparency is obviously desirable. For this purpose, films of polyethylene terephthalate have been found particularly suitable.
Additional considerations which those skilled in the art in formulating and using tellurium-based film compositions may utilize are apparent from U.S. Patent No.
4,142,896.
This invention is further illustrated by the following examples:

dm~ 39 -J~ .

I 158g~2 ~, 2.1 gms of cJlyceryl benzyl ether and 0.625 gms o~ tellurium bis-acetophenone dichloride are added to a mixtuxe o~ 42 ml oE methylene chloride and 58 ml of methyl~
ethyl ketone. ~ 2% solution of silicone oil in methylene chloride, 2.1 ml, is added to aid in preparing a smooth coating.
The mixture is stirred at room temperature for 30 minutes and then 0.625 gms of the phenyl isocyanate adduct of benzoyl hydrazine is added as a masked reducing agent. The polymeric binder (CAB-500-5, 10.42 gms) is then added, followed by 0.31 gms of 2-isopropoxynaphthoquinone.
The resulting solution was stirred in complete darkness for 1 hour and then coated on a M~LAR substrate at an average coverage of approximately 2 gms of tellurium-bis-acetylphenone dichloride per square meter. The film was then heated in an oven at 65C. for 2-4 hours to remove the solvents.

Example 2 2.0 gms of p~methoxy benzyl-l-glyceryl ether, and 0.625 gms tellurium-bis-acetophenone dichloride (TeBAC) were added to a mixture of 42 ml methylene chloride and 58 ml methylethyl ketone, along with 2.0 ml of a 2% solu-tion of silicon oil in methylene chloride.
The mixture was stirred at room temperature for 30 minutes,- then 0.625 gms of masked reducing agent of the formula ~ 158912 ~ C-N-N-C-N-_ ~

was added, and the mixture stirred for lO minutes. The polymeric binder, Eastman CAB 500-5, in the amount of 10.42 gms, was added, followed by 0.31 gms of 2-isopropoxy-naphthoquinone (IPNQ). The solution was stirred in com-plete darkness for 1 hour.
The resulting solution was coated in a standard meniscus coater on a substrate of 5 mil polyethylene tereptha-B late (~eline~ type O), at a coverage approximating 2 gms of TeBAC/meter2, and the resulting film heated in an oven at 65C. for 3 hours.
When exposed to imaging energy of 104 erg/cm2 at 365 nm and heated to 1~0C. for 30 seconds, this film gave an optical density of 2.2, with a density of 0.35 in the unimaged area. Gamma of the film was 2Ø

Example 3 2.0 gms p-methoxy benzyl-l-glyceryl ether, and - 20 0.625 gms of TeBAC were added to 42 ml of methylene chloride and stirred for 3 hours at 50bC. in a closed bottle 58 ml of methyl ethyl ketone and 2 ml of 2% silicon oii in CH2Cl2 were added, and then the masked reducing agent, polymer, and IPNQ as in Example 2.
The mixture was stirred in darkness for l hour at room temperature, and coated as above.

After coating, the film was heated in an oven at 65C. for 45 minutes. Photographic response was identical to that of the film prepared in Example 2.

--'11-- .

23~57 , Example 4 2.5 ~ms o-chloro benzyl-l-glyceryl ether, and 0.600 gms telluriuM-bis-aCetopllenone dichloride were added to a mixture of 42 ml methylene chloride and 58 ml methyl ethyl ketone.
The mixture was stirred at room temperature for 30 minutes, then 0.625 gms of the adduct of benzoyl hydrazine and phenyl isocyanate (masked reducing agent) was added, and the mixture stirred for 10 minutes. The polymeric binder, Union Carbide VAGH in the amount of 10~42 gms, was added, followed by 0.31 gms of 2-isopropoxynaphthoquinone (IPNQ).
The solution was then stirred in complete darkness for 1 hour.
The resulting. solution was coated with a standard meniscus coater onto a 5 mil substrate of polyethylene tereptha-late (Melinex type O), at a cove.age approximating 2 gms of TeBAC/m2, and the resulting film heated in an oven for 2-1/2 hours at 65~C.
Films thus prepared exhibit an optical density of 2.0 in the image area and 0.3 in the background areas with a gamrna o~ 3.0, when exposed to an energy of 8 x 103 erg/cm2 at 365 nm and heated to 130C. for l minute.

