DE2117053A1 - Photosensitive recording material and its use - Google Patents

Description

AGIA-GEVAEßT AG

06 APR. ! 971

Phdtosensitive.es registration material and its use.

Priority: Great Britain, April 9, 1979, ^{Note No.} ^ ⁶ 999/70 Gevaert-Agfa NV, Mortsel, Belgium (company name changed to Agfa-Gevaert IT.V. from April 1, 1971)

The present invention relates to photothermographic Reproduction of information, as well as on materials intended for this purpose.

According to a well-known thermographic process a heat-sensitive copying material is used, which is above-r half a certain temperature turns dark. In the method in which such a copying material is used, the original having infrared-absorbing image parts is in thermally conductive contact with the copying layer using infrared rays exposed. The parts of the copy layer corresponding to the image parts of the original reach one above the relevant limit temperature lying temperature, as a result a dark reaction product forms. This known method is therefore based on the fact that, according to the image, in the original accumulated heat is transferred to the heat-sensitive layer of the copying material.

Because the heat-sensitive reagents left in the parts of the receiving layer that are not exposed to heat are not neutralized, the copy paper remains heat-sensitive and becomes the image-bearing layer with total blackening threatened by uniform warming. This disadvantage and also the fact that only templates with infrared absorbing Image parts on an infrared reflective base for copying on the heat sensitive material come into question, make the procedure less suitable for practice.

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In order to overcome the disadvantages of the above-mentioned method, a new one, in US Pat. No. Wr. 3,094-417 photothermographic.es process developed. In this procedure are the difficulties related to color insensitivity and image stabilization of the copy material overcome. The visible image is created by the action of light and heat on the sensitive layer. Therefore the name "double spectrum method".

According to one embodiment of the method in question a light-sensitive interleaf for the information required Exposure applied. This interleaf contains a first reagent that reacts chemically with an exposed converting photochemically reducible dye into a compound which a second, a receiving material incorporated Is unreactive to the reagent.

The aforementioned photochemically reducible dye is through its property of silver ions in a dilute solution of silver nitrate and triethanoammonium nitrate. reduce marked.

A method based on the photochemical reduction of photochemically reducible dyes is e.g. Fr. 903,942 which of US Pat No. 3 145 104 corresponds. The chemical substances which are in a chemical reaction relationship to the relevant photochemically reducible dyes, are polymers containing mercapto groups. These groups become when the photochemically reducible dye is irradiated oxidizes and forms disulfide groups which cross-link the polymer chains.

According to the above-mentioned in the US Patent No. methods described. 3094417 the first and second reagent are capable of chemically very quickly react with each other at a transition temperature of about 90 ° C to about 150 ⁰ C to form a visible reaction product.

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The first and second reagents are characterized by having positive results in preferably the following manner the test carried out.

Assuming that a heat-sensitive copier system that is in the essentially consists of two substances A and B, which are able to react with one another, is only available the substance A, i.e. the above-mentioned first reagent, dissolved in a small amount in an inert liquid solvent. That Solvent must not react with any of the reagents concerned, the actinic light used during exposure not absorb and not be changed by this light.

The concentration of substance A is just high enough to result in a clearly visible reaction product with substance B, ie the above-mentioned second reagent. Part of the solution in a small, transparent quartz test tube is exposed to radiation (3000-4200 JL) from a high pressure mercury lamp from a distance of 15 ^cm for 45 minutes. A second part of the solution is kept aside for comparison. A small amount of the substance B is on each of the two parts, ie the irradiated and non-irradiated be s part, if necessary, while being heated at about 6O ⁰ C on a water bath, added, whereupon they are colorimetrically compared. A system in which the color of the test solution differs greatly from the color of the comparison solution or is significantly weaker than this is, according to the above-mentioned US Pat the invention described there comes into question. The B-H6 lamp is a commercial product from General Electric (USA); their power in the spectral range 3200-4000 A is 109.3 watts (see British patent specification 966 694).

Examples of reagent A (first reagent) to be used in conjunction with a reagent B (second reagent) of appropriate choice are:

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4-methoxy-1-naphthol, dithiooxamide-ascorbyl palmitate, 1-phenyldithiohydrazocarbonamide, E ', lI ^l - "bis (p-toluenesulfoiiy" l) -H', N ^l -dichlorethylene diamine, tin (II) sulfate, 2-methyl -5-hexadecylbenzoehinone, and N-nitroso-diphenylamine.

According to one characteristic of the invention, the finding is used made that Pyrazolin-5-one-Derivate.mit at least one Hydrogen atom in the 4-position precious metal salts of certain organic Acids "are able to reduce at elevated temperature.

