DE1950785C - Image recording material with a photo-crosslinkable layer - Google Patents

Description

The invention relates to an image recording material, consisting of a layer support and a light- crosslinkable layer applied thereon

(1) a cross-linkable polymer whose grids, which are capable of cross-linking, contain aldehydes are reactive, and

(2) a photosensitive crosslinking agent for the polymer, which when exposed to light filled up and its decomposition products cause the crosslinking of the polymer.

The surprising discovery lay in the invention based on that bostimmle heterocyclic compounds with a heterocyclic nitrogen atom which is substituted by a radical of the formula - OR is where R is an alkyl, aryl or acyl radical, outstandingly effective crosslinking agents for polymers with reactive groups, e.g., hydroxyl groups and amino groups.

The subject matter of the invention is thus based on ίο an image recording painting consisting of a Layer support and at least one light-crosslinkable layer applied thereon

It is well known that polymers with a wide variety of reactive radicals can be formed with the help of allow so-called crosslinking agents to crosslink. Typical known crosslinking agents consist of Aldehydes, e.g. B. from formaldehyde. The cross-linking dcs Polymers can be made immediately after the addition of the crosslinking agent. In cases where a Quci crosslinking of the polymer at bare If the crosslinking agent is not added, the crosslinking can be achieved by adding external energy, for example by the action of light or heat. The cross-linked polymers are harder and more insoluble than the non-crosslinked polymers and cannot be removed from them cross-linked polymers e.g. B. separate in that an exposed layer containing the polymer treated with a solvent for the uncrosslinked polymer. It becomes a photographic one Recording material with a layer of a crosslinkable polymer and a crosslinking agents distributed therein irradiated image-appropriately, for example with light or heat rays, so the polymer is hardened in the areas in which the radiation occurs, so that for example an image can be created by washing out the uncured areas.

Photographic imaging materials in which the crosslinking of the polymers is effected by Supply of external energy takes place with the help of radiation-sensitive crosslinking agents, are z. B. from the French patent 1,411,746 and British patents 1,062,884 and 1,116,240. The known radiation-sensitive crosslinking agents are polycarboxylic acid azides, Disulfonyldiazides or quaternary diazoquinoline compounds. The one used to manufacture the Image recording materials used polymers have as reactive radicals z. B. Hydroxy, Amino, thiol or lactam residues on or are N-methylol ester or N-methylol ether derivatives of Acrylamide or methacrylamide polymers.

Disadvantages of the known recording materials of this type is that their photosensitivity leaves something to be desired that they are only to UV light are sufficiently sensitive or that the crosslinking agent is sensitized with a sensitizer Need to become.

The object of the invention is to provide an image recording material with a light-crosslinkable layer, which contains photosensitive crosslinking agents and against various forms of radiation energy is highly sensitive, for example to electron beams, UV light, the visible Light to infrared light, and does not require any additional sensitizer.

(1) a crosslinkable polymer, whose residues capable of crosslinking with aldehydes are responsive and

(2) a photosensitive crosslinking agent for the polymer, which when exposed to light disintegrates and its decomposition products cause cross-linking of the polymer, and is characterized in that it is a crosslinking agent with a residue

OR

contains one of the following formulas

4 — R «

OR

R ₁ Χ ^Θ II

OR

R ₄ - ^ ₀ ^ -R ₂ X ^e

^V N- '

OR

or

R,

q ₂ NOR ₅ -N

R.