Example 5 2.5 gms o p-benzyloxy benzyl-l-glyceryl ether, and 0.7 gms tellurium-bis-pinacolone dichloride were stirred in a mixture of 80 ml methylene chloride and 20 ml dimethyl formamide,-at room temperature for 3 hours.
To this was then added 0.6 gms of masked reducing agent of the formula -~2-23~7 ... . .

~ 15~12 ~ C-N-N-C-N-C - ~

and the mixture was stirred for 10 minutes~ 12 gms of the polymeric binder polyvinyl formal (Monsanto Formvar) was added, followed by 0.4 gms of 2-tert-butyl anthraquinone (BAQ). The solution was then stirred for 1 hour at room temperature in darkness.
Films were prepared ~y casting the solution on glass plates, with a coverage approximating 1.5 gms of organo-tellurium/m2. A~ter drying at room temperature for 1 hour, the films were heated in an oven at 65C.
for 2 hours.
Films thus prepared exhibit an optical density of 1.5 in the image area, and 0.2 in the background, and a gamma of approximately 1.5, when exposed to an imaging energy flux of 8 x 104 erg/cm2 at 365 nm and heated to 110C. for 90 seconds.

3.0 gms p-m~thoxy benzyl-l-glyceryl ether, and 1.18 gms of tellurium dichloride were stirxed in 42 m] of methylene chloride and 58 ml of methyl ethyl ketone for 2 hours.

To this mixture was added 0.625 gms of benzoyl-hydrazine-phenylisocyanate adduct (masked reducing ayent), 10.42 gms of polymeric binder, Eastman CAB 500-5, and 0.625 gms 2-isopropoxynaphthoquinone, The mixture was then stirred for 1 hour in complete darkness at room tem-perature.

-~3-23~57 1 ~58~a~2 The mixture was then coated on a substrate of polyethylene terepthalate (Melinex type O) at a coverage approximating 3.5 gms o TeC12/m2. The resulting film was heated in an oven for 3 hours at 65C.
When exposed to an imaging energy of 105 erg/cm2 at 365 nm and heat processed at 150C. for 30 seconds, these films gave an image optical density of 3.0 and a background density of 0.7. Gamma of these films was ap-proximately 3Ø

Example 7 0.210 gms of TeO2 and 0.050 gms of TeC14 were stirred for 30 minutes in 5 ml of 2-methoxyethanol, then this mixture was added to 1.0 gms of~o~chloro benzyl-l-glyceryl ether in 42 ml methylene chloride and 58 ml methyl ethyl ketone. The mixture was stirred for an additional hour. 0.625 gms of the masked reducing agent of the formula .

~ ~ Cl 10.42 gms of polymer Eastman CAB 500-5, and 0.32C gms of 2-isopropoxynaphthoquinone were added and the mixture stirred for 1 hour.
Films were meniscus coated on 5 mll polyethylene terepthalate (Melinex type O) at a coverage of 0.4 gms TeO2/m2, and heated in an oven at 60C. for 3 hours. The resulting films gave an optical density o~ 2.5 in the image -4~-23~57 `` - I15~ 2 area and 0.7 in the background area, and exhibited a gamma of approximately 3.5 when irradiated with an energy of 105 erg/cm2 at 365 nm and heat processed at 165C. for lO
seconds.

Example 8 0.210 gma of TeO2 and 0.090 gms of TeBAC were stirred for 10 minutes in 5 ml of methoxyethanol, then this mixture was added to 2.0 gms o O-methoxy benzyl glyceryl ether in 42 ml of methylene chloride and S8 ml of methyl ethyl ketone and stirred for l hour. 0.550 gms of benzoyl hydrazine-phenyl isocyanate adduct (masked re-duciny agent), 10.42 gms of polymeric binder, Eastman CAB 500-5, and 0.300 gms of 2-isopropoxynaphthoquinone were added and the mixture stirred for 2 hours in complete darkness.
Films were meniscus coated on 5 mil polyethylene terepthalate (Melinex type O) at a coverage of 0.4 gms TeO2/m2, and heated in an oven for 3 hours at 65C. The resulting films gave an image optical density of 2.0, and a background density of 0.5 when exposed to imaging energy of 5 x 104 erg/cm2 at 365 nm and heat processed at 140C.
'or 30 seconds. Gamma of these films is approximately 2.5.

