DE2042054A1 - Photographic dry copying process - Google Patents

Description

AGFA-GEVAERTAG

LEVERKUSEN

^{za / pk} 24 Aug 1970

Photographic dry copying process

The invention relates to a photographic dry copying process and a photosensitive material for carrying out this method.

Photographic processes that produce copies of a Deliver template are known per se. These are essentially materials that are sensitive to light or heat Layers included. These layers are exposed or heated imagewise, which triggers a coloring reaction, which :: leads to the formation of the image.

The known photosensitive materials of the above type with which negative copy images can be produced are however, disadvantageous in several respects. Such is their sensitivity to light unsatisfactory, especially in the visible region of the spectrum, so that copying times that are too long are required and the reproduction of colored originals causes difficulties.

2098 10/0773

BATH

The finished images also remain sensitive to light, and their stabilization against daylight can generally be achieved can only be achieved through a rather complicated follow-up treatment.

Processes for making copies are also known by imagewise exposure of a photosensitive layer comprising a photosensitive compound and an image-receiving layer contains transferable, image-forming compound, the image-forming compound at the exposed areas Compound is converted into a non-transferable compound, bringing the exposed layer into contact with an image-receiving layer, which contains compounds which react with the image-forming compound to form colored compounds, and Heating the layers in contact to a temperature at which the image-forming compound differs from the unexposed Places the photosensitive layer is transferred into the image-receiving layer.

This process includes, for example, the so-called heat development processes, in which light-sensitive materials having a silver halide emulsion layer are used, the contain a photographic developer. After exposure, it is brought into contact with an image-receiving layer by heating containing substances that react with the developer to produce dyes. The developer is in the heat are transferred from the unexposed areas of the photosensitive layer into the image-receiving layer, in which case Place the receiving layer forming a colored image.

A disadvantage of these known heat development or developer sublimation processes is the inadequate storage stability of the developer-containing silver halide emulsion layers by the content of substances that increase the residual moisture in the layers, such as salts that form hydrates, or Glycols, and due to the increased sensitivity to oxidation of most developer substances in these weakly or uncured Emulsion layers with high residual moisture.

AG 691 - 2 -

~ 209810/0773

This type of copying process also includes that in the U.S. Patent 3,094-417. In this process, light-sensitive layers are used, which contain a volatile compound and a dye. When exposed, the volatile compound becomes (4-methoxy-l-naphthol) converted into a non-volatile product. Subsequent heating can convert this compound from the unexposed areas into a receiving material where it reacts with a silver salt (silver behenate) to form a colored positive image.

The last-mentioned method has the disadvantage that the sensitivity of the layers is relatively low and the Shelf life of the material is limited. *

The invention is based on the object of photographic dry copying processes and photosensitive processes suitable for them To develop materials that have sufficient photosensitivity and durability and that contain dyes, which make the material sensitive to the required spectral range and which produce multicolored and allow black images.

A process has now been found for the production of copies by imagewise exposure of a photosensitive layer which contains a sensitizer and a similar in an image

Receiving layer contains transferable, image-forming compound, the image-forming compound at the exposed areas is converted into a non-transferable compound, bringing the exposed layer into contact with an image-receiving layer, which contains compounds which react with the image-forming compound to form colored compounds and Heating the layers in contact to a temperature at which the image-forming compound is separated from the unexposed areas of the light-sensitive layer is transferred into the image-receiving layer, whereby a light-sensitive Layer containing, as sensitizers, halogenated polymethine dyes of the following general Formulas and as image-generating,

^A ~ ^{G G91} " ³ " 209810/0773 _ΛΙΗ4 ,

BATH ORIGINAL

transferable compound is a reducing agent transferable at a temperature between 80 ° and 200 °, which when the material is exposed in nich-. volatile reduction products is transferred, is used i

N (+) R ¹

Γ ⁰ ,

fr

Anion

R * Hal

Anion

CH-C. C = CH

R anion

A-G 691

2098 10/0773

BATH ORIGINAL

where mean:

Hal = Cl, Br, J;

R = 1) a saturated or unsaturated aliphatic Group with preferably up to 6 carbon atoms, which can be substituted, e.g. with halogen or Phenyl, hydroxyl, amino, carboxyl, suIfο, suIfoamino, Sulfamoyl, carboxyamino, carbamoyl, Alkoxycarbonyl, alkoxy, aroxy, carboxyalkyl, sulfato or thiosulfato groups;

2) Cycloalkyl such as cyclohexyl or

3) aryl, especially a group from the phenyl series;

R = hydrogen, alkyl with preferably up to 3 carbon atoms, Aryl such as phenyl or cycloalkyl such as cyclohexyl,

R, R = identical or different, namely hydrogen or hydroxyl, but where at least one of the radicals is one Means hydroxyl group;

R? = Hydrogen, alkyl or alkoxy with preferably up to 5 carbon atoms, halogen, in particular chlorine, bromine, iodine or a trifluoromethyl group, aryl, in particular a phenyl group;

R = aryl such as phenyl, heterocyclic rings such as thienyl, or furyl, which can also be substituted;

X = that to complete a benzo or naphtho ring, the at least one halogen such as Cl, Br, J or contains a trifluoromethyl group, necessary ring members, e.g. to complete a 5-iodobenzothiazole, 5-iodobenzelenazole, 6-iodobenzothiazole, 6-bromobenzothiazole, 5-bromobenzoxazole or a 5-iodobenzoxazole ring and the like;

Z, Z = hydrogen, alkyl with preferably up to 3 carbon atoms or alkoxycarbonyl groups with preferably up to

1 2

4 carbon atoms, Z and Z can also be used to complete a 5- or 6-membered ring are required methylene groups;

Y = 0, S, Se, -CH = CH-,> N-alkyl,> N-aryl; Anion = any anion, e.g. halide such as chloride, bromide, or iodide, perchlorate, sulfate, methyl sulfate, p-toluenesulphate and the like, the anion is omitted, if R contains an acidic group in anionic form,

so that a betaine is present; , __ _{Λ A} _ * 209810/0773

A-G 691 - 5 -

O, 1, 2;

the ring members required to complete an isocyclic or heterocyclic ketomethylene ring; come into question, ι the ketomethylene rings customary in cyanine chemistry, such as, for example those from the rhodanine series, such as 3-ethylrhodanine, 3-allylrhodanine, 3-cyclohexylrhodanine, those of the 2-thio-2,4-oxazolidinedione series, such as 3-ethyl-2-thio-2,4-oxazolidinedione, those of the thiohydantoin series, such as l, 3-dimethyl-2-thiohydantoin, l-methyl-3-phenyl-2-thiohydantoin, those of the barbituric acid or thiobarbituric acid series, such as 1,3-diethyl-thiobarbituric acid, 1,3-Diphenylthiobarbituric acid, those of the isoxazolone, the oxindole, the 2-thio-2,5-thiazolidinedione, the 2,4-imidazolidinedione series or the following Structural formulas marked ketomethylene rings:

Q = the one to complete a 5- or 6-limb Heteroringes required members, the heterocyclic group can be a fused benzene or naphthalene ring and contain further substituents; Possible ones are those customary in cyanine chemistry Heterocycles such as those of the thiazole series