A second characteristic of the invention "is based on the fact that the aforementioned pyrazolin-5-one derivatives are able to react with exposed light-sensitive substances, which converted into a form with an oxidizing effect during exposure. A special class of such photosensitive Substances form the so-called photo-reducible, i.e. photochemically reducible dyes.

Although most of them according to the inventive method pyrazolin-5-one derivatives used have the abovementioned properties, surprisingly they do not give the expected Results in the experiment described above (reaction of a first reagent A with a second reagent B) and therefore cannot be selected for such an attempt.

From the following description of comparative experiments the differences in behavior of two pyrazolin-5-one compounds occur as compared to 4-methoxy-1-naphthol described in the aforementioned U.S. Patent 3,094,417 clearly evident.

procedure

There are three 0.05% strength by weight solutions of the following compounds

(I) (II) and (III) produced in 2-butanone:

(I) 4-methoxy-1-naphthol,

(II) N-phenyl-J-methyl-pyrazoline ^ -ön,

(III) N- (2,5-dichlorophenyl) -3-methylpyrazolin-5-one.

From each solution, 10 ml are kept in the dark and 10 ml poured into a small transparent quartz test glass. the

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three samples in the quartz test tubes are removed in the same way for 3 hours with the IJV radiation of a 20 cm High pressure mercury vapor lamp of 125 watt "exposed. The High pressure mercury vapor lamp is a product of Philips Gloeilampenfabrieken, Eindhoven, Netherlands.

All exposed and unexposed samples are mixed with 50 mg of silver behenate and then gradually heated ^{to 95 ° C. on a water bath.}

The 4-methoxy-1-naphthol-containing pattern in comparison with the unexposed samples before reaching the temperature of 60 ⁰ C a significant weakening of its Färbintensität. In contrast, the exposed and unexposed pyrazolin-5-one-containing samples show no change in their hue or weakening of their color intensity that can be perceived by the naked eye, even at 95.degree. The color at temperatures of 60-80 and 95 ° C varies from gray to light brown to deep brown.

The following description relates to another comparative experiment , the purpose of which is to demonstrate the different behaviors of 4-methoxy-1-naphthol (compound I) and Ή- (2,5-dichlorophenyl) -3-methylpyrazolin-5-one (compound II) to show with UV irradiation in the spectral range above 300 nm.

A so-called photochemical is used as the "exposure device" "RAYOEET TYPE RS" reactor with four "RUL 3500!" Ultraviolet tubes (Total power: 800 W; radiation in the spectral range 300-400 nm).

The experiment is carried out with 0.005% strength by weight solutions of the compounds I and II carried out in n-propanol.

100 ml of each solution are put into a Pyrex glass tube with brazen Cast inside diameter of 4 cm. The glass tubes are arranged parallel to the lights at a distance of 10 cm. The irradiation time is 45 minutes. Of any solution a reference sample is left unirradiated.

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The irradiated and non-irradiated samples are then with 25 mg of a mixture of silver behenate and behenic acid (weight ratio 1: 1) are added per 10 ml of Lb'sung. In the one below The table shows the visible results of the color reaction that takes place.

Tabel

link non-irradiated pattern irradiated pattern I.
II blue solution + gray down
blow
colorless solution + ocher color
good rainfall yellow solution + whiter
Precipitation
colorless solution +
0ekerfarbeniger Nieder
blow

The compound II, i.e. the pyrazolin-5-one, is thus changed remained.

The absorption maximum of the pyrazolin-5-ones is below 320 nm, namely at approx. 280 nm. This is probably the reason why you do not get the expected test results with irradiation in the Spectral range 320-400 nm according to the test method described in British patent specification 966 694 mentioned above give.

The pyrazolin-5-one compounds are preferred in the present invention applied in an admission procedure comprising the following stages:

1) imagewise exposure of a recording material to be activated electromagnetic radiation, which recording material

"contains a photochemically reducible dye that is present in chemical reaction relationship with the pyrazolidon-5-one as the first reagent, the exposure lasting as long as this and takes place with sufficient strength to reduce the reducing power of the pyrazolin-5-one molecules on the exposed Bodies to destroy, and

2) uniform heating of the recording material in such Circumstances that the pyrazolin-5-one compound is on hand or by physical transmission with a second Reagent comes into contact, which is a result of chemical reaction

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between the "two reagents to a physical" resp. chemically detectable change, such as a color change, leads.

According to a preferred embodiment of the invention, in a photothermographic recording process, an intermediate recording material applied, which is a transferable pyrazolin-5-one compound contains in a chemical reaction relationship to a photochemically reducible dye, which in a first Level according to information provided by an electromagnetic radiation is exposed for the purpose of activating the dye with a view to destroying the reducing compound of the relevant Pyrazolin-5-one compound in the exposed areas, and where in a second stage the material is heated to remove the unchanged molecules of the reducing pyrazolin-5-one compound for example by evaporation or melting of any binding agent present therefor from the interleaf to transfer to a receiving material, i.e. for example a layer containing a reducible compound, which with the pyrazolin-5-one compound to form a of the reagents is able to react in a product of different colors.