Example 9 0.480 gms of H2TeCl6 and 3.0 gms of p-methoxybenzyl-l-glyceryl ether were stirred in a mixture of 42 ml methylene chloride and 58 ml methyl ethyl ketone for 2 hours. 0.625 gms of benzoyl hydrazine-pllenyl isocyanate adduet (masked re-ducing agent), 10.42 gms of polymer, Eastman CAB 500-5, and ~ 5-23~57 O.S00 gms of 2-isopropoxynaphthoquinone were added and the mixture stirred for 1 additional hour in complete darkness.
The solution was then coated on 5 mil polyethylene terepthalate (Melinex type O) at a cover~y~ of 1.6 gms of H2TeC16/m2 and heated in an oven at 70C. for 3 hours. The resulting films gave an image optical density of 1.5 and a background density of 0.1 when exposed to imag ng energy of 8 x 104 erg/cm2 at 365 nm and heat processed at 175C.
or 30 seconds. Gamma of these films is approximately 3.

Additional illustrations of the manner in which this invention may be practiced will be apparent from the following formulations which may be prepared and coated in a manner analogous to Examples 1 and 2:

Example 10 ~ O

.700 gms of ~ N ~ - C - N -C=O
NH

2.1 gms of p-methoxybenzyl glyceryl ether . 0 gm5 of Styrene glycol .625 gms of TeB~C
10.42 gms of Polymer C~B 500-5 58 ml of MEK
42 ml of CH2C12 .310 gms of IPNQ

~6-23~57 1 15~12 Example 11 ,500 gms of ~ ~ N-C-N-2.0 gms of o-chlorobenzyl glyceryl ether l.0 gms of Styrene glycol .625 gms of TeBAC
10.42 gms of CAB 500-5 58 ml of M~EK
42 ml of CH2Cl2 .310 gms of IPNQ

Example 12 O
~ O : H O
.90 gms of ~ ~ - C - N - C -~ ~N~ H
C - N - C -O O
.

2.1 gms of o-chlorobenzyl glyceryl ether 1.0 gms of Skyrene glycol .625 gms of TeBAC
10.42 gms of CAB 500-5 58 ml of MEK
42 ml of CII2Cl2 .310 yms of IPNQ

-~7 23~57 1 ~5~2 Ex~mple 13 O

1.0 ~ms of ~ ~ ~C-N-3-C - N - C
Il 11 ~
O O

2.1 gms of o-chlorobenzyl glyceryl ether 1.0 gms of Styrene glycol .625 gms of TeBAC
10.42 gms of CAB 500-5 58 ml of MEK
42 ml of C~2C12 .310 gms of I~NQ
Example 14 o _D o ~ ~
.900 gms of ~ C ~ C - N - C -H

2.1 gms of o-chlorobenzyl glyceryl ether 1.0 gms of Styrene glycol .625 gms of TeBAC
10.42 gms of CAB 500-5 58 ml of MEK
42 ml of CH2C12 .310 gms of IPNQ

11 1~8~a~2 Example 15 -H H

.90 gms o N - C - N ~d 2.1 gms o o-chlorobenzyl glyceryl ether 1.0 ~ms of Styrene glycol .625 gms of TeBAC
10.42 gms of C~B 500-5 58 ml of MEK
42 ml of CH2C12 .310 gms of IPNQ

_~9

Claims (61)

WE CLAIM:

