DE3033554C2 - - Google Patents

Description

The invention relates to a radiation-sensitive, in particular photographically active mixture the genus mentioned in the preamble of claim 1 and on an image recording material produced therefrom and a process for producing Images using this material.

Such a mixture is already known (DE-OS 27 19 023). A diol is used as the reducing agent precursor, which has both a hydrogen donor as well as a reducing agent that forms with a reducible Tellurium compound reacts when electromagnetic Radiation falls on. As a binder or matrix material for the mixture serve z. B. Polyvinyl formal resins.

Such a mixture is also known (DE-OS 28 08 010), where as a photo-oxidizing agent a photosensitive 4- (2'-nitrophenyl) -1,4-dihydropyridine present and as Reducing agent is a heat-activated sulfonyl hydrazide compound is used, creating a temperature range between 60 and 200 ° C is developed.

Corresponding radiation-sensitive mixtures with tellurium compounds are also known from US-PS 41 42 896. The tellurium compound is represented by the following formula represents:

R _x -Te-X _y

With
R = an organic radical with at least one carbonyl group,
X = a halide, preferably chlorine,
x = 2, 2 or 3, and
x + y = 4.

The organic radical R can either be two independent Be radicals or form a ring connection. Another Group of compounds described in US Pat. No. 4,142,896 are organic tellurium compounds that as tellurium tetrahalide adducts of ethylene or acetylene hydrocarbons viewed or labeled as such can. Some of these connections have the following Formulas:

and

With
R and R¹ = each an ethylene hydrocarbon residue, and
X = a halogen, preferably chlorine.

Another category of photosensitive tellurium compounds, that have proven to be useful halogenated tellurium compounds, e.g. B. Connections of formula

TeCl _n Br _m

With
n is an integer from 2-4, and
n + m = 4.

The use of such halogenated tellurium compounds Imaging process is specified in US-PS 40 66 460.

Another category of usable tellurium compounds is specified in US-PS 41 06 939. These connections are Tellurium tetrahalide adducts of aromatic amines, where the one bound directly or indirectly to the aromatic ring Nitrogen substituted by alkyls with 1-4 carbon atoms and the adduct contains no diazo groups.

The tellurium compounds given above can be used in conjunction with a reducing agent precursor, which acts as a sensitizer. The Reductant precursor is a compound that is under the action of activation energy radiant energy absorbed and labile hydrogen from a suitable Hydrogen donor deprives so that a strong reducing agent arises. The strong reducing agent reduces the tellurium compound, which is a change in darkness has the consequence that this for the recording of information suitable is. In general, the aforementioned Reaction denoted by the following mechanism will:

With
PQ = the reducing agent precursor senibilizer;
1 _PQ = its first excited singlet state;
3 _PQ = its triplet state;
RH = the hydrogen donor;
PQ · H₂ = the reducing agent precursor in the reduced state; and
(R₁) ₂ · Te · X₂ = the image-forming reducible tellurium compound.

In this context it should be noted that the Hydrogen donor need not necessarily be provided although a variety of alcohols are used if desired can be. If not a specially designed hydrogen donor is present, the labile hydrogen can sometimes also from the organic used as binders Resins are extracted. In other cases, the Sensitizer to be its own hydrogen donor; it is known to do this with at least one preferred Sensitizer is the case, namely with isoproxynaphthoquinone.

A modification of the Tellur photo process is in the BE-PS 8 54 193 indicated where certain diols of the formula

R₁₀-CHOH-Z-CHOH-R₁₁

as a hydrogen donor for use in conjunction with the above photosensitizer can be used. In the formula above are R₁₀ and R₁₁ hydrogen and various organic substituents. Z can be a direct one Carbon-carbon linkage between the two hydroxy substituted carbon atoms or one of different chain groups. Regarding the A more detailed explanation of the diols mentioned is given on the BE-PS 854 193 referenced. It is stated that this Diols serve as hydrogen donors. Later investigations have shown, however, that this is not complete correct is. In fact, much of the diol appears to form a complex with the tellurium compound.

This finding has led to the discovery of diols of the following general formula

R-O-CH₂CHOH-CH₂OH

performed when used in photographic films have improved properties on a tellurium basis.

The radical R can be a simple aliphatic group (e.g. Alkyl or alkenyl). Alternatively, the radical R contain a carbonyl group (e.g. an acyl radical). However, the radical R is preferably aromatic. The best results are achieved when the aromatic Ring through a methylene grouping from ether oxygen separates.

Another modification when using tellurium compounds a so-called. "Masked" reducing agent used (BE-PS 8 63 052). So are several Compounds known as phenidone, the organotelluric compounds to reduce. The reduction capacity of such  Compounds can be "masked" by appropriate substitution, i.e. H. to be inhibited. In such cases, if the substituent by the in the photo reduction of the Tellurium compound released reaction products cleavable is that masked reducing agents are used the photo response property by the following Reinforce mechanism:

Since the tellurium compounds commonly used as By-products of the hydrogen halide reduction reaction release (especially hydrogen chloride) and the reducing agents, e.g. B. phenidone, amino compounds, the most effective masking agents are those Compounds that convert the amino nitrogen to an amide. So the following connection is a typical one masked reducing agent:

The invention is based, more radiation-sensitive mixtures of the aforementioned To find genus and use as "photo material" in the broadest sense.

The invention is characterized in claim 1 and in the dependent claims and the following description further training of the same claimed and described.

For practical use, the components, e.g. B. a tellurium derivative, a reducing agent precursor and the optional ingredients, such as glycol, with a masked reducing agent in particular in a binder combined into an emulsion. A latent Image can be made by exposure to an appropriate imaging energy generated and then by heating of the exposed film. Alternatively, you can the latent image also using an electron beam or an electric current as activation energy be generated; the reducing agent Precursors are eliminated because the electrons are directly on the Soak in the tellurium compound. Other types of activation energy are known to the person skilled in the art and are among the corresponding ones Conditions also applicable.