A-G 6Ql

209810/0773

BATH ORIGINAL

(e.g. thiazole, 4-methylthiazole, 5-methylthiazole, 4,5-dimethylthiazole, 4-phenylthiazole, 5-phenylthiazole, 4,5-diphenylthiazole, etc.), those of the benzothiazole series? (e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzthiazole, 7-chlorobenzothiazole, 6-bromobenzthiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzthiazole, 5,6-methylbenzthiazole, 4-phenylbenzthiazole, 5-phenylbenzthiazole, 6-phenylbenzthiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 4-methoxybenzthiazole, 5-methoxybenzthiazole, 6-methoxybenzthiazole, 5-Äthoxybenzthiazol, 6-Äthoxybenzthiazol, 5,6-Dimethoxybenzthiazol, 5,6- Methylenedioxybenzthiazole, 5-diethylaminobenzothiazole, 6-diethylaminobenzothiazole, 5-carboxybenzthiazole, 5-sulfobenzothiazole, tetrahydrobenzthiazole, 7-oxotetrahydrobenzthiazole, etc.), those of the naphthothiazole series, those of the naphthothiazole, 2-thiazole, 2-thiazole, 2-thiazole, 2-thiazole, 2-thiazole, 2-thiazole, 2-thiazole series (e.g. d_7thiazole, 5-methoxynaphtho / _ "" 2, l-d_7thiazole, 5-ethoxynaphtho / ~ 2,1-dJT "thiazole, 7-methoxynaphtho / ~ 2, l-d__7thiazole, 8-methoxynaphtho £ ~ 1, 2-d_7thiazole, etc. .), those of the selenazole series (eg 4-methylselenazole or 4-phenylselenazole) those of the benzoselenazole series he (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5,6-dimethylbenzoselenazole, 5-hydroxybenzoselenazole, 5-methoxybenzoselenazole, tetrahydrobenzoselenazole, etc.), those of the naphthoselenazole series (e.g. naphtho / "" l, 2-d_7tho / "l, 2-d_7thelenazole -d_7selenazole), those of the oxazole series (e.g. oxazole, 4-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, etc.), those of the benzoxazole series (e.g. benzoxazole, 5-chlorobenzoxazole, 6-chlorobenzoxazole, 5,6-dimethylbenzoxazole, 5 -Phenylbenzoxazole, 5-hydroxybenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 6-dialkylaminobenzoxazole, 5-carboxybenzoxazole, 5-sulfobenzoxazole, 5-sulfonamidobenzoxazole, 5-ß-carboxyviny series (eg 1,2-d_7oxazole, naphtho / "2, l-d___ 7oxazole or naphtho /""2,3-d__7oxazoli those of the imidazole series (e.g. 1-methylimidazole, l-ethyl-4-phenylimidazole, l-butyl-4,5-dimethylimidazole etc.), those of the benzimidazole series (e.g. 1-methylbenzimidazole, l-butyl-4-methylbenzimidazole, l-ethyl-5,6-dichlorobenzimidazole, l-ethyl-5-trifluoromethylbenzimidazole, etc.), those of the naphthimidazole series (e.g.

AG 691 - 7 -

209810/0773

l-methylnaphtho / ~ 1,2-d__7imidazole or l-ethylnaphtho / "" 2,3-d__7imidazole) those of the 3,3-dialkylindolenine series (e.g. 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3 -Dimethyl-5-methoxyindolenine, etc.), those of the 2-pyridine series (e.g. pyridine, 3-methylpyridine, 4-methylpyridine, 5-methylpyridine, 6-methylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 3,6 -Dimethylpyridine, 4,5-dimethylpyridine, 4, β-dimethylpyridine, 4-chloropyridine, 5-chloropyridine, 6-chloropyridine, 3-hydroxypyridine, 4-hydroxypyridine, 5-hydroxypyridine, 6-hydroxypyridine, 3-phenylpyridine, 4-phenylpyridine , 6-phenylpyridine etc.), those of the 4-pyridine series (e.g. 2-methylpyridine, 3-methylpyridine, 2,3-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 2-chloropyridine, 3-chloropyridine, 2 -Hydroxypyridine, 3-hydroxypyridine, etc.), those of the 2-quinoline series (e.g. quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline , 6-hydroxyquinoline, 8- Hydroxyquinoline, 5-0xo-5,6,7,8-tetrahydroquinoline, etc.), those of the 4-quinoline series (e.g. quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), those of the isoquinoline series (e.g. isoquinoline or 3,4-Dihydroisoquinoline), those of the thiazoline series (for example thiazoline, 4-methylthiazoline, etc.) and also those of the pyrroline, tetrahydropyridine, thiadiazole, oxadiazole, pyrimidine, triazine or benzothiazine series. The Heterocyc li's rings and aryl groups may be further substituted in any desired manner, for example by further alky! Groups of preferably up to 3 carbon atoms, such as methyl or ethyl, halogen such as chlorine, bromine, iodine or trifluoromethyl group, hydroxyl, alkoxy having preferably up to 3 carbon atoms such as methoxy or ethoxy, hydroxyalkyl, alkylthio, aryl such as phenyl or aralkyl such as benzyl, amino, substituted amino and the like.

For example, the following compounds are suitable:

AG 691 . - 8th -

209810/0773

C ₂ H ₅

CH

2 '' 5

Br

CH ₃ Y-CH = C-CH

CH: N
CH ₃

CH ₃ SO ^

CH

2 ⁿ 5 CH

₂ Π 5

Br

₄ JY ^ ^s y-CH ^ C H-CH = C H-CH = f- ^C

CH

C ₉ H ι ₂ Π5

Tos.

A-G 691

209810/0773

V-CH-C-CH = f NW N

CH-

CH-

Jy ^ Y ^b "j) -CH ^ CH

⁰ VC H = CH-CH = f ^ Y

C ₂ H ₅

CH

2 ^ΓΙ 5 Br

NWNC ₂ H ₅ C ₂ H ₅

Tos

A-G 691

- 1 O - 209810/0773

H = CH-CH-CH ₂ H ₅ C

Tos

■ J

CH
O

OH

CH- / 3 ° HO J

Cl

CH
O

OH

Cl

CH

N L-O

OH

0,

16 fySy _CH r \

HO ^J

A-G.691

- 11 -

209810/0773

> CH

Cl

S = f °> C H

OH

Cl

C ₂ H ₅ CH,

, Cl

HO Cl

CH

Cl

OH

Cl

A-G 209810/0773

CH.

CH
O

OH

NH
C ₂ H ₅

OH

Br Tos

CH = CH- / VOH

Tos.