1. In a composition responsive to activating energy for forming an imaging film, which composition com-prises (a) an image-forming tellurium compound;
(b) a reductant precursor which will abstract labile hydrogen from a hydrogen donor under the influence of acti-vating radiation to become a reducing agent with respect to the image-forming tellurium compound;
(c) a source of labile hydrogen for reaction with said reductant precursor; and (d) a matrix in which said tellurium compound, reductant precursor and source of labile hydrogen are com-bined in amounts effective to form a composition which may be applied to a substrate, the improvement wherein there is included in said composition a masked reducing agent of the formula ; or wherein R1 is alkyl, alkanoyl, alkoxycarbonyl, phenyl, benzyl, benzoyl, nitrophenyl, benzylcarbonyl, di-phenylmethyl, diphenylethyl, diphenylpropylcarbonyl or amino carbonyl; R2, R3 and R4 each and independently are hydrogen, alkyl, phenyl, or amino; and R5 is phenyl, nitrophenyl, halo-phenyl, alkyl, mono-, di- or tri-haloacetyl, benzoyl, alkyl-phenyl, or alkyl-p-isocyanophenyl, said alkyl grouping in the radicals R1 through R5 having from 1 to 7 carbon atoms, and wherein Y is hydrogen or , said compound containing at least one group in said compound, the amount of said masked reducing agent being at least 1% by weight of said image-forming tellurium compound.

2. The improved image-forming composition accord-ing to claim 1, wherein there is additionally provided a diol of the formula wherein each of R10 and R11 independently represents hydrogen, a hydrocarbon group, including straight chain, branched chain and cyclic hydrocarbon groups, hydroxyalkyl groups, alkoxycarbonyl groups, cycloalkyl groups or aryl groups; and Z represents a direct C-C bond between the carbon atoms on either side of it, or an arylene group, the group (-C?C-), the group (-CR12=CR13)n, wherein n represents 1 or 2, and each of R12 and R13 represents hydrogen or an alkyl group or taken from part of a carbocyclic or heterocyclic ring, said diol being provided in an amount equivalent to at least 2 moles thereof per 1 mole of tellurium in said image forming compound.

3. The improved image-forming composition accord-ing to claim 1, wherein there is provided a diol of the formula wherein R7 is alkyl, alkanoyl, thiazolinyl, alkenyl, benzyl, alkylbenzyl, alkoxybenzyl, hydroxyalkylbenzyl, and halobenzyl; the alkyl radical having from 1 to 7 carbon atoms; and X is oxygen or sulphur.

4. The improved image-forming composition accord-ing to claim 1, wherein said tellurium compound is selected from the group consisting of Rx-Te-Haly ;

(Hal - R8)x - Te - Haly ; and TeClnBrm in the foregoing formulae, R being an organic radical con-taining at least 1 carbonyl group, R8 being the residue of an ethyleneic hydrocarbon, Hal being halogen, x being 1, 2 or 3; and x + y = 4; n being an integer from 1 to 4 and m + n = 4.

5. The improved image-forming composition accord-ing to claim 3, wherein said tellurium compound is selected from the group consisting of Rx-Te-Haly ;

(Hal - R8)x - Te - Haly ; and TeClnBrm in the foregoing formulae, R being an organic radical con-taining at least 1 carbonyl group, R8 being the residue of an ethyleneic hydrocarbon; Hal being halogen, x being 1, 2 or 3, and x + y = 4; n being an integer from 1 to 4 and m + n = 4.

6. The improved image-forming composition accord-ing to claim 4 wherein said reductant precursor is selected from the group consisting of 2-isopropoxynaphthoquinone;
2-t-butyl-anthraquinone; 1,10-phenanthrenequinone; 1,1'-dibenzoylferrocene; 1-phenyl-1,2-propanedione; 2-hydroxy-1,4-naphthoquinone; benzil; furil; diacetylferrocene; acetyl-ferrocene; 1,4-bis (phenyl glyoxal) benzene; o-naphthoquinone;
4,5-pyrinequinone; 4,5,9,10-pyrinequinone; benzophenone;
acetophenone; 1,5-diphenyl-1,3,5-pentanetrione; ninhydrin;
4,4'-dibromobenzophenone; 1,8-dichloroanthraquinone;
1,2-benzanthraquinone; 2-methylanthraquinone; 1-chloro-anthraquinone; 7,8,9,10-tetrahydronaphthacenequinone;
9,10-anthraquinone; and 1,4-dimethylanthraquinone.