The following masked reducing agents are possible:  

with Y = hydrogen or

the connection being at least one

contains.

In the above formula, R1 can be: alkyl, Alkanoyl, alkoxycarbonyl, phenyl, benzyl, benzoyl, Nitrophenyl, benzylcarbonyl, diphenylmethyl, diphenylethyl, or diphenylpropylcarbonyl or aminocarbonyl.

R², R³ and R⁴ are each independently hydrogen, Alkyl or phenyl and amino.

R⁵ can be phenyl, Nitrophenyl, halophenyl, alkyl, mono-, di- or trihaloacetyl, Benzoyl, alkylphenyl or alkyl-p-isocyanophenyl.

The masking group can be attached to one or both amino Nitrogen positions of the reducing agent substituted be. The above alkyl groups can be up to to have seven carbon atoms.

These compounds are easily accessible by reaction the parent hydrazine or pyrazolidine with an isocyanate of the formula

R⁵-N = C = O.

The following connections are for the connections mentioned representative:

The emulsions according to the invention will now be described in detail explained.

Contains an emulsion composed according to the invention a tellurium compound, a reducing agent precursor and a suitable binder, a carrier which can form a photosensitive film, and a masked reducing agent according to the above Description. A diol is optionally provided, and preferably a glyceryl compound.

The prior art describes a number of imaging Tellurium compounds, and these are in the invention essentially usable. In the invention essentially used these and other tellurium compounds, that in the presence of a reducing agent precursor experienced analog reduction reactions.

Many tellurium compounds have been found to determine Have properties that make them particularly useful make suitable in imaging processes. In general these are connections from which as a result of the above mentioned elementary imaging and development steps Tellurium is deposited. Tellurium has chain-forming Character, and it is generally derived from the Tellurium compounds deposited for photographic use Purposes are suitable (preferably including fine Needles or tips), the connections very quickly Form nuclei and can grow as crystallites, which in Form of chains and to a large extent or mainly grow as needles or tips. Such chains or Needles are opaque and show very good Light scattering properties so that after developing good darkness by heat or other means arises.  

Oxide-forming and other effects are essentially due to Surface effects limited, whereas those that one Cause degradation by the body of the needles or chains, do not occur.

The imaging tellurium compound is preferably a Organotellur compound, such as that used for. B. in US-PS 41 42 896 is specified. These compounds are organic tellurium compounds, the inherently sensitizer properties have (and / or with a separate sensitizer are miscible), the tellurium directly with at least a carbon atom or the organic radical of Organotelluric material is chained; the organic Tellurium compound has a certain structure and one detectable property resulting from the exposure with imaging energy in the form of particle or Wave radiation can change so that a material with it different structure and another detectable property is produced. That from the imaging step emerging material with different structure and different detectable properties is sometimes called "imaging Connection ".

A particularly advantageously used in the invention Subgroup of organotellur compounds used for imaging includes those compounds that a Organoradical and halogen included, which are directly attached to the Tellurium atom are bound, the organoradical at least contains a carbonyl group. Certain of these connections are adducts of tellurium halides, in particular Tellurium tetrachloride, with organic compounds, in particular Ketones or similar chromophores, the at least one carbonyl group in the organic Connection included. They can thus be used as organotellur compounds or adducts referred to or labeled  that contain halogen, namely chlorine, bromine, iodine and fluorine, which is bonded directly to the tellurium atom. Most of this particular class or group of imaging compounds have two carbonyl-containing ones Organoradicals. Those particularly suitable for the invention Compounds have chlorine as halogen, but in other halogens may be present in certain cases, although this is generally not quite as satisfactory is. The imaging connections should be chosen this way be that they are in any particular, yet to be explained Matrix material are soluble or homogeneously dispersible. Many of this group of organotellur imaging compounds have the following formula

R _x -Te-Hal _y

With
R = an organo radical with at least one carbonyl group,
Hal = halogen, especially chlorine,
x = 1, 2 or 3, and
x + y = 4,

provided that Te directly with the carbon is chained in an organoradical. Prefers is × = 2 or 3.

Other compounds can be designated by the following formula will:

R₂-Te-Hal₄

With
R = an organic radical containing carbonyl, and
Hal = halogen.

The radical R can be aliphatic, cycloaliphatic or aromatic (one or two seeds) or a combination and can be in the chain or rings of one or contain several heteroatoms. It can be unsubstituted or by various organic or inorganic Radicals can be substituted that have the desired imaging effect either support or at least do not bother; such a radical is e.g. B. C₁-C₆-alkyl, corresponding oxyalkyl radicals, acetyl, Nitro, C≡N, Cl, Br, F etc. In general they have the aforementioned organotelluric compounds which have a trihalogen group, such as B. acetophenon tellurium trichloride, contain a lower melting point (∼70-80 ° C) and are more water-absorbent and less stable as those essentially similar compounds, which contain two halogen atoms and are therefore such trihalogens for use in the invention less he wishes.

A more limited class of this particular subset of imaging organotellur compounds has the formula

(Ar-CO-CH₂) ₂Te-Hal₂

With
Ar = an aromatic hydrocarbon radical which may be substituted or unsubstituted as indicated above, and
Hal = halogen, especially chlorine.

This connection subgroup provides in particular when Hal is chlorine, advantageous embodiments of the The invention relates to the imaging organotellur compounds, which can be used in the invention.  

Another subset of imaging organotellur compounds, which can be used for the invention and are not a carbonyl group in an organo radical contain, but where tellurium directly with carbon connected are those connections that are considered Tellurium tetrahalide adducts of ethylene or acetylene Hydrocarbons are viewed or characterized can. These connections are generally characterized by produces that 1-2 moles, especially 2 moles, of the ethylene or acetylene hydrocarbon with 1 mol tellurium tetrahalide are implemented, with TeCl₄ particularly preferred becomes. Certain of these connections have the following formula:

With
R⁸ and R⁹ = each the rest of an ethylene hydrocarbon, e.g. B. an alkene or a cycloalkene,
Hal = chlorine, bromine or iodine, especially chlorine,
x = 1-3, and
x + y = 1.