Pyrazolin-5-one compounds which are suitable for use in one Admission procedures according to the invention come into question have the following general formula:

Ji

O = C ^
RjFi-C-C-Rp

* ₃

where mean:

R _-1 = a hydrogen atom, an organic group, such as a substituted or unsubstituted aliphatic or carbocyclic group (e.g. an alkyl group, preferably an alkyl group containing 1 to 6 carbon atoms), a cycloalkyl group (e.g. a cyclohexyl or cyclopentyl group ), a substituted alkyl group (e.g. a benzyl group, a cyanoalkyl group, a halogenated alkyl group,

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an amino-substituted alkyl group, a dialkylaminoalkyl group), an aryl group (e.g. a phenyl group), a substituted aryl group with any of the substituents alkyl, halogen, amino, substituted amino (e.g. alkylated amino), alkoxy, nitro, acyl, and / or acylamino, one heterocyclic group and one substituted heterocyclic group (e.g. a benzothiazolyl group),

a hydrogen atom, an organic group such as a substituted or unsubstituted aliphatic or carbocyclic group (e.g. an alkyl group, preferably an alkyl group containing 1 to 6 carbon atoms), a cycloalkyl group (e.g. a cyclohexyl or cyclopentyl group), a substituted alkyl group ( e.g. a benzyl group, a carboxy-substituted alkyl group, a halogenated alkyl group, a hydroxyl-substituted alkyl group, an alkoxy-substituted alkyl group), a "well or not etherified hydroxyl group, an ester group, an amino group, a substituted amino group (e.g. a well or unsubstituted acylamino group), a ureido group , a substituted ureido group, a thioureido group, an N-carbamic acid ester group, a carbonamide group (-COIiHp), an aryl group (e.g. a phenyl group), a substituted aryl group (substituted e.g. with an alkyl group, an alkoxy group, a nitro group or a halogen atom, such as for example a chlorine, bromine or Fluorine atom) a well or unsubstituted heterocyclic group (e.g. a pyridyl group), a hydrogen atom, a saturated or olefinically unsaturated aliphatic group such as an alkyl group with Λ to 6 carbon atoms, a substituted group of the same kind (e.g. substituted with a phenyl -, Benzyl or phenylethyl group, with a halogen atom, such as one. Chlorine or bromine atom, with a cyano, with an alkoxy ^: group, with an alkoxycarbonyl group or with an anilinocarbonyl group), a dialkylaminoalkyl group, a substituted or unsubstituted aryl group (e.g. a phenyl group or one with an alkyl group or a preferably 3 C -Atoms-containing alkoxy group, a

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ITitro group or a nitrile group substituted aryl group), an amino group or a substituted amino group (e.g. one containing 1 to 3 carbon atoms Alkyl group substituted amino group, a cycloalkylamino group, a phenyl-substituted amino group, an acyl-substituted amino group, the acyl group being preferred of short-chain aliphatic carboxylic acids originates from), an alkoxy group (preferably an alkoxy group having 1 to 3 carbon atoms), a halogen atom (e.g. a Chlorine atom) or a -COEHo group, E ^ = a hydrogen atom, "an alkyl group (e.g. one from 1 alkyl group consisting of up to 5 carbon atoms) or a 4-aminophenylamino group,

where at least one of the two substituents R, and E ^ is a hydrogen atom.

Here follows a list of IL, E ₂ ""'^ 3 ~ ^ ²¹ * ³ - β / i-Si substituents, of pyrazolin-5-one derivatives which are suitable for the process according to the present invention:

Cl OCH ₃

OCH

£ ^, - (CH ₂ J ₅ -CH ₃ , Cl

Cl N0_

(I ²

Cl ^iH 3 <f \

Cl

-N (C ₂ H ₅ ) ₂ -, -, ζ ^ -Cl, - <Q> -NHCOC ₁₇ H ₃₅ , -CH ₂ -CH ₂ -CN, Cl

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- <d>' -f ^ ii-

, or a - <£! $> .- KEp group,

= H, KH ₂ , -CH ₅ -, -COOC ₂ H ₅ , -KHCOCH ₂ , CH I

GK-.

KHCOOC ₂ H ₅ , nC

K-pyridyl, m-nitrophenyl, -OH,

H, -CH _x , -CH ₀ -GH ₀ -CH, -CH ₀ - <f ~%, -J -CH ₂ -K (C ₂ H ^) ₂ , -CH ₂ -K ^ * H ~ ^> , -CH - (^ -COK (CH ₅ ) ₂ , -COK (CH ₅ ) ₂ , -C (C ₆ H ₅ ) ₅ , - (* 5 -CH ₂ -COOC ₂ H ₅ , -CORH ₂ ,

-KH-

one -

^ C ₂ H ₅ , -MHCOCH ₅ , Br,

Oh, or

Group,

R ₂ , = hydrogen atom or a methyl group.