7. The improved image-forming composition according to claim 5 wherein said reductant precursor is selected from the group consisting of 2-isopropoxynaphthoquinone; 2-t-butyl-anthraquinone; 1,10-phenanthrenequinone; 1,1'-dibenzoyl-ferrocene; 1-phenyl-1,2-propanedione; 2-hydroxy-1,4-naphtho-quinone; benzil; furil; diacetylferrocene; acetylferrocene;
l,4-bis (phenyl glyoxal) benzene; o-naphthoquinone; 4,5-pyrinequinone; 4,5,9,10-pyrinequinone; benzophenone;
acetophenone; 1,5-diphenyl-1,3,5-pentanetrione; ninhydrin;
4,4'-dibromobenzophenone; 1,8-dichloroanthraquinone;
1,2-benzanthraquinone; 2-methylanthraquinone; 1-chloro-anthraquinone; 7,8,9,10-tetrahydronaphthacenequinone;
9,10-anthraquinone; and 1,4-dimethylanthraquinone.

8, The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

9. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

10. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

11. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

12. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is ??

13. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

14. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

15. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

16. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

17. The improved image-forming composition accord-ing to one of claims 1- 3 wherein said masked reducing agent is

18. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is ?????

19. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

20. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

21. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

22. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

23. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

24. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

25. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

26. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

27. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

28. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

29. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

30. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

31. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

32. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

33. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

34. The improved image-formed composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

35. The improved image-forming composition accord-ing to one of claims 1- 3 wherein said masked reducing agent is

36. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

37. The improved image-forming composition accord-ing to one of claims 1- 3 wherein said masked reducing agent is

38. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

39. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

40. The improved image-froming composition accord-ing to one of claims 1- 3 wherein said masked reducing agent is

41. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

42. The improved image-forming composition accord-ing to one of claims 1- 3 wherein said masked reducing agent is

43. The improved image-forming composition accord-ing to one of claims 1- 3 wherein said masked reducing agent is

44. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

45. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

46. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

47. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

48. The improved image-forming composition accord-ing to one of claims 1-3 wherein said masked reducing agent is

49. In a film for forming an image comprising a composition on a substrate wherein said composition con-tains (a) an image-forming tellurium compound;
(b) a reductant precursor which will abstract labile hydrogen from a hydrogen donor under the influence of activating radiation to become a reducing agent with respect to the image-forming tellurium compound;
(c) a source of labile hydrogen for reaction with said reductant precursor; and (d) a matrix in which said tellurium compound, reductant precursor and source of labile hydrogen are com-bined in amounts effective to form a composition which may be applied to a substrate, the improvement wherein there is provided in said composition a masked reducing agent of the formula R1-NY-NY2 ;

; or wherein R1 is alkyl, alkanoyl, alkoxycarbonyl, phenyl, benzyl, benzoyl, nitrophenyl, benzylcarbonyl, diphenylmethyl, diphenylethyl, diphenylpropylcarbonyl or amino carbonyl; R2, R3 and R4 each and independently are hydrogen, alkyl, phenyl, or amino; and R5 is phenyl, nitro-phenyl, halophenyl, alkyl, mono-, di- or tri-haloalkyl, benzoyl, alkylphenyl, or alkyl-p-isocyanophenyl, said alkyl grouping in the radicals R1 through R5 having from 1 to 7 carbon atoms; and wherein Y is hydrogen or , said compound containing at least one group, the amount of said masked reducing agent being at least 1% by weight of said image-forming tellurium compound.

50. The improved film according to claim 49, wherein there is additionally provided a diol of the formula wherein each of R10 and R11 independently represents hydrogen, a hydrocarbon group, including straight chain, branched chain and cyclic hydrocarbon groups, hydroxyalkyl groups, alkoxy-carbonyl groups, cycloalkyl groups or aryl groups; and Z
represents a direct C-C bond between the carbon atoms on either side of it, or the group (-C?C), the group (-CR12=CR13)n, wherein n represents 1 or 2, and each of R12 and R13 represents hydrogen or an alkyl group or taken from part of a carbocyclic or heterocyclic ring, said diol being provided in an amount equivalent to at least 2 moles thereof per 1 mole of tellurium in said image-forming compound.