Cl

Y-CH = CH- /

C ₂ H ₅

'Se ^ -CH = CH ^ (VO H C ₇ H

2 ⁿ 5

Cl

Tos

A-G 691

- 13 -

209810/0773

29

Cl

TrCH-CH NW

CHx

OH

Cl

30th

NW Λ

Tos'

31 Br

= C H

(+) ₂ M ₅ Tos)

32

Cl

Cl '

Y-CH = CH- / Y-OH Tos

[VJW

C ₂ H ₅

NW

OH Tos

A-G

- 14 209810/0773

35

H ₅ -SO ^

C, H

₂ π ₅

36 H ₅ CO

H ₅ C CH ₃

OH r H ₅ -SO ^

C ₉ H,

HO Br

C ₂ H ₅ -SO,

C ₂ H ₅ -SO ₄ ¹

AG 209810/0773

I) T ⁰ VCH = CH CH _x

OH

2U42054

"CH

NW C ₂ H ₅

OH

CH -SO ^l

^ 2 5 ^OW 4

V NW

4 H ₅

OH

C ₂ H ₅ -SO, ¹

F ₃ C

f \ | WC ₂ H ₅

C ₂ H ₅

CF,

A-G

- 16 209810/0773

CH-CH = CH

IN THE

₃ CH = CC H = f

9
CH-OH

CH-SOi " ¹

CH:

ei dp <

CH-CH

■ OH

CH

CH

C ₂ H ₅

^s γ-CH = CC H = f ^S NW N

NW

f N

C ₂ H ₅

SO ₂
NH-CO-CH ClO

A-G 691

- 17 -

209810/0773

The mono-, tri- and pentamethine cyanines of the formula I can be synthesized by known methods, see e.g. F.M. Hamer (The Cyanine Dyes and related Compounds ", 1964. The dyes of the formulas H-V are obtained from Condensation of 2-methyl quaternary salts of heterocyclic bases or of ketomethylene compounds with the corresponding aldehydes in solvents such as alcohol, pyridine or glacial acetic acid with the addition of a base such as triethylamine or piperidine.

The production of the connections 17 and 28 is described in detail below. The remaining connections are in analog Way received.

Connection 17 :

2.0 g of 1,3-diethylthiobarbituric acid are refluxed for 5 minutes with 3 »7 g of 3,5-diiodo-4-hydroxybenzaldehyde in 30 ml of glacial acetic acid with the addition of 3 ml of piperidine. The mixture is cooled, the dye is filtered off with suction and recrystallized from methanol. This gives 3.6 g of the dye of mp .: 248 ⁰ C (dec.).

Verbi ndun g 28;

4.0 g of 2-M3thyl-3-ütLyl-benzselenazole tosylate are heated for 15 minutes on the steam bath with 3.7 g of 3,5-diiodo-4-hydroxybenzaldehyde in 50 ml of alcohol with the addition of 2 ml of triethylamine. The dye precipitates after a short time. The mixture is cooled, the dye is filtered off with suction, washed with alcohol and recrystallized from dimethylformamide. 3.7 g, mp .: 237 ⁰ C (dec.).

The image-forming compounds are photosensitive or transferable in the temperature range between 80-200 ° Exposure to exposure with the above compounds reacting reducing agents suitable as the known photographic Developer substances. The following reducing agents, for example, are particularly suitable:

209810/0773

AG 691 - 18 -

L. Phenols and naphthols , in particular benzenes and naphthalenes, which contain at least two aromatic hydroxyl groups, which can be partially etherified, or those which have a hydroxyl and an ami io- or substituted amino group, in benzene derivatives in para- or ortho- Position are substituted, e.g. the compounds listed in Table 1:

Table 1

1-hydroxy-4-methoxynaphthalene 1-hydroxy-4-ethoxynaphthalene 1-Hydroxy-2-methyl-4-methoxynaphthalene 4,4'-dimethoxynaphthalene-1,1'-dihydroxy-2,2'-binaphthyl 1,4-dihydroxynaphthalene 1-hydroxy-4-aminonaphthalene 1,2,3-trihydroxy-5-acetylbenzene, 3,4,5-trihydroxybenzoic acid methyl ester Ethyl 3,4,5-trihydroxybenzoate, 1,2,3,4-tetrahydro-8-hydroxyquinoline l- / ~ 2-methylsulfonamidoethyl_7-l, 2,3,4-tetrahydro-6-

hydroxyquinoline 4-methylaminophenol
4-isopropylideneaminophenol 4-aminophenol

4-hydroxyaniline methanesulfonic acid 4-hydroxy-3-methylaniline methanesulfonic acid 1-hydroxy-4-propoxynaphthalene.

Reference is also made to those described in German patents 159 758, 1 200 679, 1 203 129 and 1 203 605 Aminophenol developer.

2. Pyrazolidone (3) derivatives of the following formula:

^X CC =

^R 9 ^χ ί ¹

R ₈ 2098 10/0773

AG 691 - 19 -

wherein Ro is hydrogen, alkyl or aryl which may be substituted for example with lower alkyl, alkoxy eggs is halogen, R ₇ is hydrogen and Rg, R _10, R _11, R ₁₂ ^represents hydrogen, alkyl, aryl, or a substituted alkyl or Aryl group.

The compounds given in the following table have proven to be useful:

Table 2

l-phenyl-3-pyrazolidone, l-m-toluyl-3-pyrazolidone, l-p-toluyl-3-pyrazolidone, l-phenyl-4-methyl-3-pyrazolidone, l-phenyl-5-methyl-3-pyrazolidone, 1 ^ -Dimethyl ^ -pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, l-phenyl ^^ - dimethyl ^ -pyrazolidone, l- (3-chlorophenyl) -4-methyl-3-pyrazolidone, l- (4-chlorophenyl) -4-methyl-3-pyrazolidone, l- (3-chlorophenyl) -3-pyrazolidone, l- (4-chlorophenyl) -3-pyrazolidone, l- (4-toluyl) -4-methyl-3-pyrazolidone, 1- (2-toluyl) -4-methyl-3-pyrazolidone, 1- (4-toluyl) -3-pyrazolidone, l- (3-toluyl-3-pyrazolidone, 1- (3-toluyl) -4,4-dimethyl-3-pyrazolidone, 1- (2-trifluoroethyl) -4,4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone.

The above compounds can be prepared according to the procedures described in U.K. Patents 679,677 and 679,678 are prepared, which are accessible by reacting acrylonitrile derivatives with the corresponding hydrazine compounds "Phenimines" are saponified to give the 3-pyrazolidones.

2098 1 07 077

A-G 691 - 20 -

Furthermore, 3-pyrazolidones can be prepared by the process described in British patent specification 703 669, with the end products are obtained by direct condensation of esters of acrylic acid or their derivatives with hydraζinen. This process is particularly suitable for reactions with hydrazine itself. The 3-pyrazolidones of oily consistency can be converted into salts, e.g. hydrochloride, sulfate or 1,5-naphthalene disulfonate, as crystalline compounds obtained. The representation of 4,4-dialkyl-3-pyrazolidones is in the US patent 2 772 282. There are 2,2-dialkyl-ß-chloropropionic acid chlorides reacted with hydrazines.

The 3-pyrazolidones can be used as free bases or in the form of their salts.

3. N, N-dialkyl phenylenediamine derivatives, in particular those whose alkyl groups preferably contain up to 3 carbon atoms and whose phenylene nucleus can be substituted by alkyl or alkoxy groups.

The free primary amino group can be blocked, for example in the form of a Schiff base by reaction with Aldehydes, especially benzaldehyde or a sulfomethyl group, which can be introduced by a Mannich reaction. The phenylenediamine derivatives with a blocked primary amino groups are particularly suitable insofar as they can be used to easily produce stable layers permit.

The compounds given in the following table have proven to be useful:

Table 3:

N, N-diethyl-p-phenylenediamine sulfate, N, N'-dibenzylidene-p-phenylenediamine N, N-diethyl-N ^f -sulfomethyl-p-phenylenediamine

- ²¹ - 209810/0773

N, N-Dimethyl-N * -sulfomethyl-p-phenylenediamine ^ - U 4 2 0 5 3-methyl-4-suifomethylamino-N _} N-diethylaniline N-benzylidene-N ', N' -diethy1-p-phenylenediamine 3 -Methoxy-4-sulfomethylamino-N, N-diethylaniline.