The table below shows 35 different preferred pyrazolin-5-one compounds for the process according to the invention listed.

Tabel

H ^C 6 ^H 5 R ₂ KH ₂ Margin no E I R
² K ^ H d. CH ₅ Pyrazolin-5-one R. C ₆ H ₅ CH ₅ H Grief Cyclohexyl CH ₅ H - 1 p_-To Iy _- I CH _x H 2 H 3 H M-

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6th m-chlorpheny1 CH ₃ H I ₂ CO-NHCgH ₅ . 7th 2,5-dichlorophenyl CH, H CH ₃ 8th 3-nitrophenyl CH ₃ H _r s- 9 4-nitrophenyl H C ₂ H ₅ 10 ° 6 ^H 5 -COOC ₂ H ₅ H -NHCOCH ₃ 11 1-phenylethyl ^C 6 ^H 5 H -OC ₂ H ₅ 12th ^G 6 ^H 5 -CH ₂ COOC ₂ H ₅ H CH _x 13th ^C 6 ^H 5 Pyridyl-4 H 1- (Benzthiazolyl-2) -3,4-dimethyl-4- (4-diethylaminophenyl- 14th 2-diethylaminoethyl CH ₃ H amino) pyrazolin-5-one 15th 2,4,6-trichlorophenyl CH ₃ Ή 16 2,4,5-trichloropheny1 OH,
JP H 17th 2-cyanathyl ° 6 ^H 5 H 1-Phenyl-3 _} 4 ~ dimethyl-4- (4-diethylaminophenylamino) - 18th 3,5-dimethylphenyl -COOC ₂ H ₅ H pyrazolin-5-one 19th ^C 6 ^H 5 OH H 20th 3-nitrophenyl CH ₃ CH ₃ 21st 3-aminophenyl CH ₃ CH ₃ 22nd 3-nitrophenyl CH ₃ Benzyl 23 2-ethoxyphenyl C ₆ H ₅ CH ₃ 24 ^C 6 ^H 5 ^G 6 ^H 5 CH,
3 25th ° 6 ^H 5 ^G 6 ^H 5 C ₂ H ₅ 26th ^C 6 ^H 5 —CHp — CHp — CHp-CHp- 27 ^C 6 ^H 5 OH, -CI
0 28 ° 6 ^H 5 -COOC ₂ H ₅ 29 ° 6 ^H 5 —CH p — CH p — CH / · 30th 3-nitrophenyl OH,
j? 31 ^C 6 ^H 5 CH ₃ 32 -COOC ₂ H ₅ 33 ^C 6 ^H 5 OH, 34 35

The pyrazolin-5-one compounds with at least one hydrogen atom in 4-digit are "well-known Zvd.schenprodukte for the production of Purpiir azomethine dyes, which are generally used in in the manufacture of silver halide based color photographic materials.

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The pyrazolin-5-one compounds can be removed by condensation a suitable hydrazine with a suitable active methylene keto compound, such as a suitable acyl acetate. For the production of special pyrazolin-5-one compounds, let refer to the literature for the preparation of pyrazolones for color photography (see e.g. Glafkides: Photographic Chemistry, Vol. II, Fountain Press, London 1960, p. 601, and U.S. Patents 3,462,270, 3,325,482 and 3 393 071.

Photosensitive dyes, which are used for the local process Possible candidates can easily be selected by chemical testing in solution, with reduction of silver ions to metallic Silver takes place. It is as follows as described in the aforementioned US Pat. No. 3,094-417 Test procedure

A solution is prepared which contains about 0.001 mol of silver nitrate, 0.01 mol of triethanolammonium nitrate (obtained, for example, by neutralizing triethanolamine with nitric acid) and 0.0001 mol of the dye to be tested per liter of a suitable inert, neutral, non-photosensitive liquid solvent contains. The concentrations are not critical and are only given here according to their order of magnitude. Water is the preferred solvent for water-soluble dyes, while methanol, dioxane or mixtures thereof with water are best suited for the preparation of solutions of water-insoluble or only partially water-soluble dyes. Two portions of 15 ml are held in Pyrex Reagenzgläsera on a water bath at 50 ⁰ C. One part is protected against the effects of light, while the other part is exposed for 30 minutes with a projection tungsten filament lamp of 500 watts at a distance of 20 cm, ie with an illuminance of approx. 64-5,600 lux. The two glasses are then compared visually with one another. The unexposed glass with the comparison solution shows tiny ^: visible traces of precipitated silver mostly in the form of a fine black powder. However, the amount of precipitated silver is significantly greater in the presence of an activatable dye. This can already be seen visually, or better still

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determine quantitative analysis. The Silbernie & slain shows in the form of dense black flakes or in the form a sirber mirror on the well-cleaned glass wall. Although it is not always necessary, the silver precipitate leaves itself to an excessively organic form due to its insolubility Differentiate the solvent from the precipitated amounts of the dye or other substances.