Q ₉ 2X «IV

in which Z denotes the atoms required to complete an optionally substituted, 5- or ole-membered, heterocyclic ring, R denotes an optionally substituted alkyl, aryl or acyl radical, R ₁ denotes an optionally substituted methine or polymethine group with a terminal heterocyclic ring customary for cyanine dyes , an optionally substituted alkyl radical, an anilinovinyl radical, an optionally substituted aryl radical, a hydrogen atom, an aldehyde radical, an optionally substituted styryl radical or an acyl radical, R ₂ and R ₄ each a hydrogen atom or an optionally substituted alkyl or aryl radical, R ₅ an alkylene radical or alkylenoxy radical with 1 to

■ i carbon atoms in the alkylene chain or one reads the form

wtirin denotes s and ι each a number from I to H, ι / = 0 or I and R ₁₁ , an aryl radical, R ₈ an optionally substituted methine or polymethine group with a central heterocyclic ring customary for merocyanine dyes; an optionally substituted allylidene radical or an aldehyde radical, Q ₂ and Q ₀ the atoms required to complete a 5- or 6-membered heterocyclic ring and X ° a acidic ion.

Rio is preferably an arylene radical of the phenylene or naphthylene series. The heterocyclic ring represented by Z can optionally contain other have incondensed rings; d. H. polycyclic Be nature.

If R is an alkyl radical, it is preferred that this Has 1 to 8 carbon atoms and is substituted. lsi to the heterocyclic ring formed by Z. if another ring is condensed on, i.e. if a polycyclic ring is present, then R, in can be more advantageous Be a substituted or unsubstituted alkyl radical.

_{If R 1} in the given structural formula II represents a methine group with a terminal heterocyclic ring customary for cyanine dyes, the melhing group can be substituted or unsubstituted, for example substituted by an alkyl or aryl radical, and z. B. have one of the following structural formulas:

If Ri has the meaning of an optionally substituted one Styryl resles, this preferably has the formula

-CH = CH

wherein R _{2 is} a hydrogen atom, an alkyl radical with

ίο preferably 1 'to 8 carbon atoms, an aryl radical, preferably of the phenyl or naphthyl series or an amino group, including a dialkylamino group, for example a dimethylamino radical.

If R has the meaning of an optionally substituted alkyl radical, this preferably has 1 to 8 carbon atoms and consists for example from a methyl, ethyl or butyl radical, or, for example, from a sulfoalkyl radical, e.g. B. the

Formula - CH ₂ SO ₃ -, or an aralkyl radical, e.g. B. a benzyl or pyridinato-oxyalkylsalzrest, z. B. of the formula - (CH ₂ ) ₃ —O - Y, where Y is an optionally substituted pyridinium salt radical.
If R is an acyl radical, this preferably has the formula

—C — R “

- CH = - C (CH ₃ ) = - C (C ₁₁ H ₅ ) -
- CH = CH - CH = -

Heterocyclic rings customary for cyanine dyes, through which the methine group is terminated can, for example, in the book by M e s and Jones, "The Theory of the Photographic Process ", Verlag MacMillan, 3rd Edition, pp. 198 to 232, described.

If R _{1 is} an optionally substituted alkyl radical, this preferably has 1 to 8 carbon atoms.

If R _{1 has} the meaning of an optionally substituted aryl radical, this preferably consists of an aryl radical from the phenyl or naphthyl series, for example a phenyl, naphthyl or tolyl radical.

If R _{1 has} the meaning of an acyl radical, this preferably has the formula

-C-R

wherein R is hydrogen or an alkyl group having 1 to 8 carbon atoms.

If R _{1 has} the meaning of an anilinovinyl radical, this preferably has the formula

-CH = CH-N

wherein R _{3 has} the meaning of a hydrogen atom or an alkyl radical having preferably 1 to 8 carbon atoms.

in which R _{6 is} an alkyl radical having 1 to 8 carbon atoms or an aryl radical, preferably of the phenyl or naphthyl series, ie, for example, a methyl, ethyl, propyl, butyl, phenyl or naphthyl radical.

The 5- or o-membered heterocyclic ring completed by Z can, in addition to that in the ring, already existing nitrogen atom optionally contain at least one further hetero atom, for example an oxygen, sulfur, selenium or nitrogen atom. Preferably, Z is the one to complete a pyridine or quinoline ring required atoms.