Examples of the ethylene and acetylene hydrocarbons, which can be added with tellurium tetrahalides, so that such imaging organotellur compounds are: Propylene; 1-butene; Isobutylene; 2-butene; 2,3-dimethyl-2- Butene; 3,3-dimethyl-1-butene; 2,4-dimethyl-1-pentene; 4,4-dimethyl-1-pentene; 2,5-dimethyl-3-hexene; Dipenten;  1,1-diphenylethylene; Hepten-1; Witches-1; 2-ethyl-1-hexene; 2-isopropyl-1-hexene; 2-methyl-1-pentene; 2-methyl-2- Penten; 2-ethyl-2-pentene; 3-methyl-1-pentene; Piperylene; Vinylcyclohexene; Vinyl cyclopentene; 2-vinylnaphthalene; 1,2,4-trivinylcyclohexene; 4-methyl-1-cyclohexene; 3-methyl-1-cyclohexene; 1-methyl-1-cyclohexene; 1-methyl 1-cyclopentene; Cycloheptene; Cyclopentene; Cyclohexene; 4,4-dimethyl-1-cyclohexene; 2-methylbutene-1; 3-methylbutene 1; and octene-1; low alkyl and low Alkoxy derivatives of various of the alkenes, e.g. B. Cyclohexene; 1-pentine; 2-pentine; 1-hexyne and 3-methyl 1-butyne.

The preparation of the aforementioned organic tellurium compounds as well as a number of examples are in the U.S. Patent 41 42 696 indicated.

As previously said, tetrahalides are tellurium, wherein the halogen is at least either chlorine or bromine, also as an imaging material according to the invention applicable. Such tellurium halides are in the US-PS 40 66 460 described in detail. Certain of these imaging materials have the following formula:

TeCl _n Br _m

With
n = an integer from 1-4, and
m + n = 4.

Typical tellurium tetrahalides are TeCl₄, TeCl₂Br₂ and TeClBr₃, with TeCl₄ particularly well suited is. These tellurium tetrahalides and their use as imaging agents Compounds are in US-PS 40 66 460 in described.  

Another group of imaging compounds are certain compounds derived from tellurium tetrahalides are derived, which are described in US Pat. No. 4,106,939 are. These complex compounds are adducts of Tellurium tetrahalide with aromatic amines, e.g. B. that Tellurium tetrachloride adduct of dimethylaniline, which is none Has diazo groups. In particular, these Tellurium tetrahalide adducts formed in that a Tellurium tetrahalide combined with an aromatic amine being, directly or indirectly to the aromatic Radically bound nitrogen through alkyls with 1-4 carbon atoms is substituted; the imaging end Organotellur material is free of diazo groups.

These aromatic amine adducts of tellurium tetrahalides are fully described in US-PS 41 06 939.

The active tellurium compounds can, if desired be formed in situ, e.g. B. by using a Tellurium oxide or a tellurium salt in connection with a suitable organic compound. Sometimes it will formation accelerated in situ by the presence of an acid. For example, tellurium oxide or alkali metal tellurates with one of the glycols explained later an active complex of tellurium and an organic Form a connection. It is believed that the reaction analogous to the reaction between organic tellurium compounds such as those described above and a diol expires. Information available so far suggests that the reaction is favored by an acidic medium becomes. Small amounts of an acid, e.g. B. anhydrous Hydrogen chloride can be added. Alternatively is the required acidity by halogen Get tellurium compounds.  

Include in addition to the imaging tellurium compound the imaging systems according to the invention a reducing agent precursor or sensitizer, which, as already explained, is a connection that the property under the influence of activation energy has that he is unstable with a hydrogen donor Extracts hydrogen and thus a reducing agent in with respect to the imaging tellurium compound. The activated reducing agent then reduces the tellurium compound to create the desired image. The hydrogen donor can be an external source of hydrogen, e.g. B. a specially provided for this purpose Be alcohol. However, the hydrogen donor can also well be a suitable group that is part of the molecular structure of the reducing agent precursor.

Preferred reducing agents which can be used for the invention Precursors are quinones, especially 2-isopropoxynaphthoquinone, 9,10-phenanthrenequinone and 2-t-butylanthraquinone. While benzophenone is not a quinone, it is just like a number of the simpler ketones as reducing agents Forerunners can be used.

An important factor when choosing the reducing agent The precursor is the spectral range within which the Address reducing agent precursors. For this reason the simple ketones are not general for recording of visible light usable because of their spectral sensitivity is in the distant UV range. Further Reductant precursors and their approximate spectral sensitivity ranges are as follows:  

Below are examples of reducing agent precursors which are sensitive in a range up to approx. 400 nm and can therefore only be used in the UV range: benzophenone, Acetophenone, 1,5-diphenyl-1,3,5-pentantrione, ninhydrin, 4,4'-dibromobenzophenone and 1,8-dichloroanthraquinone.

There are various other reducing agent precursors can be used, in particular those of the substituted type or unsubstituted polynuclear quinones, one of which some have already been mentioned above and others the following are: 1,2-benzanthraquinone, 2-methylanthraquinone, 1-chloroanthraquinone, 7,8,9,10-tetrahydronaphthacenequinone, 9,10-anthraquinone and 1,4-dimethylanthraquinone. Of course are not all reductant precursors effective or equally effective with any particular imaging material, even when considering the application of imaging energy in the sensitivity range of the  respective reducing agent precursor is taken into account and further contemplates appropriate combinations certain imaging materials and certain Reductant precursors must be selected to achieve desired or optimal results. However, such a selection can be relatively easy to be hit.