There is a strong silver deposit on the test halogen-containing fluorescein dyes, such as erythrosine, rose bengal, D & C Orange 15 and "Aizen Acid Phloxine PB", as well as when testing pararosaniline dyes such as calcozin violet Ex.Cone, according to the procedure described above.

Many other dyes have proven to be less useful, but not useless for the process according to the invention. Examples of such dyes are pure Eosin OJ, Rhodanin B Extra S, Pontacyl Violet S4B, Pontachrom Azure Blue B, Phenosafranin, Fast Fat Blue B, Artisil Orange 3EP> Tinon Yellow GE-F, Calcozin Blue ZF (methylene blue), Aizen New Methylene Blue HHX, Setoflavin T, Proflavine Hydrochloride, Azo Scarlet Y and Eryptocyanin. Dye mixtures can also be used. The dyes suitable for the process according to the invention are in any case organic compounds which absorb the light in the visible part of the spectrum in the wavelength range above approx. 420 nm, convert silver ions in the test conditions described above into precipitating metallic silver and, when exposed to light, the pyrazoline 5- on compounds at a higher temperature, for example at 90-15O ⁰ C ₅ weaken the reduction compounds shown.

Another attempt to know whether a dye is suitable or not for the system according to the invention is based on the photo-oxidation of a compound containing a mercapto group, such as a thiol polymer, by the subject Dyes.

Dyes which accelerate the oxidation of the mercapto groups of thiol polymers when exposed to visible light, are for example in British Patent 903,942 mentioned above

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described. There are e.g. Rose Bengal, Phloxin, Erythrosin, Eosin, fluorescein, akriflavin, thionin, riboflavin, chlorophylls, Hematoporphyrin, Prof lavin, methylene blue and the like. These dyes therefore include members of the fluorescein "and of the thiazine family, as well as certain acridines and porphyrins. Many of these dyes are fluorescent. They are described, for example, in U.S. Patents 2,850,445 and 2,875 04-7.

Although the amount of photochemically reducible dye with respect to the pyrazolin-5-one compound can vary between widely spaced limits, it is advisable to Use as little dye off as possible to avoid the light to allow the dye-containing layer to penetrate as well as possible and, moreover, eeflexexposure to the touch with opaque templates to enable.

The photosensitive layers according to the invention contain at least one pyrazolin-5-one compound, preferably in a proportion of 1 mol per 0.1-0.2 mol of photochemically reducible compounds Dye. The amount of the pyrazolin-5-one compound in the layers is preferably 0.1-1.5 g / liter but largely the respective requirements of the copying process and the type of photochemically reducible dye or the photochemically reducible dyes and the reducing Substance in the receiving layer or in the receiving material adjust.

In the production of the photosensitive according to the invention Materials are the photochemically reducible dye or the photochemically reducible dyes and those caused by heating reducing pyrazoline-5-compound transferable in the vaporized or molten state together in the form a suitable solution, preferably in the presence of a suitable film-forming binder, on a suitable substrate applied.

Suitable binders for the photosensitive layer are all kinds of high-molecular natural substances, modified natural substances and plastics such as proteins (e.g. gelatin), cellulose derivatives (e.g. cellulose ethers, such as ethyl cellulose,

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Cellulose esters, carboxymethyl cellulose), alginic acid and their Derivatives, starch ethers, galactomannan, polyvinyl alcohol, Poly-N-vinylpyrrolidone, from α, / S-ethylenically unsaturated compounds derived polymers such as homo- and mixed vinyl polymers such as polyvinyl chloride, mixed polymers of vinyl chloride and vinyl acetate, partially saponified polyvinyl acetate, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, Polymethacrylic acid esters and polyethylene.

The weight ratio of the pyrazoline 5- ^o & -V "compound to the binder is, for example, 0.02-0.3.

The photosensitive material consists of a self-supporting layer or one supported by a suitable backing material photosensitive layer. Suitable documents are e.g. paper (preferably glassine paper) and plastic films, as they are known from silver halide photography. The light-sensitive layer can also be applied to glass or apply another suitable material from which it can be easily peeled off and transferred to a permanent surface.

One together with a light-sensitive material serving as an intermediate material Material used receiving layer or separate material contains a substance which acts as a reaction component in a color reaction with the reducing pyrazolin-5-one Ver binding of the photosensitive layer is involved. Such substances belong to the most diverse groups of chemical Compounds so that it proves practically impossible to link them by any particular chemical structure mark.