The methine group represented by R ₈ may be a methine group as defined in connection with R ₁ . Terminal heterocyclic rings customary for merocyanine dyes are described, for example, in the aforementioned book by Me and Jones, "The Theory of the Photographic Process".

If R _{8 has} the meaning of an optionally substituted allylidene radical, this can, for example. wise from a Dicyanoallylidenrest, an Alkylcarboxyallylidenrest or an Alkylsulfonylally-

lidenrest exist, the alkyl groups of these radicals preferably having 1 to 8 carbon atoms.

If R ₂ and R ₄ are alkyl radicals, they preferably have 1 to 12 carbon atoms, in particular 1 to 4 carbon atoms. If R ₂ and R _{4 have} the meaning of aryl radicals, these preferably consist of aryl radicals of the phenyl or naphthyl series, that is, R ₂ and R ₄ can be, for example, methyl, ethyl, propyl, isopropyl, butyl, decyl or dodecyl radicals or phenyl, tolyl, naphthyl, methoxyphenyl, chlorophenyl or nitrophenyl radicals.

Q ₂ and Q ₉ are preferably those 5- or

o-membered heterocyclic ring, which stands for Cynninfurbslol'fe are typical and uui3er don already exist Nitrogen atoms may contain another heteroatom, for example an oxygen, Sulfur, selenium or nitrogen atom.

For example, X can be a acid anion, like es in cyanine dyes !! occurs, for example oin chloride, bromide, iodide, perchlorate sullamal, Thiocyanates p-toluene sulfomite, methyl sulfate or Tctrafluorobcrate anion.

The invention achieves that recording materials with light-crosslinkable layers are available which, according to the invention, by selecting one light-sensitive crosslinking agents contained in light sources of different spectral energy distribution can be adapted so that compared to known photo-crosslinkable layers an increased Photosensitivity is achieved. A case of a special spectral sensitizer is included not mandatory.

The crosslinking agents used according to the invention can be activated or broken down by the action of energy in the most varied of forms. Mention may be made: .elektromagnetische radiation, including radiation from the ultraviolet, visible and infnirof ^'> "He Percicbfi" spectrum, X-rays, electron beams and laser beams; 2. Wiirme and third printing!.

Preferably been crosslinking agents and the

used to break down the crosslinking agents

Radiation so coordinated that the

Crosslinking agent its maximum absorption in the

Possesses area of activating radiation.

The crosslinking agents used in the present invention become more electromagnetic

When exposed to radiation, they are destroyed by a kind of heterolytic cleavage of the nitrogen atom-oxygen atom bond, whereby they form an RO ^ ion, a dye base and a Siiureanion '. The RO ^u 'ion can then be broken down further to form an aldehyde and a hydrogen ion.

The aldehyde itself is the crosslinking agent and leads to crosslinking in those domains the polymer with which it is in contact,

The degradation mechanism that starts in the individual case depends somewhat on the structure of the network connection used. However, based on observations, the degradation is progressing for the most of the crosslinking agents made up of dyes when subjected to electromagnetic exposure Exposed to radiation (e.g. exposure to light) according to the following reaction scheme:

CH == CH - CH = C

O-CH ₃

hv

CH ₃ O ¹

CH ₃ O®

ClO ₄ ⁰

ClO ₄ ⁰

+ LJ-CH = CH-CH =

CH ₂ O + H ^Q

Crosslinking agents with an ionic or cationic radical produce an aldehyde on irradiation with a potential biting group. The use of such crosslinking agents makes it possible to color the cross-linked polymers easily with common cationic or anionic dyes, since the crosslinking agents, when irradiated, simultaneously crosslink the polymer and introduce it cause of acidic groups in the polymer.

The scope of action of such crosslinking agents results, for example, from the following reaction scheme, which breaks down a crosslinking agent with the formation of an anionic mordant describes:

CH ₃

OCH ₂ CH ₂ CH ₂ SO ₃ O
⁰ O ₃ SCH ₂ CH ₂ CHO + polymer

H® + ^e O ₃ SCH ₂ CH ₂ CHO

CH,

Polymer with acidic caustic residue

By using such crosslinking agents, for example, the absorption capacity of the Increase polymers for kaiionic dyes such as methylene blue.