In connection with the above statements is too note that reducing agent precursors have ηπ * states, both singlet and triplet states, have less energy than π, π * states, and in any case in most cases, connections are theirs have lowest energy π, π * states with respect to Light sensitivity ineffective, although limited in some Cases compounds that pass the test that they are a have lower energy η → π * than π → π * transitions, exist, do not act as a reducing agent precursor. However, the above point of view is generally effective to determine beforehand whether a certain connection as a reducing agent precursor for use in the invention works. In any case, if necessary a simple empirical preliminary test can be carried out by a test emulsion using the desired imaging compound and reducing agent Precursor is produced.

In some cases, an external sensitizer is not required. For example, most organotelluric compounds photolysed directly at wavelengths in the range of 250-300 nm; certain other tellurium compounds, in particular the halides, are for the blue parts of the visible Spectrum sensitive. When imaging through Electrons should not be an additional sensitizer needed because the electron has a direct decomposition of the imaging material.  

According to the invention, a diol can also be present reacts with the tellurium compound to form an active one Intermediate complex. The chemistry of the complex is true not clear, but it is believed that the complex generally requires about 2 mol of diol per mol of tellurium. If present, the diol is preferred in a quantity exceeding the minimum quantity is used, since the diol also acts as a source of unstable hydrogen and those for the reaction of the reducing agent precursor is required hydrogen source.

The present invention in which new masked reducing agents can be used without a diol be carried out, but preferably a diol is used. It was found that by the presence of a Diols greatly reduced the darkness of unexposed areas (i.e., the contrast between the exposed and unexposed areas is improved), in particular, if a masked reducing agent is present is. It is therefore possible to use masked reducing agents to be used in the absence of a diol, but for tellurium Film compositions containing masked reducing agents contain, there is a tendency of a relatively strong Darkness in the unexposed areas because the Reduction capacity of the masked reducing agent not completely suppressed by the masking group becomes.

A group of diols used for the production of Imaging compounds that can be used are diols formula

With
R¹⁰ and R¹¹ each represent hydrogen, a hydrocarbon group including straight chain, branched chain and ring hydrocarbon groups, hydroxyalkyl groups, alkoxycarbonyl groups, cycloalkyl groups or aryl groups; and
Z = an arylene group (e.g. phenylene), the group (-C≡C-), the group (-CR¹² = CR¹³) _n
with n = an integer, e.g. B. 1 or 2, and
R¹² and R¹³ = each hydrogen or an alkyl group, or taken from part of a carbocyclic or heterocyclic ring.

Z can also be omitted, i. H. the two hydroxy-substituted Carbon is directly linked to one another. The The table below indicates the number of diols that can be used:

A more detailed description of the above diols can be found in DE-OS 27 19 023. However, the diol is preferably more complex than the diols according to the DE-OS. The preferred diols are Compounds with the formula

R⁷-O-CH₂-CHOH-CH₂OH.

in the above compound R⁷ can be: alkyl, Acyl, thiazolinyl, alkenyl, phenyl, alkylphenyl, alkenylphenyl, Hydroxyalkylphenyl, benzyl, alkylbenzyl, alkoxybenzyl, Hydroxyalkylbenzyl and halobenzyl and the like Radical.

The thio analogs of the above compounds can also be used (i.e. compounds in which the radical R⁷ by a sulfur compound instead of Oxygen compound with which glycerin is linked).

Preferred compounds having the above structure are those in which the radical R⁷ benzyl or a substituted Is benzyl. The use of the diols with the The aforementioned structure is preferred because it is the blackening the unexposed areas more effectively than the diols reduce the DE-OS 27 19 023.

Except for the main ingredients listed above The composition affected here can contain additives be provided for various purposes. For example, it was found that certain substances have an unexposed shelf life Dry film compositions according to the invention increase, and in some cases, they also increase sensitivity of the film compositions. Examples of such Additives found in the molecules ether or polyether bonds are substances or polymers such as: Polyethylene 20 sorbitan monolaurate, polyethylene 20 sorbitan monooleate, Polyox-10, Polyox-80, Polyox-750, polyethylene glycol- 400 distearate, polyethylene glycol 600 distearate, Poly (1,3-dioxolane), poly (tetrahydrofuran), poly (1,3- dioxepane), poly (1,3-dioxane), polyacetaldehydes, polyoxymethylenes, Fatty acid esters of polyoxymethylenes, poly (cyclohexane) - Methylene oxide), poly (4-methyl-1,3-dioxane), polyoxetanes, Polyphenylene oxides, poly [3,3-bis (halogenomethyl) - oxocyclobutane], poly (oxypropylene) glycol epoxy resins, and Copolymers of propylene oxides and styrene oxides.  

Such substances can affect the imaging film compositions in different amounts, usually in Range of 5-20% by weight of the solid film compositions, be added. In certain cases, increase or increase the shelf life under certain storage conditions, by up to 50% or sometimes even significantly more, and they also increase in various cases the film sensitivity.

The addition of reducing sugars to the imaging films generally causes increased darkness the image area (image blackening - background blackening), when the film is exposed as before and then e.g. B. is developed at about 120-150 ° C for 15 s, especially when the imaging film either fresh or not older than about a day after manufacturing is. If such films with imaging energy exposed and then developed a positive image (i.e. the darkness is in in the unexposed areas more than in the exposed areas Areas) as opposed to the negative system that normally is practiced in the invention. The addition from reducing sugars to imaging compositions also allows developing the image after Expose with imaging energy at lower temperatures and even at room temperature over a period of time of several hours, e.g. B. usually 10, 12 or 15 h. The reducing sugars that can be used are numerous, e.g. B. dextrose, glucose, arabinose, erythrose, Fructose, galactose, fucose, mannose and ribose. Especially dextrose, arabinose, galactose, Fucose and ribose. The reducing sugars are different Quantities can be used, but usually in equivalent amounts or slightly less or more on the amount of organotelluric materials in the imaging Compositions.  

In many cases, a small one may be desirable Amount of a silicone oil or similar substance add like this for better coating of smooth continuous films is known.