A practical attempt to check whether any compound used in a receiving layer or material is suitable for reacting with the pyrazolin-5-one compound to cause a discernible color change is to warm the participants in the action in any of the abovementioned binders or in an inert solvent at a ^{temperature above 60 °} C. in the presence of the reagent to be tested for the receiving layer

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or the receiving material ', where one notes the degree of the color change in the layer or in Reagierglas example at a temperature between 80 and 120 ⁰ C.

The pyrazolin-5-one compounds are particularly reactive with the exposed photochemically reducible dyes, which is extremely beneficial for obtaining clear prints in the receiving layer or the receiving material within proves that the irradiation and processing time is not too long.

Suitable reactants for the reducing pyrazolin-5-one compounds include the following.

1) Noble metal compounds, such as silver compounds, which in the circumstances of the copying process according to the invention are extremely insensitive to light, e.g. silver salts are more aliphatic Carboxylic acids which have a thioether group are provided, such as the type described in British Patent Specification 1 111 4-92, or also long-chain silver salts of aliphatic carboxylic acids with at least 14 carbon atoms, such as silver behenate, silver stearate, silver palmitate and the like.

2) Diazonium salts, which with the pyrazole: bi-5-one compound by the action of the active hydrogen atom or the active Hydrogen atoms in the 4-position opposite the 5-OB group be able to react. By coupling known from diazotype chemistry, they form dyes with these pyrazolones.

3) Compounds which are in oxidized! Form or under oxidizing Under certain circumstances form a dye with the pyrazolin-5-one, e.g. p-phenylenediamines and its derivatives derived from Azomethine dyes known from silver halide color photography form.

In addition to the reagents that build up the image, the layer or the material in which the picture is created, also all sorts of accessories Contains sentences, such as image tone influencers (e.g. 1- (2S) -phthalazinone) and accelerators of the reaction providing the image dye, such as sterically hindered phenols, which are involved in the Heating reaction participants for the reduction reaction

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(e.g. 2,4,6-tri-tert-butylphenol). Suitable image receiving rails have long been known from the patent literature, e.g. from the aforementioned U.S. Patent 3,094,417, U.S. Patents 3,094,619 and 3,094,620, the German patents 895 101, 1 003 577, 1 004 043, 1 159 758 and 1 165 410, the Dutch patent specification 277 086 and the Belgian patent specifications 6O9O57 and 614 064.

The spectral sensitivity of photosensitive materials depends on the type of photοchemically reducible used Dye as well as the amplification or expansion of the spectral sensitivity by means of spectral sensitizing dyes away.

The photochemically reducible dyes can be used together with photochemical oxidizing agents such as those in the British Biimidazolyl compounds described in US Pat. No. 997,396.

These photochemical oxidizing agents can be spectrally sensitized. For example, the biimidazolyl compounds with fluorescent coumarin derivatives according to FIG be sensitized to the following general formula:

in which:

X and Y each represent a hydrogen atom, a well-substituted or unsubstituted one Alkyl group or an alkoxy group,

Z is a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an amino group or a substituted amino group (preferably a dialkylamino group), and

W is a hydrogen atom, a well or unsubstituted alkyl or aryl group such as a phenyl group with an alkoxy or a dialkylamino group in the o- or p-position.

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The aforementioned coumarin derivatives are preferably with a Dialkylamino or an alkoxy group in the 3- and / or 7-position of the coumarin internal substituted.

The biimidazolyl compounds have an inherent sensitivity to UV radiation in the wavelength range below 300 nm. But they can easily be used for the longer wavelengths as optical sensitizers or spectral sensitizers sensitize dyes known from silver halide photography.

All kinds of cyanine, merocyanine, styryl and rhodacyanine dyes are preferably to be used as sensitizers of this type choose as they are e.g. from F .M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, pages 90, 100, 433,502 and 511 are.

The best sensitizers for the photochemically reducible dyes, such as a biimidazolyl compound, can be easily according to the sensitometric experiments known to Lachmann choose.

The addition of sensitizers has not only an increase in spectral sensitivity, but also a significant increase the general sensitivity as a consequence, which of course turns out to be extremely desirable for shortening the copying time proves. The spectral sensitization of the recording layers according to the invention in the visible spectral range, i.e. even in the Green and red, not only enable flawless monochrome copying of color documents, but also copying in natural colors through a suitable choice of the image-generating system, with dyes for the image structure according to the subtracting method Come about.

The information-based irradiation takes place e.g. with the visible Radiation from a lightbulb or fluorescent lamp instead, the exposure time and exposure level are preferred chosen such that the ability of the recording material to generate a visible reaction product when heated is destroyed in contact with a receiving sheet containing silver behenate.