In a corresponding manner, according to the invention, when appropriate crosslinking agents are used also form cationic pickling agents, for example according to the following reaction equation:

hv

2X®

Ν — CH ₂ (CH ₂ J _n CHO

® Ν — CH ₂ (CH ₂ J _n CH O + polymer polymer with a basic caustic residue

The use of such crosslinking agents thus makes the polymers more receptive to anionic ones Make dyes.

There are no cleavable connections if the group

—N— 'OR

Is part of an indole ring.

According to one embodiment of the invention, the image recording materials according to the invention contain one Crosslinking agent of one of the following formulas:

,. Qi ^

N CH-CHC-

OR

L = L

L = C (-CH = CH) NR ₃ X »(A)

N =

OR

C.
E.

Λ -C =

-NR ₃ X (B)

U--

OR

Q ₂ - / _

Φ = CH-CH C-

Q ₂ -

C (-CH = CH-IfTr-NR ₃ X <(D)

wherein R denotes an optionally substituted alkyl or aryl or acyl resl, R ₂ denotes an optionally present alkyl or aryl group of the meaning already given, R ₃ denotes an optionally substituted alkyl, acyl, alkenyl, aryl or alkoxy group, Qi, Q ₂ , Q ₃ and Q _{7 are} the atoms required to complete 5- or 6-membered heterocyclic rings, L is an optionally substituted one

65 methine group, D, E and J each represent a hydrogen atom or an alkyl or aryl radical, X ° an acid anion, G an anilino or aryl radical, g = 1 or 2, m - 1, 2 or 3 and η = 1, 2, 3 or 4.

According to a further particularly advantageous embodiment of the invention, the image recording material contains a crosslinking agent of the specified formulas, in which Qj, Q ₂ , Q ₃ and Q ₇ are the

Completion of pyridine or quinoline rings represent the atoms required.

Qii Q21 Ch <Q7 ^{un <} 3 Qg can be used for

stand the atoms that form

a thiazole ring, e.g. B. a thiazole, 4-methylthiazole, 3-ethylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4- (2-thienyl) thiazole, benzothiazole, 4-chlorobenzothiazole, 4- or

5 - nitrobenzothiazole, 5 - chlorobenzothiazole,

6 - chlorobenzothiazole, 7 - chlorobenzothiazole,

4 - methylbenzothiazole, 5 - methylbenzothiazole, 6 - methylbenzothiazole, 6 - nitrobenzothiazole,

5 - bromobenzothiazole, 6 - bromobenzothiazole, S-chloro-o-nitrobenzothiazole, 4-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 6-iodobenzothiazole -Äthoxybenzothiazol-, 5-Äthoxybenzothiazol-, tetrahydrobenzothiazole, 5,6-Dimethoxybenzothiazol-, 5,6-Dioxymelhylenbenzothiazol-, 5-Hydroxybenzothiazol-, 6-Hydroxybenzothiazol-, u-naphthothiazole, ji - naphthothiazole, / ί / ί - Naphthothiazol-, S-Metlioxy - ^ / if-naphthothiazol-, 5-ethoxy - ^ - naphthothiazol-, 8-methoxy-a-naphlhothiazol-, 7-methoxy - «- naphthothiazol-, 4'-methoxythianaphtheno-7 ', 6 ', 4,5-thiazole or a naphthothiazole ring substituted by a nilro radical;

an oxazole ring, e.g. B. a 4-MethyloxazoI-, 4-nitro-oxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethoxazole, 5-phenyloxazole, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 5- or 6-nitrobenzoxazole, S-chloro-o-nitrobenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazoi-, 4,6-dimethylbenzoxazole-, 5 - methoxybenzoxazole,