The image-forming substances of the above type are known per se. The production is from the German patent specifications 1 159 758 and 1 203 129 or the literature.

4. Pyrazolin-5-one derivatives

Pyrazolin-5-one derivatives in the 4-position are preferred contain at least one hydrogen or one 4-aminophenylamino group.

Pyrazolin-5-one compounds of the following are preferred Formula:

^R 16

R.

Ii

^R 13

where mean:

= (1) hydrogen, (2) saturated or olefinic unsaturated aliphatic group with preferably up to 6 carbon atoms, which can be substituted, e.g. with Phenyl as in the benzyl grouping, with cyano, with halogen, e.g. fluorine, with amino, whereby the amino group may in turn be substituted, e.g. alkylated amino groups, especially dialkylamino, the alkyl groups on the amino group being preferred contain up to 3 carbon atoms, (3) aryl, in particular a grouping of the phenyl series, the aryl ring may in turn be substituted, e.g., with alkyl

AG 691 -22 -

209810/0773

or alkoxy with preferably up to 3 carbon atoms, nitro, halogen, such as fluorine, chlorine or bromine, amino, substituted Amino groups, e.g. alkylated, (4) a heterocyclic one Group, e.g., benzthiazolyl or (5) cycloalkyl such as cyclohexyl or cyclopentyl;

R ₁ = (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group with preferably up to 6 carbon atoms, it being possible for the aliphatic group to carry further substituents, for example phenyl, as in the case of a benzyl or phenylethyl group, halogen such as fluorine, chlorine or bromine, alkoxycarbonyl, hydroxyl or alkoxy, (3) aryl, in particular a grouping of the phenyl series, where the aryl ring can be substituted, e.g. with alkyl or alkoxy with preferably up to 3 carbon atoms, ( with nitro, Halogen, such as chlorine or bromine, (4) a heterocyclic grouping, e.g. pyridyl, (5) cycloalkyl, such as cyclohexyl or cyclopentyl, (6) hydroxyl, where the hydroxyl group can be etherified, in particular with short-chain aliphatic radicals with up to 3 C- Atoms, (7) amino, it being possible for the amino group to be substituted, for example with alkyl, preferably with up to 3 carbon atoms, (8) alkoxycarbonyl with up to 5 carbon atoms;

R-15 = (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group having preferably up to 6 C-atoms which may be substituted, for example with phenyl, such as in the case of benzyl or phenylethyl groups, etc., with halogen, such as chlorine or bromine, with nitrile, alkoxy, alkoxycarbonyl or anilinocarbonyl, (3) aryl, in particular a grouping of the phenyl series, where the aryl ring can in turn be substituted, e.g. with alkyl or alkoxy with preferably up to 3 carbon atoms, nitro, nitrile, ( 4) Amino, it being possible for the amino groups to be substituted, for example with alkyl having preferably up to 3 carbon atoms, cycloalkyl, phenyl or acyl, in particular acyl groups of short-chain aliphatic carboxylic acids, (5) alkoxy preferably having up to 3 carbon atoms;

- ²⁵ - 2 0 9 8 10/0773

* 16 ⁼ hydrogen or a 4-aminophenylamino group or 4-dialkylaminophenylamino group.

In addition, R ₁ and R ₂ together can represent the ring members required to complete a 5- or 6-membered carbocyclic or heterocyclic ring.

Suitable compounds are listed in the following table:

Table 4:

Il

N,

Pyrazole R ₁₃ ^C 6 ^H 5
H 5-on No. ^C 6 ^H 5
Cyclohexyl 1
2 p-tolyl 3
4th m-chlorophenyl 5 2,5-diehlophenyl 6th 3-nitropheny1 7th 4-nitrophenyl 8th ^C 6 ^H 5
1-phenylethyl 9 ^C 6 ^H «5
^C 6 ^H 5
2-diethylaminoeth 10
11 -24 12th
13th
14th A-G 691

14th

NH,
CH,
CR-.
CH ^
CH ^
CH ^
CH ^

^l 3

cn-,

CH ₃
-COOC ₂ H ₅

^C 6 ^H 5
-CH ₂ COOC ₂ H ^

Pyridyl-4
CH,

H H H H H H H H H H H H H H

09810/0773

Pyrazoline ^R 13 ^R 14 -CH ₂ -Ci CH ₃ l- / ~ benzothiazolyl-2 7-3,4- ^R 15 5-on No. 2,4,6-trichlorophenyl CH ₃ CH ₃ H 15th 2,4,5-triehlophenyl CH ₃ -COOC ₂ H ₅ H 16 2-cyanoethyl ^C 6 ^H 5 CH ₃ H 17th 3,5-dimethylphenyl -COOC ₂ H ₅ H 18th ^C 6 ^H 5 OH H 19th 3-nitrophenyl CH ₃ CH ₃ 20th 3-aminophenyl CH ₃ CH ₃ 21 3-nitrophenyl CH ₃ Benzyl 22nd 2-ethoxyphenyl C ₆ H ₅ CH ₃ 23 ^C 6 ^H 5 C ₆ H ₅ CH ₃ 24 ^C 6 ^H 5 ^C 6 ^H 5 C ₂ H ₅ 25th ^C 6 ^H 5 -CH ₂ -CH P-CHp-CH ₂ ^- 26th ^C 6 ^H 5 CH ₃ -CH ₂ -CO-NHC ₆ H ₅ 27 ^C 6 ^H 5 -COOC ₂ H ₅ CH ₃ 28 ^C 6 ^H 5 τ C * XJ C! 29 3-nitrophenyl C ₂ H ₅ 30th ^C 6 ^H 5 -NHCOCH ₃ 31 ^C 6 ^H 5 -OC ₂ H ₅ 32 ^C 6 ^H 5 CH ₃ 33 34

dimethyl-4- / 4-diethylaminophenylamino_7-pyrazolin-5-one

35 l-Phenyl-3,4-dimethyl-4- / ~ 4-diethylaminophenyl-amino__ _< 7-pyrazolin-5-one

The pyrazolin-5-one derivatives are known from the literature Methods made. Reference is made, for example, to the monograph by R.H. and Wiley "Pyrazolones, Pyrazolidones and Derivatives" (1964) and the German patent specification 1,155,675.

The photosensitive layers contain at least one

2 Sensitizer in quantities of 10-300 mg / m

209810/0773.

and one or more image-constricting compounds in amounts of 0.02-0.5 g / m ". This concentration range has proven to be suitable proven, although it is of course also possible to work outside this concentration range. the Concentration essentially depends on the requirements of the respective reproductive process.

Particularly suitable combinations of the sensitizers with the image-forming reducing agents can be used can be found out by simple experiments. Suitable tests for this are described below. Around To achieve optimal results, the selection of the solvent or the one for the production of the photosensitive Layer used binder of importance. Particularly suitable combinations for the respective application of the components involved can be determined by the usual tests familiar to the average person skilled in the art will.

A sensitizer can be used to produce the photosensitive layer and image-forming compound suspended or dissolved in solvents and mixed with a binder be applied to the substrate.