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The heating of the "exposed recording material can take place in accordance with any arbitrary suitable method. Its purpose is to enable the image-generating chemical reaction" or to promote. The heating takes place, for example, with heated plates or rollers, infrared ^{radiators, electrical resistors or an electrical KB 1} heating element.

The present inventive method enables production a directly readable positive image by reflex exposure on a receiving material containing an imaging reagent for those transferred from a photosensitive intermediate layer Contains pyrazolin-5-one compound. The copies do not need to be stabilized and their image background is practically colorless.

Although for the creation of visible images on very bright Background is the application of an intermediate material and a receiving system, the present invention also enables copies to be made by means of a light and heat sensitive single sheet material. For example, those in the above-mentioned US patent are recommended 3 O ° A 417 described procedure.

Thus, for example, a copy material can be used, consisting of a thin, transparent paper-like base, which is provided with a layer in which a substance is incorporated which is produced by reaction with the pyrazolin-5-one compound in question capable of producing a colored reaction product, but not in direct chemical contact with it Pyrazolin-5-one compound is located. Direct chemical contact, for example, by means of a thin, non-transparent, highly pigmented, vapor-permeable binder layer Avoid leaving the binder in the solvent component of the casting liquid with which the photosensitive top layer is applied is insoluble.

The application of the monosheet photothermographic material results in a reflex exposure process, a copy that can be read directly through the back of the transparent substrate.

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A suitable pigment such as titanium dioxide and zinc oxide with with an average grain size of 1 to 5 jp the heat penetration of a volatile pyrazolin-5-one compound by a suitable binder such as ethyl cellulose.

According to another embodiment of the invention is replacing permeable layer with a normally impermeable thin layer of a fusible film-forming material, that melts and becomes compatible with the underlying binder for the reducing substance. (See the British U.S. Patent 1,184,054 and U.S. Patent 3,223,838).

Instead of transferring the reducing agent in the vapor state also the possibility of doing the same in a fusible medium, such as in a fusible waxy or resinous medium transfer. The transfer process can be carried out using a suitable solvent that causes a certain swelling, accelerate, e.g. according to the method described in British patent specification 1,135,371. Heat transfer of a polymeric substrate without swelling caused by a solvent finds e.g. according to that in the Belgian patent 700 472 (which is the British patent 1 195 corresponds to), the procedure described takes place.

The following examples illustrate the present invention. The percentages given are percentages by weight, if not otherwise specified.

example 1

A tracing paper is made with a pouring liquid of the following Composition coated with a pour number of 25 g / m2 :

N- (2,5-dichlorophenyl) -3-methylpyrazolin-5-one 1 g Erythrosine 0.440 g '

Ethyl cellulose 50 g

Methyl ethyl ketone up to 5OO g

The dried photosensitive layer obtained in this way is in contact with a graphic according to the Eeflex method

GV.458 109845/1174

Original "exposed, which is made up of parts' different optical Dense existing image in addition to non-image areas, the photosensitive side of the copy material with the printed Side of the original is in contact. The exposure lasts 30 seconds and takes place with a 5 cm from the copy material remote tungsten filament light bulb of 150 watts instead. That exposed The material is then pressed against a receiving material with its light-sensitive layer at 125 ° C for 5 seconds, consisting of a thin colorless arranged on a base Layer which is made from a Gemjash Silver behenate, phthalazinone as picture tone influencer, 2,6-di-tert-butyl-4-methylphenol as a heat sensitive eductor, Poly-tert-butyl methacrylate as a binder (3 parts per 10 parts Silver behenate) and 86 parts of acetone. The dry receiving layer contains an amount of silver behenate equivalent to 0.2 g of silver, 4-00 mg phthalazinone and 4-0 mg 2,6-di-tert-butyl-4-methylphenol per m2.

The result is a directly readable, sharp, dark brown positive copy of the original.

Examples 2 and 3

Example 1 is repeated, but with N- (2-chlorophenyl) -3-niethylpyrazolin-5-one (Example 2) or H- (4-nitrophenyl) -3-methylpyrazolin-5-one (Example 3) instead of the pyrazolin-5-one used in Example 1.

Example 4-

Example 1 is repeated, but with N-phenyl-3 »4-dimethylpyrazolin-5-one instead of the pyrazolin-5-one used there.

The result is a gray-brown copy of the original.