51. The improved film according to claim 49 wherein there is provided a diol of the formula wherein R7 is alkyl, alkanoyl, thiazolinyl, alkenyl, benzyl, alkylbenzyl, alkoxybenzyl, hydroxyalkylbenzyl, and halobenzyl; the alkyl radical having from 1 to 7 carbon atoms;
and X is oxygen or sulphur.

52. The improved film according to claim 49, 50 or 51, wherein said tellurium compound is selected from the group consisting of Rx-Te-Haly ;

; and TeClnBrm in the foregoing formulae, R being an organic radical con-taining at least one carbonyl group, R8 being the residue of an ethyleneic hydrocarbon, Hal being halogen, x being 1, 2 or 3; and x + y = 4; n being an integer from 1 to 4 and m + n = 4.

53. The improved film according to claim 49 wherein said reductant precursor is selected from the group consisting of 2-isopropoxynaphthoquinone; 2-t-butyl-anthraquinone; 1,10-phenanthrenequinone; 1,1'-dibenzoylferrocene;
1-phenyl-1,2-propanedione; 2-hydroxy-1,4-naphthoquinone;
benzil; furil; diacetylferrocene; acetylferrocene; 1,4-bis (phenyl glyoxal) benzene; o-naphthoquinone; 4,5-pyrine-quinone; 4,5,9,10-pyrinequinone; benzophenone; acetophenone;
1,5-diphenyl-1,3,5-pentanetrione; ninhydrin; 4,4'-dibromo-benzophenone; 1,8-dichloroanthraquinone; 1,2-benzanthra-quinone; 2-methylanthraquinone; 1-chloroanthraquinone;
7,8,9,10-tetrahydronaphthacenequinone; 9,10-anthraquinone;
and 1,4-dimethylanthraquinone.

54. The improved film according to claim 53 wherein said reductant precursor is selected from the group consisting of 2-isopropoxynaphthoquinone; 2-t-butyl-anthraquinone; 1,10-phenanthrenequinone; 1,1'-dibenzoyl-ferrocene; 1-phenyl-1,2-propanedione; 2-hydroxy-1,4-naphtho-quinone; benzil; furil; diacetylferrocene; acetylferrocene;
1,4-bis (phenyl glyoxal) benzene; o-naphthoquinone; 4,5-pyrinequinone; 4,5,9,10-pyrinequinone; benzophenone; aceto-phenone; 1,5-diphenyl-1,3,5-pentanetrione; ninhydrin; 4,4'-dibromobenzophenone; 1,8-dichloroanthraquinone; 1,2-benzanthra-quinone; 2-methyl-anthraquinone; 1-chloroanthraquinone;
7,8,9,10-tetrahydronaphthacenequinone; 9,10-anthraquinone;
and 1,4-dimethylanthraquinone.

55. In a method for recording electromagnetic radiation, wherein said radiation impinges upon a photo-sensitive film to produce a change in at least one property thereof, which film is a photosensitive composition carried by a substrate, the photosensitive composition containing (a) an image-forming tellurium compound;
(b) a reductant precursor which will abstract labile hydrogen from a hydrogen donor under the influence of activating radiation to become a reducing agent with respect to the image-forming tellurium compound;
(c) a source of labile hydrogen for reaction with said reductant precursor; and (d) a matrix in which said tellurium compound, reductant precursor and source of labile hydrogen are com-bined in amounts effective to form a photosensitive composi-tion which may be applied to a substrate, the improvement wherein there is included in said photosensitive composition a masked reducing agent of the formula R1-NY-NY2 ;

; or wherein R1 is alkyl, alkanoyl, alkoxycarbonyl, phenyl, benzyl, benzoyl, nitrophenyl, benzylcarbonyl, di-phenylmethyl, diphenylethyl, diphenylpropylcarbonyl or amino carbonyl; R2, R3 and R4 each and independently are hydrogen, alkyl, phenyl, or amino; and R5 is phenyl, nitrophenyl, halo-phenyl, alkyl, mono-, di- or tri-haloacetyl, benzoyl, alkyl-phenyl, or alkyl-p-isocyanophenyl, said alkyl grouping in the radicals R1 through R5 having from 1 to 7 carbon atoms, and wherein Y is H or , there being at least one group in said compound;
the amount of said masked reducing agent being at least 1% by weight of said image-forming tellurium compound.