The usual natural or synthetic film-forming polymers are suitable as binders for the light-sensitive layer, for example proteins, especially gelatin, cellulose derivatives, especially cellulose ethers, cellulose esters or carboxymethyl cellulose, alginic acid and derivatives thereof, starch ether or galactomannan, also polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate or wholly or partially saponified polyvinyl acetate or "copolymers of vinyl acetate, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters _f polymethacrylate, polyethylene, among others

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The photosensitive layers can be applied as self-supporting layers or on a support be applied. Suitable substrates are e.g. paper, in particular baryta-coated or laminated paper, cellulose ester, e.g. cellulose triacetate, polyester, especially based on ethylene terephthalate, glass, etc.

The image receiving material preferably consists of an image receiving layer, which is applied to a suitable substrate. Both as a binder for the image receiving layer, As well as the support, essentially the same substances are suitable as those described above for the photosensitive Material have been described.

When selecting the binders for the light-sensitive layer and the image-receiving layer, it is important to ensure that: that the layers do not stick together in the warmth. However, these difficulties are different from other known transfer methods, e.g. the silver salt diffusion process or heat development process, known and easily solved using the experience in these known areas.

The image-receiving layer contains compounds which, under the conditions of the process according to the invention, are not or only to the smallest possible extent to visible light should be sensitive and those with the transferred image-forming compounds to form colored products react. A variety of compounds have been found suitable for this purpose. These connections belong chemically in the most diverse classes, so that a uniform classification in chemical terms is not possible is. Useful compounds or combinations of an image-forming compound used in the photosensitive Layer is arranged, and the reactant for the reaction providing the image dye in the image receiving layer however, they are sufficiently defined by manual tests that are easy to carry out for the average person skilled in the art. So

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the two reactants must react with brief heating of a few seconds to a temperature between about 80 and 200 ⁰ C to form a stable image dye. In order to select suitable image-forming compounds, a second test is then required, which is intended to show whether the image-forming compound reacts sufficiently quickly in the presence of the sensitizer on exposure that heating of the mixture thus exposed together with the reaction partner of the image-receiving layer no longer produces a colored compound .

The following classes of compounds, for example, are suitable as reaction partners in the image-receiving layer for the image-forming compounds:

1. Heavy metal compounds, especially of metals of III. to V main group as well as the I., II. and VI. until VIII. Subgroup of the periodic table of the elements, e.g. compounds of the following heavy metals: cadmium, Mercury, iron, cobalt, nickel, copper, silver, gold, bismuth or thallium. Salts of these are particularly suitable Metals with long-chain aliphatic carboxylic acids, e.g. nickel stearate, cobalt palmitate, iron stearate, the Addition compound of bismuth nitrate with amines, e.g. triethanolamine. Silver compounds have proven to be particularly useful proved to be largely insensitive to light under the conditions of the copying process according to the invention are, for example, the silver salts of aliphatic as described in British Patent 1,111,492 Carboxylic acids with a thioether grouping or silver salts of long-chain fatty acids, such as silver behenate, silver palmitate, Silver stearate, etc.

When using the heavy metal compounds mentioned above, brown to black copies are generally obtained. That Image consists of the metal in question and / or a reaction product of the transferred image-forming compound.

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2. The image-receiving layer can also contain oxidizing agents and dye components which ^{react imagewise with the transferred image-generating compound c 1} irch oxidative coupling to form dyes, for example the coupling components known in color photography which couple with oxidized phenylenediamine derivatives to form dyes, or compounds which in their oxidized form under oxidizing conditions, for example with the pyrazolin-5-one compounds, form colored coupling products. Suitable reaction partners are, for example, oxidation products of p-phenylenediamines or their derivatives, which form azomethine dyes with the pyrazolin-5-one compounds, as are known from color photography.

3. Diazonium salts with the transferred reducing agents, e.g. the aminophenols, aminonaphthols, phenylenediamine derivatives or pyrazolin-5-one compounds react to form a colored product. In principle, this corresponds to Reaction of those used under the known photographic diazotype process.

4. Leucophthalocyanines are also suitable as reactants for the reaction which provides the image dye.

As far as leuco phthalocyanines are not made from finished phthalocyanines have been or could be produced, they are also referred to as phthalocyanine precursors. This expression for example, in the article by B.R.A. Brooks, J.G. Burt, B.F. Skiles and M.S. Whelen, J.Org.Chem., 24, p. 383 (1959) was used. In the relevant chapter of Ulimann's Encyklopadie der technischen Chemie, 3rd edition, 13th volume, the designation "Phthalocyano Metal Complexes" for the same Types of substances used for which the term "leuco-phthalocyanine" is used in the present context. The last The expression mentioned is explained, for example, in US Pat. No. 2,772,285. It only relates there to the leuco copper phthalocyanine, but also applies accordingly

209810/0773

for the corresponding complexes with other metals forming phthalocyanines. According to this, leuco phthalocyanines are colorless or only slightly colored products in which the phthalocyanine structure is already fully formed and which can be converted into phthalocyanines by a reduction process. In this reduction process, components that form the leuco-phthalocyanine molecule can optionally be split off at the same time contains bound beyond that of the phthalocyanine. The production of such leuco phthalocyanines can e.g. by first adding a phthalocyanine, e.g. metal-free phthalocyanine or CuPc (Pc = phthalocyanine), NiPc, CoPc or ZnPc, and then provides this with additional ligands under oxidative conditions or by not getting a reaction mixture which is per se suitable for the preparation of a phthalocyanine up to that for it required temperature or by doing this to the Phthalocyaniri formation eliminates the required reduction potential.

Metal-containing leuco phthalocyanines are particularly suitable, since the metal-free ones are relatively unstable. Very cheap are the very stable and little colored leuco cobalt phthalocyanines.

Special mention should be made of leuco-cobalt phthalocyanines, as described in the Zeitschrift für Angewandte Chemie, 68, p. 145 (1956), such as, for example, the phthalocyanine-cobalt-lühylenediamine complex. Instead of ethylenediamine, other diamines or polyamines can be incorporated as ligands, such as propylenediamine = · (1,2) and - (1,3), monoäthylpr opylenediamine- (1,3), hydroxyethylethylenediamine, N-methyl-N- ß-hydroxyethylpropylenediamine, N, N ^f -diethylethylenediamine, H, N ~ di- (ß-aminoethyl) -ethylenediamine, N, N'-di- (ß-aminoethyl) -ethylenediamine _f N, N-di- / ~ "ß - (ß-aminoethyl) -aminoäthyl__7-aniin- or monoamines, such as 3- (2-Äthylhexyloxy) -propylamin- (1) or stearylamine The solubility properties of the corresponding Leuco-CoPc depend on the type of built-in amine.

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In another embodiment of the invention Process do not need partners for a dye-forming reaction in the image receiving layer at all. This applies e.g. for the imaging phenols or naphthols that are produced when heated by themselves or in the presence of atmospheric oxygen provide sufficiently colored compounds. In this case, plain plain paper can be used as the image receiving material be used.

The image receiving layers can besides the actual image forming Reaction partners contain other additives that favorably influence the color tone, contrast, stability, etc. of the copy. Such image receiving layers are already known and, for example, in German Auslegeschriften No. 895 101, 1 003 577, 1 159 758, 1 004 043 and 1 165 410, the Dutch patent specification 277 086 and the Belgian patent specification 614 064 and 609 057.

The image-receiving layers can also use white pigments such as zinc oxide, silicon dioxide or titanium dioxide as fillers To improve the whiteness and to influence the tendency of the layers to stick, as well as to improve the storage stability of terpene resins and contain organic acids. Such image receiving layers are in the American Patent Nos. 3,074,809 and 3,107,174.