5 - ethoxybenzoxazole, 5 - chlorobenzoxazole,

6 - methoxybenzoxazole, 5 - hydroxybenzoxazole, 6-hydroxybenzoxazole, a-naphthoxazole, / f-naphthoxazole or one by a nitro radical substituted naphthoxazole ring;

a selenazole ring, e.g. B. a 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 5- or 6-nitrobenzoselenazole, 5-chloro-6- nitrobenzoselenazole, tetrahydrobenzoselenazole, «- naphthoselenazole, ^ -naphthoselenazole or a naphthoselenazole ring substituted by a nitro radical;

a thiazoline ring, e.g. B. a thiazoline, 4- methylthiazoline or 4-nitrothiazoline ring. a pyridine ring, e.g. B. a 2-pyridine, 5- methylene-2-pyridine, 4-pyridine, 3-methyl-4-pyridine or a pyridine ring substituted by a nitro radical;

a quinoline ring, e.g. B. a 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-chloro-2-quinoline, o-nitro-1-quinoline, 8-chloro-2-quinoline -, o-methoxy ^ -quinoline-, 8-ethoxy-2-quinoline. S-Hydroxy ^ -quinoline-, 4-quinoline-, 6-methoxy-4-quinoline-, o-Nitrcwt-quinoline-, 7-methyl-4-quinoline-, e-chloro- ^ quinoline-, 1-isoquinoline- , ■ o-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline or 3-isoquinoline ring; a 3,3-dialkylindolenin ring, preferably with

a nitro or cyano residue. z. B. a 3,3-dimethyl-5- or 6-nitroindolenine, 3,3-dimethyl-5- or 6-cyanoindolenine ring:
an imidazole ring, e.g. B. an imidazole, 1-alkyl- 'imidazole-, l-alkyl-4-phenylimidazole-, 1-alkyl-4,5-dimethylimidazole-, benzimidazole-, 1-alkylbenzimidazole-, 1-alkyl-5-nitrobenzimidazole- . 1 - aryl - 5,6 - dichlorobenzimidazole, 1 - alkyla-naphthimidazole ring;

an imidazo [4,5-b] quinoxaline ring, e.g. A 1-alkyl-imidazo [4,5-b] quinoxaline ring, e.g. B. a 1 - ethylimidazo [4,5 - b] quinoxaline, 6 - chloro-1 - ethylimidazo [4,5 - b] quinoxaline, 1 - alkenylimidazo [4,5-b] quinoxaline, e.g., 1-allylimidazo-L4-5 - b] quinoxaline-, 6 - chloro -1 - allylimidazo- [4,5-b] -quinoxaline-, 1 -Arylimidazo ^ .S-bjquinoxaline-, z. B. a 1-phenylimidazo [4,5-b] quinoxaline or 6-chloro-1-phenylimidazo [4,5-b] quinoxaline ring;

a 3,3-dialkyl-3H-pyrrolo [2,3-b] pyridinrine.

e.g. a 3,3-dimethyl-3H-pyrrolo [2,3-b] -

pyridine or 3,3-diethyl-3H-pyrrolo [2,3-b] py-

ridine ring or a thiazolo [4,5-b] quinoline ring

If R _{3 has} the meaning of an optionally sub-

substituted alkyl radical, this preferably has

1 to 12, especially 1 to 4 carbon atoms.