The film composition according to the invention is thereby completes the components and optional Components are dissolved in a suitable matrix. The matrix should be as strong in the active ingredients be as concentrated as possible, d. H. is preferred lowest amount of matrix used. You should be so sufficient be dimensioned so that they are the various active Holds components together in a solid solution. An additional set of matrix can be used however, there is obviously a risk of one Dilution of the concentration of active ingredients, thereby the light response time of the film composition slows down becomes. The choice of matrix materials must of course in a corresponding relation to the active components be made so that for any particular composition the best solubility is given.

The matrix materials into which the organotellur imaging materials and, if necessary, the separate sensitizers inserted are used to obtain the image film or the Film coating, are solid at room temperature, and they can be selected from a relatively large number of fabrics will. Desirably, they are at least partially amorphous, and in particular they should be glassy polar amorphous substances with a glass transition temperature of not be more than about 200 ° C, this temperature can even be about 50 ° C and preferably in the range 80-120 ° C. They are generally polymeric. Examples of such substances are: cyanoethylated starches,  Celluloses and amyloses with a cyanoethylation Degree of substitution of ≧ 2, polyvinylbenzophenone, polyvinylidene chloride, Polyethylene terephthalate, Cellulose esters and ethers such as cellulose acetate, cellulose propionate, Cellulose butyrate, methyl cellulose, ethyl cellulose, Hydroxypropyl cellulose, polyvinyl carbazole, Polyvinyl chloride, polyvinyl methyl ketone, polyvinyl alcohol, Polyvinyl pyrrolidone, polyvinyl methyl ether, polyacrylic and polymethacrylic alkyl esters such as polymethyl methacrylates and polyethyl methacrylate, copolymers of polyvinyl methyl ether and maleic anhydride, various Classes of polyvinyl formal resins. Polyvinyl formal 15/95% can be used particularly well, which is a white, free flowing powder with a molecular weight in the range of 24,000-40,000 and a formal salary, expressed as polyvinyl formal content, of approx. 82% is highly heat-resistant, very wear-resistant and durable against substances such as aliphatic hydrocarbons as well It is mineral, animal and vegetable oils. These polymeric substances or resins and their production known. They not only act as carriers for the organotelluric materials, Sensitizers and others about in the imaging film or coating containing ingredients and keep them together and act as dry or essentially dry film-forming agents Fabrics for making thin films and give the finished imaging film mechanical strength, but many of these substances or resins apparently play also a chemical or physical role in the imaging process, by - which is very important - act as a source of easily extracted hydrogen and thus an essential role in the mechanism of Play formation of the latent image, as explained earlier becomes. In certain cases it may be desirable to use the  To reduce matrix viscosity, which z. B. by addition certain plasticizers, e.g. B. dibutyl phthalate or Diphenyl phthalate, can be done; these additions result in the creation of images, which is what is desired to have a greater density, the however, also tend to have a reinforced background veil to create.

It should be noted that matrix materials of the type that contain basic groups with the organotellur imaging materials can form a complex, and the Use of such substances should therefore, as far as such Complex formation occurs, can be avoided.

When making the films or thin layers of the Imaging material compositions, generally prepared in the form of solutions or homogeneous dispersions and applied as a layer or layer to a substrate it is particularly desirable to use the ingredients dissolve in an organic solvent or disperse homogeneously. Examples of suitable ones Solvents are methyl ethyl ketone (MEK), dimethylformamide (DMF), chloroform, tetrahydrofuran (THF), Dimethylacetamide (DMA), dioxane, dichloromethane and ethylene dichloride or compatible mixtures of such organic Solvents with other organic solvents. After the solution or the homogeneous dispersion in a suitable Way applied as a film on a substrate the main proportions of these organic solvents evaporates, preferably at relatively low Temperatures; sometimes it is desirable to use evaporation to be carried out under subatmospheric pressures or in a vacuum, until the film or coating dries feels; such a dry-feeling coating  is especially for handling and processing purposes he wishes. Such films or coatings feel dry, but it should be noted that this does not mean that the film is not an organic solvent contains. In fact, it was found to be it is often very desirable that the finished films or Coatings before being exposed to imaging energy a lower percentage, usually approx. 2-3% by weight based on the weight of the film or coating, organic solvent, e.g. B. dimethylformamide (DMF), included because the presence of the solvent is evident a favorable role in terms of sensitivity of the system relative to the formation of the latent image and / or the image obtained after development plays. The removal of all or essentially all of the DMF or other organic solvent Solvent from the unused film before Mapping and developing often leads to a diminution of sensitivity. If in any case the unused Imaging film was dried so largely that essentially no more organic solvent is present and the sensitivity is too strong the sensitivity can be restored be that a small amount of organic Solvent before exposing the film to imaging energy is added to this.

The film or coating thickness is different, however, it is usually in the range of approx. 1-35 µm, with a thickness of approx. 5-15 µm a good average is. If the thickness is expressed in mm, they between about 0.0005 and 0.05 mm or higher, e.g. B. are between 0.05 and 5 mm, the selected one Thickness depends on the intended use of the film.  

The production of organotellur imaging materials as well as the coating, handling and processing processes, insofar as they are required, are under appropriate lighting conditions performed what is obvious to a person skilled in the art. For example, this is done Preparation of the coating compositions and the Coating and drying advantageously in amberlit filtered light (weak transmission at 550 nm). Before exposure, the dry film is desirably kept in the dark. In certain cases should a contact of certain components with certain Metals are avoided when there are undesirable reactions how reductions could occur. In general, should the vessels or containers, stirrers etc. made of glass or other glassy fabrics or fabrics that are opposite the coating components are inert to contamination or possible undesirable reactions to avoid. It is usually beneficial the imaging compositions just prior to application to manufacture on the selected carrier. Under suitable Storage conditions, which is usually darkness and as far as possible exclusion of air or oxidizing Atmospheres and humidity conditions means the stability of the imaging compositions is good.