The color tone of the resulting images can be e.g. with connections the 1- (2H) -phthalazinone series affect such Toners are described in U.S. Patents 3,080,254 and 3,446,648. Additives have also proven to be cheap which accelerate the reduction reaction in the image receiving layer. For this purpose, e.g. sterically hindered phenols, e.g. 2,6-di-tert-butyi-p-cresol suitable. Such connections are described in US Pat. No. 3,218,166. Furthermore, the image tone and density can be reduced certain metal salts such as copper (II) stearate improved will. Such metal ion image intensifiers and their use are described in German Auslegeschrift 1,572,209.

- ³¹ - 209810/0773

For exposing the photosensitive layers according to the invention the light sources customary in reproduction technology, such as mercury lamps, iodine quartz lamps or incandescent lamps, can be used. The spectral sensitivity of the light-sensitive material depends on the nature of the dye or the Dye reducing agent combination.

The exposure can take place either in contact, optically or in reflex.

The transfer of the image-forming compounds from the unexposed areas of the light-sensitive layers to the image-receiving layer takes place in the heat at temperatures between 80 and 200 ^° C. The heating can take place, for example, by guiding the exposed light-sensitive layer in contact with the image-receiving layer over hot plates or rollers or also by irradiation with UR light. The most favorable temperature and heating time naturally depend on the nature of the image-forming compound; it can be determined by a few simple experiments.

After a modification of the material according to the invention, it is also possible to use the image-receiving layer and the light-sensitive Unite layer on a carrier. In this case it is necessary to use a transparent support, on top of that the image-receiving layer, e.g. a layer made of a copolymer of styrene and isobutylene silver behenate semi-soap dispersed, and to apply the photosensitive layer, e.g. an ethyl cellulose layer, to the image-receiving layer, which contains the sensitizer and the reducing agent.

By combining the dyes to be used in the manner according to the invention with the photoreducible dyes mentioned, for example, in American patent specification 3,094,417, such as erythrosine, the sensitivity of these light-sensitive layers can advantageously be increased or in a manner dependent on the absorption of the compounds according to the invention other spectral regions are expanded.

-32- 209810/0 773

Photosensitive material:

The following casting solution is applied to a layer of glassine paper:

30 mg of dye no.

50 mg of 1-hydroxy-4-methoxynaphthalene

2.5 g ethyl cellulose (5% dissolved in butanone-2) 150 ml butanone-2

The layer is dried in the usual way.

The image receiving material is prepared by grinding for 6 hours

2.1 g of silver behenate semi-soap

1.66 g terpene resin

0.86 g of 1- (2H) -phthalazinone

4.8 g zinc oxide

0.56 g silica gel

0.37 g of 2,6-di-tert-butyl-4-methylphenol

0.034 g of tetrachlorophthalic anhydride

15 g of an 8% ethyl methacrylate solution in pentanone-3

80 g of a 1.5% polyvinyl acetate solution in butyl acetate

30 g of butyl acetate

in a ball mill, drawing on paper and drying.

The dried layer contains approx. 0.2 g silver per m.

Processing :

The photosensitive material is exposed behind a γ 2 wedge for 5 minutes with an iodine quartz lamp of 1000 watts from a distance of 30 cm.

The exposed layer is then brought into contact with the image receiving layer and ^{heated to a temperature of 125 °} C. for 10 seconds, or processed in a commercially available heat development device.

For comparison, the following non-halogenated compounds are included in Table 5:

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Comparative dye ;

Y-CH = CH-CH -f

N ( ₊ ) r

CH:

CH:

To s.

O ⁵ V-CH = CH-CH

C ₂ H ₅

C-)

> -CH = CH- / ~ \ -

OH Cl

C ₂ H ₅

C ₂ H

₂ H ₅

H ₅ Q "'

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I. A. Table 5 23 2042054 Dye number, B. 24 Levels ΫΖ Comparison f. C. Levels Vz dye no. 25th 4th η D. 26th 1-2 ti - 27 4th η - 28 4th 1 - 29 4th 2 1-2 30th 5 3 6th 31 1 4th 3 32 11 VJl 3 33 7th 6th 7th 34 6th 7th 11 35 5 8th 5-6 36 6th 9 1-2 37 5 10 2 38 9 11 1 39 2-3 12th 6th 40 10 13th 2 41 12th 14th 6th 42 9 15th 1 43 3 16 2 12th 17th 2 12th 18th 5 19th 7th 20th 2 21 2-3 22nd 4th Example 2 3

Photosensitive material:

The following casting solution is applied to a layer of glassine paper: 30 mg of compound 17

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50 mg of 1-hydroxy-4-methoxynaphthalene 2.5 g of ethyl cellulose
150 ml of ethyl acetate

The layer is dried in the usual way.

Processing ;

The photosensitive material is transparent through a positive Template for 30 seconds with a normal incandescent lamp (tungsten filament) of 1000 watts at a distance of 5 - 10 cm exposed.

Instead of a transparent template, a text printed on conventional paper can also be used as a template. With the reflex exposure required here, times between 15 and 25 seconds are required for the exposure under otherwise equal conditions required.

Subsequently, the exposed layer is in contact with the Brought the image-receiving layer described in Example 1 and the layers are for 5-20 seconds at a temperature of Heated to 125 ° -l40 ° or processed in a commercially available heat generator.

A sharp, positive black copy of the original is obtained.

Instead of the connection 17 and instead of the above image-forming Connection can also be used in other combinations. The results are in Table 6 below compiled:

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Tabel

Dye no.

Image-generating compound amount in color of the

mg copy

17 5

30 5

30 30

30th

30th

30th

1-hydroxy-5-methoxynaphthalene Link 7 from table

»33 Il 1!

H 26 ""

I! 20 ""

1,2,3,4-tetrahydro-8-hydroxy

quinoline

1-phenyl-3-pyrazolidone

1-phenyl-5-methyl-3-pyrazolidone

N-benzylidene-N ', N'-diethyl-p-

phenylenediamine

1-phenyl-5-methyl-3-pyrazolidone

50 grey black 100 grey black 150 grey black 150 grey black 100 grey black 50 black-brown 50 dark brown 50 dark brown 50 dark brown 50 dark brown

Instead of the silver behenate used here in the image receiving layer other silver compounds, such as silver stearate or silver salts of octadecyl mercaptoacetic acid, 2-octadecylmercapto-5-carboxymethylmercapto-l, 3,4-thiadiazole, (as described in US Pat. No. 3,330,663), among others. The selection of the appropriate compounds is aimed depending on the intended use and the desired image color.

Example 3 Photosensitive Material:

A photosensitive layer is made from a solution of

mg of the compound

100 mg Ν, Ν-diethyl-N'-sulfomethyl-p-phenylenediamine 100 mg Na acetate
100 ml of ethanol
50 ml of a 1.5% solution of a cellulose ether

in ethanol by pouring onto paper and drying.

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2 0 9 8 10/0773

Image receiving material :

A layer is made from a solution of

1.5 g l-phenyl-3-methylpyrczolon- (5)

1 g sodium bromate 35 ml of water 15 ml of a 5% aqueous polyvinyl alcohol solution

by potting on paper and drying.

Processing :

Processing is as in Example 2. A red positive is obtained.