GV.458

109845 / 117A

Claims (1)

Claims [Λ, Photosensitive recording material, characterized in that it contains a pyrazolin-5-one compound with at least one hydrogen atom in the 4-position in chemical reaction relationship with a dye, so that when the recording material is exposed to the action of a dye absorbable, activating electromagnetic radiation is exposed, a chemical reaction takes place between the dye and the pyrazolin-5-one compound with an image-wise change in the chemical properties of the latter compound. 2. Photosensitive recording material according to claim 1, characterized in that the dye is a dye which can be activated by colored light, which upon the action of light absorbed by it contains silver ions in addition to the dye silver nitrate and triethanoammonium nitrate Trial resolution reduced. 3. Photosensitive recording material according to claim 1 or 2, characterized in that the dye is a halogen-containing Is fluorescein dye or a pararosaniline dye. 4. Photosensitive recording material according to any one of the preceding claims 1-3 »characterized in that the pyrazolin-5-one compound is one of the following general ones Structural formula corresponding chemical compound is: Yes i, in which: Ry, a hydrogen atom or an unsubstituted or substituted aliphatic, carbocyclic or heterocyclic group; R _{2 is} a hydrogen atom, a substituted or unsubstituted aliphatic, carbocyclic or heterocyclic group, a hydroxyl group, an ester group, an amino group, ^{CT 458} 109845/1174 a substituted amino group, an alkoxy group or a Carbonamide group;
R, a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, an alkoxy group, an aryl group or a carbonamide group; Rn is a hydrogen atom or an alkyl group, where at least one of the two substituents R 1 and R ^ a Is hydrogen atom. 5. Photosensitive recording material according to claim 1, characterized in that the reactivity of the in one inert solvent dissolved pyrazolin-5-one compound compared to silver behenate, no significant change due to exposure for up to 3 hours at room temperature a HPR high pressure mercury vapor lamp that is 20 cm away from the sample and emits in the spectral range from 300 to 420 mn of 125 watts goes down. 6. Photosensitive recording material according to any of the preceding claims, characterized in that the dye and the pyrazolin-5-one compound in a suitable film-forming binders are dispersed. 7. Photosensitive recording material according to claim 6, characterized in that the dye and the pyrazolin-5-one compound have been applied to a suitable surface. 8. The light-sensitive material according to any of the preceding claims, characterized in that the pyrazoline-5-on-Verbiidung can be transmitted by "evaporation in the temperature range of about 90 to 150 ⁰ C. 9. Photosensitive material according to any of the foregoing Claims, characterized in that it comprises a transparent base, which with one of these Dye and binder containing this pyrazolin-5-one compound in a mutual chemical reaction relationship is coated. 1 09845/1174 .10. Light sensitive recording material according to any of the preceding claims 1-8, characterized in that there is a pyrazolin-5-one compound and a chemical Contains reagent which, at ordinary or elevated temperature, produces a colored reaction product by chemical Reaction with this pyrazolin-5-one compound forms, but neither physically nor chemically in the absorption material There is a reaction relationship with this compound, and that the pyrazolin-5-one compound in the material is in chemical 'There is a reaction relationship to the dye, which is produced by this compound in relation to silver behenate at elevated (temperature shown reducing power is able to destroy. 11. Recording material according to claim 10, characterized in that it has a transparent base. 12. Recording material according to claim 10 or 11, characterized j that the pyrazolin-5-one compound and the chemical reagent are in separate layers. 13. Recording material according to claim 12, characterized in that the layers contain binding agents which are melted on State are compatible with each other. 14. Recording material according to claims 10-12, characterized in that that the pyrazolin-5-one compound from the chemical reagent by means of a vaporized pyrazolin-5-one leak Layer is separated. 15 · Registration process, characterized in that it comprises the information-based irradiation of a photosensitive recording material with an activating electromagnetic radiation, which photosensitive recording material contains a photo-reducible dye in a chemical reaction relationship to a pyrazolin-5-one compound, the molecule of which contains at least one Has hydrogen atom in the 4-position, the irradiation with an electromagnetic radiation absorbed by the dye takes place with such strength and for a long time that the reducing power shown by the pyrazolin-5-one compound at elevated temperature to the SLlberbehenat is destroyed. 109845/1174 16. The method according to claim 15, characterized in that the recording material is heated after its information-based irradiation to pyrazolin-5-one that has remained unchanged by evaporation into chemical reaction relationship with a reagent to produce a different color than to bring the reaction product containing the reagent. 17 · The method according to claim 1.5, characterized in that. it includes the following stages: 1) Information-based irradiation with a suitable electromagnetic radiation from a light-sensitive Absorbing material, the vaporizable pyrazolin-5-one compound dispersed in a suitable binder together with the dye, contains; 2) uniform heating of the exposed material in close contact with a material containing at least one substance Receiving material which at the temperature concerned with the transferred pyrazolin-5-one compound reacts to form at least one or more colored reaction products. 18. The method according to claim 17, characterized in that the receiving material contains a highly photosensitive precious metal salt. 19. The method according to claim 17 or 18, characterized in that that the exposure is a reflex exposure in contact with an opaque graphic template. 109845/1174