56. The improved method according to claim 55, wherein there is included in said photosensitive composition a diol of the formula wherein each of R10 and R11 independently represents hydrogen, a hydrocarbon group, including straight chain, branched chain and cyclic hydrocarbon groups, hydroxyalkyl groups, alkoxycarbonyl groups, cycloalkyl groups or aryl groups;
and Z represents a direct C-C bond between the carbon atoms on either side of it, or an arylene group, the group (-C?C-), the group (-CR12-CR13)n, wherein n represents a whole number, for example 1 or 2, and each of R12 and R13 represents hydrogen or an alkyl group or taken from part of a carbocyclic or heterocyclic ring, said diol being provided in an amount equivalent to at least 2 moles thereof per 1 mole of tellurium in said image forming compound.

57. The improved method according to claim 55, wherein there is included in said photosensitive composition a diol of the formula wherein R7 is alkyl, alkanoyl, thiazolinyl, alkenyl, benzyl, alkylbenzyl, alkoxybenzyl, hydroxyalkylbenzyl, and halobenzyl; the alkyl radical having from 1 to 7 carbon atoms; and X is oxygen or sulphur.

58. The improved method according to claim 56, wherein there is included in said photosensitive composition a tellurium compound selected from the group consisting of Rx-Te-Haly ;

; and TeClnBrm in the foregoing formulae, R being an organic radical con-taining at least one carbonyl group, R8 being the residue of an ethyleneic hydrocarbon, Hal being halogen, x being 1, 2 or 3; and x + y = 4, n being an integer from 1 to 4 and m + n = 4.

59. The improved method according to claim 57, wherein there is included in said photosensitive composition a tellurium compound selected from the group consisting of Rx-Te-Haly ;

; and TeClnBrm in the foregoing formulae, R being an organic radical con-taining at least one carbonyl group, R8 being the residue of an ethyleneic hydrocarbon, Hal being halogen, x being 1, 2 or 3, and x + y = 4; n being an integer from 1 to 4, and m + n = 4.

60. The improved method according to claim 58, wherein there is included in said photosensitive composi-tion a reductant precursor selected from the group consist-ing of 2-isopropoxynaphthoquinone; 2-t-butylanthraquinone;
1,10-phenanthrenequinone; 1,1'-dibenzoylferrocene; 1-phenyl-1,2-propanedione; 2-hydroxy-1,4-naphthoquinone; benzil;
furil; diacetylferrocene; acetylferrocene; 1,4-bis (phenyl glyoxal) benzene; o-naphthoquinone; 4,5-pyrinequinone;

4,5,9,10-pyrinequinone; benzophenone; acetophenone; 1,5-diphenyl-1,3,5-pentanetrione; ninhydrin; 4,4'-dibromo-benzophenone; 1,8-dichloroanthraquinone; 1,2-benzanthra-quinone; 2-methylanthraquinone; 1-chloroanthraquinone;
7,8,9,10-tetrahydronaphthacenequinone; 9,10-anthraquinone;
and 1,4-dimethylanthraquinone.

61. The improved method according to claim 59, wherein there is included in said photosensitive composition a reductant precursor selected from the group consisting of 2-isopropoxynaphthoquinone; 2-t-butylanthraquinone; 1,10-phenanthrenequinone; 1,1'-dibenzoylferrocene; 1-phenyl-1,2-propanedione; 2-hydroxy-1,4-naphthoquinone; benzil; furil;
diacetylferrocene; acetylferrocene; 1,4-bis (phenyl glyoxal) benzene; o-naphthoquinone; 4,5-pyrinequinone; 4,5,9,10-pyrinequinone; benzophenone; acetophenone; 1,5-diphenyl-1,3,5-pentanetrione; ninhydrin; 4,4'-dibromobenzophenone;
1,8-dichloroanthraquinone; 1,2-benzanthraquinone; 2-methyl-anthraquinone; 1-chloroanthraquinone; 7,8,9,10-tetrahydro-naphthacenequinone; 9,10-anthraquinone; and 1,4-dimethyl-anthraquinone.