Example 4
Photosensitive material:

A photosensitive layer is produced as in Example 3 from:

30 mg of the compound

100 mg Ν, Ν-diethyl-N'-sulfomethyl-p-phenylenediamine 100 mg sodium acetate 100 ml ethanol

50 ml of a 1.5% solution of a cellulose ether in ethanol

Image receiving material :

A layer is made on paper as a carrier from:

150 mg Ν, Ν-diethyl-p-aminophenyl-diazonium chloride-

Zinc chloride complex 10 ml of water

5 ml of a 1.5% aqueous solution of a cellulose ether.

Processing :

Processing is as in Example 2. A brown positive is obtained.

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Example 5 Photosensitive material:

A photosensitive layer is made from a solution of 30 mg of the compound

100 mg of 1- (2,5-dichlorophenyl) -3-methyl-pyrazolin-5-one

2.5 g ethyl cellulose 150 ml ethyl acetate

The solution is applied in the usual way to a layer support made of glassine paper and dried.

Image receiving layer :

At a layer support of paper barytiertem the folgen- * de casting solution is applied:

5 g of 4-dimethylaminobenzenediazonium tetrafluoborate

1 g of saponin

1 g of polyoxyethylene hydroxyethyl cellulose

100 ml of water

Processing :

It is processed as described in Example 2. A positive red image of the original is obtained on a gray background.

Example 6

Photosensitive material as in Example 1. |

Image receiving material :

50 mg of a leuco-cobalt-phthalocyanine-stearylamine complex, prepared according to the instructions given below, are dissolved in 40 g of a 1.5% polyvinyl acetate solution in acetone and 26 g of a 4% strength cellulose acetate solution in acetone, poured onto paper and dried.

39-209810/0773

Processing ;

Processing is carried out as described in Example 2. A blue positive c.-is Originals is obtained.

The Leuco-CoPc used was obtained as follows:

50 g of a crude product prepared according to German patent specification 855 710, Example 1, were converted into the nitrate by treatment with concentrated nitric acid, as described in German patent specification 839 939. 16 g of the dried nitrate were boiled in 50 ml of mineral spirits with 15 g of stearylamine for 20 minutes, the mixture was diluted with 750 ml of mineral spirits, the resulting solution was ^{filtered at 100 °} C., stirred cold for a few hours and the product which had crystallized out was filtered off with suction and dried. The 27 g of reaction product obtained in this way were dissolved in boiling ethanol, the solution was stirred while cold, and the crystals were filtered off with suction and dried. 12 g of an orange-colored substance are obtained.

Instead of the l-hydroxy-4-methoxynaphthalene can be used as image-generating Compound with the same result also 50 mg of l-phenyl-5-methyl-3-pyrazolidone be used.

Example 7

Photosensitive material as in Example 1.

Image receiving material ;

An image receiving layer is made from

5 g ferric chloride
2 g nitrilotriacetic acid
30 ml of a 5% aqueous solution of polyvinyl alcohol.

The solution is neutralized with ammonia and poured onto paper.

Processing is carried out as described in Example 2. A blue-green positive is obtained.

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Example 8

Photosensitive material as in Example 1.

Image receiving material :

1 g of bismuth nitrate is mixed with 40 g of a 1.5% solution of polyvinyl acetate in acetone and

26 g of a 4% solution of acetyl cellulose in acetone Shaken in the vibrating mill for 6 hours.

The mixture is poured onto paper and dried.

Processing :

Processing is carried out as described in Example 2. A brown positive is obtained. Instead of bismuth nitrate in the Image receiving layer can also be 0.6 g of thallium (I) chloride or use 0.8 g of mercury (II) bromide with the same success.

Example 9

Photosensitive material as in Example 1. Processing is carried out as described in Example 2.

However, the image receiving material consists of ordinary writing paper. A positive blue-green image is obtained the template.

Example 10 "

Photosensitive material as in Example 1.

Image receiving material :

A solution of 5 g of copper (II) chloride in 75 ml of H ₂ O is mixed with ammonia until the precipitate formed is dissolved and then with 30 ml of 5% strength aqueous polyvinyl alcohol, poured onto paper and dried.

Processing is carried out as described in Example 2. A gray-green positive image of the original is obtained.

AG 691 - 41 -

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Example 11

In combination with other dyes, e.g. erythrosine, which has its sensitivity at 540 nm, the in the The following table lists the sensitivity of the light-sensitive material to the blue and red dyes Spectral range -.

Photosensitive material :

The following casting solution is applied to a layer made of polyester and dried.
30 mg of erythrosine

30 mg of dye no. See Table 7 below. 50 mg of 1-hydroxy-4-methoxynaphthalene

2.5 g of ethyl cellulose
150 ml of butanone

Processing :

To determine the spectral sensitivity of the photosensitive A set of interference filters was used. The filters are at the following wavelengths permeable:

350 nm, 390 nm, 405 nm, 435 nm, 480 nm, 505 nm, 515 nm, 540 nm, 550 nm, 570 nm, 590 nm, 605 nm.

The light-sensitive material is placed behind the interference filters with an iodine quartz lamp for 5 to 30 minutes, depending on the dye of 1000 watts exposed from a distance of 30 cm. The exposed material is then compared with the im Example 1 described image receiving layer brought into contact and in a commercially available heat development device processed.

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Table 7

Dye no _ Sensitivity at nm 515 , 540 d Erythrosine 9 540 , 505, 590 , 605 Erythrosine + 11 480 , 570, 515 , 540 nm Erythrosine + 17th 540 , 505, 590 , 605 nm Erythrosine + 26th 480 , 540, 605 nm nm Erythrosine + 28 350 , 590, 605 nm nm Erythrosine + 30th 540 , 590, 605 nm Erythrosine + 33 540 , 590, Erythrosine + 44 540 , 540 Erythrosine + 515

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Claims (31)