R ₃ can thus consist, for example, of a methyl, ethyl, propyl, isopropyl, butyl, hexyl

Cyclohexyl, decyl or dodecyl radical, or one

Hydroxyalkyl radical, e.g. B. a / i-hydroxyethyl or

(M-hydroxybutyl radical, or an alkoxyalkyl radical, e.g.

a / i-methoxyethyl or c-butoxybutyl radical. or

a carboxyalkyl radical e.g. B. a / f-carboxyethyl

or o-carboxybutyl radical, or an alkoxy radical, e.g.

a methoxy or ethoxy radical, or a sulfo-

alkyl radical. z. B. a / i-sulfoethyl or r -.- sulfobutyl-

rest, or a sulfatoalkyl radical, e.g. B. a / i-sulfato

ethyl or c-sulfatobutyl radical, or an acyloxy

alkyl radical, e.g. B. a / i-Acetoxyäthyl-, v-Acetoxy-

propyl or m-butyryloxybutyl radical. or an AIk

oxycarbonylalkyl radical. z. B. a ^ -Methoxycarbo-

nylälhyl or ci-Äthoxycarbonylbutylrest, or one

Aralkyl radical. z. B. a benzyl or phenethyl radical.

If R _{3 has} the meaning of an alkynyl radical, then

if this consists, for example, of an allyl 1-prop

enyl or 2-butenyl radical.

If R _{3 has} the meaning of an optionally substituted aryl radical, this preferably consists of an optionally substituted aryl radical of the phenyl or naphthyl series and consists, for example, of a phenyl, toly-. Naphthyl, methoxyphenyl or chlorophenyl radical.

L can be, for example, a methine group substituted by an alkyl or aryl resl, for example emc group of the following structural formulas:

-CH = -C (CH ₃ ) = -C (C ₆ H ₅ ) =

Have D. E and J mean alkyl radicals. they preferably have 1 to 12, in particular 1 to 4, carbon atoms and consist, for example, of methyl, ethyl, propyl, isopropyl, butyl, decyl or dodecyl radicals.

Do D, E and J mean aryl radicals. so these preferably consist of aryl radicals Phenyl or naphthyl series and consist, for example, of phenyl, tolyl, naphthyl. Methoxyphenyl, Chlorophenyl or nitrophenyl radicals. X can in turn, for example, be a perchlorate

Tetrafluoroborate, chloride, bromide, iodide, sulfamate, Thiocyanate, p-toluenesulfonate or methyl sulfate anion being.

If G has the meaning of an aryl radical, this preferably consists of an aryl radical of the phenyl or naphthyl series, for example a phenyl, naphthyl, dialkylaminophenyl, tolyl, chlorophenyl or nitrophenyl radical. If G has the meaning of an anilino radical, this preferably has the meaning of a radical of the formula

-N

wherein R _{3 is} a hydrogen atom or an alkyl or acyl radical having 1 to 8 carbon atoms.

_{The radical R 5} shown in structural formula IV can be, for example, an ethylene, ethyleneoxy, trimethylene, trimethyleneoxy, tetramethylene, tetramethyleneoxy, propylidenoxy, ethylenedioxy or phenylenebisethoxy radical.

If R has the meaning of an optionally substituted alkyl radical, this can be expedient have up to 12, preferably 1 to 8 and in particular 1 to 4 carbon atoms, d. i.e., R can for example, a methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl, dodecyl radical or an alkaryl radical, such as a benzyl radical, or a sulfoalkyl radical, for example a ß-sulfoethyl, (o-sulfobutyl or m-sulfopropyl radical.

If R has the meaning of an acyl radical, this can be given by the formula

O
-CR

35

are reproduced, where R is an optionally substituted alkyl radical of the meaning given or an aryl radical, preferably of the phenyl or naphthyl series, d. H. for example a methyl, Phenyl, naphthyl, propyl or benzyl radical, can be.

In the formulas, Q ₂ preferably represents the atoms which are necessary to complete a pyridine or quinoline ring.

Furthermore, D, E and J preferably represent aryl radicals.

_{Advantageously, Q 1} , Q ₂ , Q ₃ , Q ₇ and Qq can also stand for the atoms which are required to complete an imidazo [4,5-b] quinoxaline ring or a thiazole, oxazole, selenazole, thiazoline substituted by a nitro radical -, pyridine, quinoline or imidazole ring are required. These rings are desensitizing rings.