The proportions of the matrix, the organotellur imaging material and the reducing agent precursor in the imaging compositions are variable. In cases where the organotellur imaging material used at the same time has the desired sensitization properties, a separate reducing agent precursor is not required. However, it may also be desirable in such cases be a separate or additional reducing agent To use precursors that have completely different sensitization properties as the organotellur imaging material used  having. In any case, in general - The organic or the possibly used Solvent excluded - in most cases the matrix material, which is normally one at room temperature solid substance is used in quantities that are larger than the amount of each of the other substances are, and is usually in very large quantities, d. H. more than 50% by weight, generally in the range up to 90% by weight, of the Total amount of substances in the picture composition are included. The organotellur Imaging material, which is usually also a solid is usually about 1 to more than 20 Parts per 100 parts of the matrix, usually approx. 5-10 parts per 100 parts of matrix material. The reducing agent Forerunner, if it is a separate component , which is usually a solid, in smaller amounts Amounts of approx. 5-20, usually approx. 6-15% by weight the imaging composition, although used in certain Cases the percentage can be much higher and approximately equal to or greater than the proportion of organotellur Illustration material is. Furthermore, with regard to said on the proportions of the aforementioned components that the areal density of the reducing agent precursor is desirably chosen so that approx. 70-95% of the film on the absorption band of the reducing agent precursor falling ions will. Significantly higher concentrations Reductant precursors would be the dark side of the Leave film unexposed so that no advantage can be achieved would. In order to achieve optimal results, the following applies in most Cases where the molar concentration of organotellur Imaging material from that of the reducing agent Precursor not far away or approximately the same should be. The concentration of the polymeric matrix material  should be so high that an essentially amorphous Film can be produced without precipitation of the organotellur Imaging material, sensitizer and others any components used. At there is an excess of polymeric matrix material Danger of reducing the sensitivity of the film.

As has been said, the diol should be at a concentration be present that is sufficient to per mole Tellurium compound to provide at least 2 mol of diol, preferred the ratio should be up to 6: 1. The work has shown that between the Diol and the tellurium compound a complex in a molar ratio of 2: 1 is formed and that excess Diol as a source of labile hydrogen for the reaction with the reducing agent precursor is useful. If desired larger amounts of diol can be used. To some extent, improved results are achieved if these larger amounts of diol are used; there is however a point above which there is an increase in Diol amount no corresponding improvement in photo response of the finished film.

The masked reducing agent according to the invention can present in amounts of 1-200% by weight of the tellurium compound be. A noticeably improved sensitivity results even with very small amounts of the masked Reducing agent, and moved within certain limits the degree of improvement is proportional to the amount of the masked reducing agent added to the film. But a law of diminishing benefits is also observed here; large amounts of the masked reducing agent can be used be added - in the order of 2-4 times the amount the tellurium compound - but above these large amounts  there is no increase in photo responsiveness Relation to the increased amount of masked reducing agent more.

The film-forming compositions discussed above are applied to any suitable support. For this are glass, porcelain, paper and various Suitable for plastic carriers. For the purposes of education translucent material is evident in film-like materials desirable. There are films made of polyethylene terephthalate particularly suitable.  

The following examples serve to explain the Invention.

Example 1

2.1 g glyceryl benzyl ether and 0.625 g tellurium bisacetophenone dichloride are a mixture of 42 ml of methylene chloride and 58 ml of methyl ethyl ketone were added. 2.1 ml one 2% solution of silicone oil in methylene chloride is added, to help prepare a smooth coating.

The mixture is stirred at room temperature for 30 min. and then 0.625 g of the phenyl isocyanate adduct of benzoyl hydrazine added as a masked reducing agent. Then 10.42 g of a polymeric binder, followed by 0.31 g of 2-isopropoxynaphthoquinone added.

The solution obtained is in complete darkness stirred for 1 h and then as a coating on a polyphthalate Substrate applied, with a medium Density of approx. 2 g tellurium bisacetylphenone dichloride per m². The film is then placed in an oven at 65 ° C for Heated for 2-4 hours to remove the solvents.

Example 2

2.0 g p-methoxybenzyl-1-glyceryl ether and 0.625 g tellurium Bisacetophenone dichloride (TeBAC) were a mixture of 42 ml of methylene chloride and 58 ml of methyl ethyl ketone together with 2.0 ml of a 2% solution of silicone oil in methylene chloride added.  

The mixture was stirred at room temperature for 30 min. then 0.625 g of masked reducing agent of the formula

added and the mixture was stirred for 10 min. The polymeric binder of Example 1 was in a 10.42 g added, followed by 0.31 g of 2-isopropoxynaphthoquinone (IPNC) The solution was in complete Darkness stirred for 1 h.

The solution obtained was in a conventional meniscus Application device on a carrier made of polyethylene terephthalate with a thickness of 127 µm applied with a thickness of approx. 2 g TeBAC / m², and the obtained film was put in an oven for Heated at 65 ° C for 3 h.

When exposed to imaging energy of 10⁴ erg / cm² at 365 nm and heating for 30 s at 140 ° C was done with this Film achieved a density of 2.2, the unexposed Area had a degree of blackening of 0.35. The film's gamma was 2.0.

Example 3

2.0 g p-methoxybenzyl-1-glyceryl ether and 0.625 g TeBAC 42 ml of methylene chloride were added and for 3 h Stirred 50 ° C in a closed bottle. 58 ml Methyl ethyl ketone and 2 ml 2% silicone solution in CH₂Cl₂ were added, followed by the masked reducing agent,  the polymer and IPNC as in Example 2.

The mixture was for 1 h at room temperature and dark stirred and on a support in the form of a layer upset.

After coating, the film was placed in an oven Heated to 65 ° C for 45 min. The photo response corresponded exactly to that of the film according to Example 2.

Example 4

2.5 g of o-chlorobenzyl-1-glyceryl ether and 0.6 g of tellurium Bisacetophenone dichloride were mixed with 42 ml Methylene chloride and 58 ml of methyl ethyl ketone were added.