Claims: ^{n £ UO4} Process for the production of copies by imagewise exposure of a light-sensitive layer which contains a sensitizer and an image- ^{forming compound which can be transferred into an image-receiving layer at temperatures between 80 and 200 °} C., the image-forming compound being converted into a non-transferable compound at the exposed areas in the presence of the sensitizer Compound is transferred, bringing the exposed layer into contact with an image-receiving layer which contains compounds which react with the image-forming compound to form colored compounds, and heating the layers in contact to a temperature at which the image-forming compound from the unexposed areas of the photosensitive layer is transferred into the image-receiving layer, characterized in that a photosensitive layer is used which contains at least one halogenated polymethine dye of the following formulas: Anion ^v Anion ffHal in 209810/0773 204205 Hal HaL IY R Has "= ^r H Λ Ρ R ^ Hal T if 4-R Aniorv where mean: = Cl, Br, J Shark
R ¹ z ¹ , z ² = 1) a saturated or unsaturated aliphatic Group, 2) cycloalkyl, 3) aryl;
= Hydrogen, alkyl, aryl or cycloalkyl; = Hydrogen or hydroxyl, but at least one of the radicals is a hydroxyl group; = Hydrogen, alkyl, alkoxy, halogen, aryl; = Aryl, heterocyclic rings that too can be substituted;
= the ring members necessary to complete a benzo or naphtho ring which contains at least one halogen or one trifluoromethyl group; 1 2 = hydrogen, alkyl, alkoxycarbonyl, Z and Z can also the one to complete a 5- or 6-limb Ring required methylene groups mean; Y = 0, S, Se, -CH = CH -, - N-alkyl,> N ~ aryl; Anion = any anion; η = 0, 1, 2; D = the one to complete an iso- or heterocyclic Ketomethylene ring required ring members; Q = the one to complete a 5 ~ or 6-limb Hetero ringes required links. AG 691 - 45 - .2 09610/077 3 2. The method according to claim 1, characterized in that as Sensitizer, a polymethine dye is used which contains at least one iodine atom. 3. The method according to claim 1, characterized in that the polymethine dye of the following formula is used: CoH _c 4. The method according to claim 1, characterized in that styryl dyes which are different from hydroxy-3,5-diiodobenzaldehyde ^ derive to be used. 5. The method according to claim 4, characterized in that styryl dyes are used with a thiazole ring. 6. The method according to claim 1, characterized in that an l-hydroxy-4-alkoxynaphthalene is used as an image-enhancing compound is used. 7. The method according to claim 6, characterized in that the image-forming compound is l-hydroxy-4-methoxynapthalene is used. W 8. The method according to claim 1, characterized in that 1,2,3,4-tetrahydro-8-hydroxyquinoline is used as the image-forming compound. 9. The method according to claim 1, characterized in that a 3-pyrazolidone derivative is used as the image-forming compound is used. 10. The method according to claim 9 »characterized in that l-phenyl-4-methyl-3-pyrazolidone is used as the imaging compound. A-G 691 - 46 - 209810/0773 11. The method according to * claim 1, characterized in that a pyrazolin-5-one compound of the following formula is used as the image-forming compound: ^R 16 II " -R ^R 13 where mean: R-I-Z = (1) hydrogen, (2) saturated or olefinic unsaturated aliphatic group, (3) aryl, (4) a heterocyclic group, or (5) cycloalkyl; R -,. = (1) hydrogen, (2) a saturated or olefinic one unsaturated aliphatic group, (3) aryl, (4) a heterocyclic moiety, (5) cycloalkyl, (6) hydroxyl, (7) amino, or (8) an alkoxycarbonyl group; R-, 5 = (1) hydrogen, (2) a saturated or olefinic one unsaturated aliphatic group, (3) aryl, (4) amino, (5) alkoxy; ^R l £ ⁼ hydrogen or a 4-aminophenylamino group Rp, and RJ ^ can also mean the ring members required to complete a carbocyclic or heterocyclic ring. 12. The method according to claim 1, characterized in that an image receiving layer is used which is one under the conditions of the process does not contain light-sensitive heavy metal compounds. 13. The method according to claim 12, characterized in that an image receiving layer is used which is one of the Conditions of the process contains little or not light-sensitive silver compound. AG 691 - 47 _ 209810/0773 14. The method according to claim33, characterized in that an image receiving layer is used, the silver salts of a long chain aliphatic carboxylic acid with 8 to 24 Contains carbon atoms. 15. The method according to claim 13, characterized in that An image receiving layer is used which is a silver salt of an aliphatic carboxylic acid bound with a thioether group is substituted, contains. 16. The method according to claim 12, characterized in that an image receiving layer containing a toner is used. 17. The method according to claim 12, characterized in that an image receiving layer is used which is a steric contains hindered phenol. 18. The method according to claim 12, characterized in that the image receiving layer contains a white pigment. 19. The method according to claim 12, characterized in that the image-receiving layer contains a terpene resin. 20. The method according to claim 12, characterized in that the image receiving layer contains a metal ion image intensifier. 21. Light-sensitive photographic material with a light-sensitive layer which contains a sensitizer and an image-forming ^{compound transferable at temperatures between 80 and 20O 0} C, the image-forming compound being converted into a non-transferable reaction product in the presence of the sensitizer at the exposed areas characterized in that it contains one of the following formulas as a sensitizer: AG 691 - 48 - 209810/0773 ry T-CH = (C-CH) _n ^ v _ ^ - NWX ₄ Anion Hal ~ w ~ ^r: R * Hal Hal R * Hal anion ^ Hal Hal R ⁴ Y. ft ¹ f IJ R anion ¹ A-G 691 - 49 209810/0773 where mean: Hal = Cl, Br, J R = 1) a saturated or unsaturated aliphatic Group, 2) cycloalkyl,;) aryl; R = hydrogen, alkyl, aryl or cycloalkyl; R, R = hydrogen or hydroxyl, but at least one of the radicals is a hydroxyl group; R * w hydrogen, alkyl, alkoxy, halogen, aryl; R * aryl, heterocyclic rings that too can be substituted; X = diö to complete a benzo or naphtho ring, the at least one halogen or one trifluoromethyl group contains »necessary ring links; 12 12 Z, Z β hydrogen, alkyl, alkoxycarbonyl, Z and Z can furthermore represent the methylene groups required to complete a 5- or 6-membered ring ; Y * O ₁ S ₁ St, -CH ^ CH -, ^ N-alkyl, ^ N-aryl; Anion * tin any anion; η ■ O, 1, 2) D «dl» sw »Vtrvollttlivung tine» iio- oitr htttrocyclüthtn K * toatthyl * nringee Trfordtrlichen Ringglitdtr; Q - * I am entitled to ink 5- or 6-glitdrigtn hetero rings required links. 22. Material according to claim 2X, did by gtktnnitlehntt that al Contains a sensitive agent in polythene additives 1st »dtr alndtittn · tin Jodato» tnthtlt. 23. Htttrial »I Antyruch al» 4Uurth ithtniuitich »tt _f AtO dtr Polyetthinfmrbttoff dti ioagtndt» Poratl tnthalttn suffered -50- 209810/0773 BATH ORIGINAL 24. Material according to claim21, characterized in that
Styryl dyes derived from hydroxy-3,5-diiodobenzaldehyde are included. 25. Material according to claim 21, characterized in that Styryl dyes with a thiazole ring are included. 26. Material according to claim 21, characterized in that an 1-hydroxy-4-alkoxynaphthalene is used as the image-forming compound is included. 27. Material according to claim 21, characterized in that the image-forming compound is l-hydroxy-4-methoxynaphthalene is included. 28. Material according to claim 21, characterized in that the image-forming compound is 1,2,3,4-tetrahydro-8-hydroxyquinoline is included. 29. Material according to claim 21, characterized in that the image-forming compound is a 3-pyrazolidone derivative
is included. 30. Material according to claim 21, characterized in that the image-forming compound is l-phenyl-4-methyl-3-pyrazolidone is included. 31. Material according to claim 21, characterized in that ale image-absorbing compound is a pyrazolin-9-one compound the following formula is included. 209810/0773 where mean: FL, = (1) hydrogen, (2) saturated or olefinic unsaturated aliphatic group, (3) aryl, (4) a heterocyclic group, or (5) cycloalkyl; ^R l4 ⁼ ( ¹ ^ hydrogen, (2) a saturated or olefinically unsaturated aliphatic group, (3) aryl, (4) a heterocyclic grouping, (5) cycloalkyl, (6) hydroxyl, (7) amino or (8) an alkoxycarbonyl group; R ₁ Cy = (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group, (3) aryl, (4) amino, (5) alkoxy; "" 16 ^ hydrogen or a 4-aminophenylamino group R- ^ and R ₁ Z ₁ . can also mean the ring members required to complete a carbocyclic or heterocyclic ring. 209810/0773 AG 691 - 52 -