The mixture was stirred for 30 min at room temperature, then 0.625 g of the adduct of benzoyl hydrazine and Phenyl isocyanate added as a masked reducing agent and the mixture was stirred for 10 min. A polymer Binder was used in an amount of 10.42 g added, followed by 0.31 g of 2-isopropoxy naphthoquinone (IPNC). The solution was then in for 1 h stirred in complete darkness.

The solution obtained was washed with a customary meniscus Applicator on a polyethylene terephthalate substrate with a thickness of 127 µm applied with a density of approx. 2 g TeBAC / m², and the film obtained was placed in an oven for 2.5 hours Heated to 65 ° C.  

Films produced in this way have a degree of blackening of 2.0 in the imaging area and 0.3 in the background as well a gamma of 3.0 after exposure to energy of 8 · 10³ erg / cm² at 365 nm and heating to 130 ° C for 1 min.

Example 5

2.5 g p-benzyloxybenzyl-1-glyceryl ether and 0.7 g Tellurium bispinacolone dichloride were mixed out 80 ml of methylene chloride and 20 ml of dimethylformamide Stir room temperature for 3 h.

Then 0.6 g masked reducing agent of the formula

added and the mixture was stirred for 10 min. 12 g polymeric binder polyvinyl formal was added, followed by 0.4 g 2-tert-butylanthraquinone (BAC). The solution was then for Stirred for 1 h at room temperature in the dark.

Films were made by placing the solution on glass plates was poured, with a density of approx. 1.5 g organotellur / m². After drying at room temperature for 1 h the films were in an oven at 65 ° C for Warmed for 2 h.

Films produced in this way have a degree of blackening of 1.5 in the image area and from 0.2 in the background as well as a gamma of about 1.5 after exposure with an energy flow of  8 · 10⁴ erg / cm² at 365 nm and heating to 110 ° C for 90 s.

Example 6

3.0 g p-methoxybenzyl-1-glyceryl ether and 1.18 g tellurium chloride were in 42 ml of methylene chloride and 58 ml Stirred methyl ethyl ketone for 2 h.

This mixture was treated with 0.625 g of a benzoyl hydrazine Phenyl isocyanate adducts as masked reducing agents, 10.42 g of polymeric binder and 0.625 g of 2-isopropoxynaphthoquinone was added. The mixture was then in complete darkness at room temperature for 1 h stirred.

A substrate made of polyethylene terephthalate was then coated with the mixture, one Density of approx. 3.5 g TeCl₂ / m². The film obtained was heated in an oven at 65 ° C for 3 h.

When exposed to an imaging energy of 10⁵ erg / cm² at 365 nm and heat treatment at 150 ° C these films achieved a degree of image blackening for 30 s of 3.0 and a background density of 0.7. The gamma of these films was approximately 3.0.

Example 7

0.21 g TeO₂ and 0.05 g TeCl₄ were in 5 ml for 30 min 2-methoxyethanol was stirred, then this mixture 1.0 g of o-chlorobenzyl-1-glyceryl ether in 42 ml of methylene chloride and 58 ml of methyl ethyl ketone were added. The mixture was stirred for another hour. 0.625 g of masked reducing agent of the formula

10.42 g of the polymeric binder and 0.32 g 2-isopropoxynaphthoquinone was added and the mixture was stirred for 1 h.

On a polyethylene terephthalate substrate with a thickness of 127 microns were films in a Meniscus applicator with a density of 0.4 g TeO₂ / m² applied and in an oven at 60 ° C for Warmed for 3 h. The films obtained had a degree of blackening 2.5 in the image area and 0.7 in the background and a gamma of approximately 3.5 when irradiated with an energy of 10⁵ erg / cm² at 365 nm and heat treatment at 165 ° C for 10 s.

Example 8

0.21 g TeO₂ and 0.09 TeBAC were in 5 ml for 10 min Stirred methoxyethanol, then this mixture 2.0 g of o-methoxybenzylglyceryl ether in 42 ml of methylene chloride and 58 ml of methyl ethyl ketone added and for 1 h stirred. 0.55 g benzoylhydrazine-phenyl isocyanate adduct as masked reducing agent, 10.42 g polymeric binder and 0.3 g of 2-isopropoxy naphthoquinone was added and the mixture for 2 h stirred in complete darkness.

Films were applied to a meniscus applicator Polyethylene terephthalate substrate, the has a thickness of 127 µm, with a density of 0.4 g TeO₂ / cm² applied and in an oven for 3 h at 65 ° C.  warmed up. The films obtained achieved a degree of blackening 2.0 in the image area and 0.5 in the background after exposure to energy of 5 · 10⁴ erg / cm² at 365 nm and heat treatment at 140 ° C for 30 s. The gamma of these films was approximately 2.5.

Example 9

0.48 g H₂TeCl₆ and 3.0 g p-methoxybenzyl-1-glyceryl ether were in a mixture of 42 ml of methylene chloride and 58 ml of methyl ethyl ketone stirred for 2 h. 0.625 g benzoyl hydrazine Phenyl isocyanate adduct as masked reducing agent, 10.42 g of polymeric binder and 0.5 g of 2-isopropoxynaphthoquinone was added and that Mix for another hour in complete darkness stirred.

The solution was then poured onto 127 µm thick polyethylene terephthalate with a density of 1.6 g H₂TeCl₆ / cm² applied and in an oven at 70 ° C. warmed for 3 h. The films obtained achieved one Image darkness level of 1.5 and a background darkness level of 0.1 after exposure to imaging energy of 8 · 10⁴ erg / cm² at 365 nm and heat treatment at 175 ° C for 30 s. The gamma was approximately 3.

Other examples of the manner in which the invention is feasible, proceed from the following approaches that prepared according to Examples 1 and 2 and can be applied as a coating.  

Example 10

2.1 g p-methoxybenzyl glyceryl ether
1.0 g styrene glycol
0.625 g TeBAC
10.42 g of polymer CAB 500-5
58 ml MEK
42 ml CH₂Cl₂
0.31 g IPNC

Example 11

2.0 g of o-chlorobenzyl glyceryl ether
1.0 g styrene glycol
0.625 g TeBAC
10.42 g CAB 500-5
58 ml MEK
42 ml CH₂Cl₂
0.31 g IPNC

Example 12

2.1 g of o-chlorobenzyl glyceryl ether
1.0 g styrene glycol
0.625 g TeBAC
10.42 g CAB 500-5
58 ml MEK
42 ml CH₂Cl₂
0.31 g IPNC

Example 13

2.1 g of o-chlorobenzyl glyceryl ether
1.0 g styrene glycol
0.625 g TeBAC
10.42 g CAB 500-5
58 ml MEK
42 ml CH₂Cl₂
0.31 g IPNC

Example 14

2.1 g of o-chlorobenzyl glyceryl ether
1.0 g styrene glycol
0.625 g TeBAC
10.42 g CAB 500-5
58 ml MEK
42 ml CH₂Cl₂
0.31 g IPNC

Example 15

2.1 g of o-chlorobenzyl glyceryl ether
1.0 g styrene glycol
0.625 g TeBAC
10.42 g CAB 500-5
58 ml MEK
42 ml CH₂Cl₂
0.31 g IPNC

Claims (52)

1. Radiation-sensitive mixture with a reducible tellurium compound, optionally a reducing agent precursor which, under the action of activating radiation, extracts unstable hydrogen from a hydrogen donor and becomes a reducing agent in relation to the imaging tellurium compound, and a hydrogen donor which optionally forms part of the molecular structure of the reducing agent. Precursor forms, characterized by the addition of a masked reducing agent, which corresponds to one of the following formulas: R¹-NY-NY₂ (I) in which
R1 = alkyl, alkanoyl, alkoxycarbonyl, phenyl, benzyl, benzoyl, nitrophenyl, benzylcarbonyl, diphenylmethyl, diphenylethyl, diphenylpropylcarbonyl or aminocarbonyl;
R², R³ and R⁴ = each and independently of one another: hydrogen, alkyl, phenyl or amino;
R⁵ = phenyl, nitrophenyl, halophenyl, alkyl, mono-, di- or trihaloacetyl, benzoyl, alkylphenyl or alkyl-p-isocyanphenyl (the alkyl group in R¹ to R⁵ having 1-7 carbon atoms) and
Y = hydrogen or represent
with at least one in the connection is contained, and with a proportion of the masked reducing agent of at least 1 wt .-% of the reducible tellurium compound. 2. Mixture according to claim 1, characterized in that in addition a diol with the formula is added, whereby
R¹⁰ and R¹¹ = each independently hydrogen, a hydrocarbon group including straight chain, branched chain and cyclic or ring hydrocarbon groups, hydroxyalkyl groups, alkoxycarbonyl groups, cycloalkyl groups or aryl groups;
Z = a direct CC bond between the carbon atoms on both sides, or an arylene group, the group (-C = C-), the group (-C¹² = CR¹³) _n (with n = 1 or 2, and R¹², R¹³ = each represent hydrogen or an alkyl group, or part of a carbocyclic or heterocyclic ring),
and in such a proportion that at least 2 moles of the diol are present per 1 mole of the tellurium compound. 3. Mixture according to claim 1, characterized in that a diol with the formula R⁷-X-CH₂-CHOH-CH₂OH is additionally added, wherein
R⁷ = alkyl, alkanoyl, thiazolinyl, alkenyl, benzyl, alkylbenzyl, alkoxybenzyl, hydroxyalkylbenzyl and halobenzyl; wherein the alkyl radical has 1-7 carbon atoms; and
X = represent oxygen or sulfur. 4. Mixture according to one of the preceding claims, characterized in that the tellurium compound is one of the following: TeCl _n Br _m , where
R = an organic radical with at least one carbonyl group,
R⁸ = the rest of an ethylene hydrocarbon,
Hal = halogen,
x = 1, 2 or 3
x + y = 4,
n = an integer from 1-4, and
represent m + n = 4. 5. Mixture according to one of the preceding claims, characterized, that as the reducing agent precursor 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 (phenylglyoxal) benzene, O-naphthoquinone, 4,5-pyrinquinone, 4,5,9,10-pyrinquinone, Benzophenone, acetophenone, 1,5-diphenyl-1,3,5-pentantrione, Ninhydrin, 4,4′-dibromobenzphenon, 1,8-dichloroanthraquinone, 1,2-benzanthraquinone, 2-methylanthraquinone, 1-chloroanthraquinone, 7,8,9,10-tetrahydronaphthacenequinone, 9,10-anthraquinone or 1,4-dimethylanthraquinone is used. 6. Mixture according to one of the preceding claims, characterized in that the masked reducing agent is. 7. Mixture according to one of the preceding claims, characterized in that the masked reducing agent is. 8. 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Mixture according to one of the preceding claims, characterized in that the masked reducing agent is. 45. Mixture according to one of the preceding claims, characterized in that the masked reducing agent is. 46. Mixture according to one of the preceding claims, characterized in that the masked reducing agent is. 47. Mixture according to one of the preceding claims, characterized, that the tellurium compound and the masked reducing agent as well as other components if necessary bound in a binder or matrix material are. 48. Mixture according to claim 47, characterized, that the binder or matrix material is at least one is partially amorphous polymer. 49. Mixture according to claim 48, characterized, that the binder or matrix material is polyvinyl formal having. 50. Mixture according to one of the preceding claims, characterized, that the proportion of masked reducing agent  up to 200% by weight of the tellurium material is. 51. Image recording material with a substrate and a radiation sensitive layer, characterized, that the radiation sensitive layer is a mixture according to any one of claims 1-50. 52. Process for the production of images, by imagewise Irradiate a recording material with actinic radiation, characterized, that uses a recording material according to claim 51 becomes.