Typical crosslinking agents which can be used according to the invention and which consist of dyes are, for example:

1. 3-ethyl-l'-methoxyoxa - ^ '- pyridocarbocyanine perchlorate,

2.1-EthoxyO-äthyloxa ^ '- pyridocarbocyanine tetrafluoroborate,

3. 3'-ethyl-1-methoxy-2-pyridothiacyanine iodide,

4. 1-Ethoxy-S-ethyl-i-pyridothiacyanine tetrafluoroborate,

5. l-benzyloxy-3'-ethyl-2-pyridothiacyanine iodide,

6. 3 '-Ethyl-1-methoxy-2-pyridothiacarbocyanine-

60

7. 1-Ethoxy-3 '-ethyl-2-pyridothiacarbocyanine tetrafluoroborate,

8. Anhydro-3'-ethyl-1- (3-sulfopropoxy) -2-pyridothiacarbocyanine hydroxide,

9. l-Benzyloxy-3'-ethyl-2-pyridothiacarbocyanine perchlorate.

10. S'-ethyl-1-methoxy ^ -pyridothiadicarbocyanine perchlorate,

11. l'-methoxy-l ^^ - trimethylindo ^ '- pyridocarbocyanine picrate,

12. 3'-Ethyl-1-methoxy-4'.5'-benzo-2-pyridothiacarbocyanine perchlorate,

13. l-ethoxy-3'-ethyl-4 ', 5'-benzo-2-pyridothiacarbocyanine tetrafiuoroborate,

14. 1'-Ethoxy-S-äthyloxa ^ '- carbocyanine tetrafiuoroborate,

15. 1'-Ethoxy-S-äthylthia ^ '- cyanintetrafiuoroborat,

16. l'-ethoxy-3-ethylthia-2'-carbocyanine tetrafluoroborate,

17. 1'-Ethoxy-S-äthylthia ^ '- dicarbocyanine tetrafluoroborate,

18. 1 -Methoxy-3'-methyW-pyridothiazolinocarbocyanine perchlorate,

19. 3'-Ethyl-1-methoxy-4-pyridothiacyanine perchlorate,

20. 3 '-Ethyl-1-methoxy ^ -pyridothiacarbocyanine-' perchlorate,

21. 1'-Ethoxy ^ -äthylAS-benzothia ^ '- carbocyanine tetrafluoroborate,

22. 2- / i-anilinovinyl-1-methoxypyridinium-p-toluenesulfonate,

23. 1-Ethyl-l'-methoxy-4,5-benzothia-4'- ~ arbocyanine perchlorate,

24. 1-Metnoxy-2-methylpyridinium-p-toluenesulfonate.

25. 1-methoxy-4-methylpyridinium-p-toluenesulfonate,

26. Anhydro-2-methyl-1 - (3-sulfopropoxy) pyridinium hydroxide,

27. 1-ethoxy-2-methylpyridinium tetrafluoroborate,

28. 1 -Benzy loxy-2-methylpyridinium bromide,

29. 1-ethoxy-2-methylquinolinium tetrafluoroborate,

30. 1,1'-ethylenedioxybispyridinium dibromide,

31. 1.1'-trimethylenedioxybispyridinium dibromide.

32.1,1'-tetramethylenedioxybis (2-methylpyridinium> dibromide,

33.1,1'-tetramethylenedioxybis (4-methylpyridinium> dibromide,

34.1,1'-tetramethylenedioxybispyridinium dibromide,

35. 1 . 1 '- pentamethylenedioxybispyridinium dibromide.

36. 1-Acetoxy-2- (4-dimethylaminostyryl) pyridinium perchlorate.

37.1 -Benzoyloxy-2- (4-dimethylaminostyryl) pyridinium perchlorate,

38. 1,3-Diethyl-5 - [(1-methoxy-2- (1 H) -pyridylidene) ethylidene] -2-thiobarbituric acid.

39. 3-Ethyl-5 - [(l-methoxy-2 (l H) -pyridylidene) ethylidene] rhodanine,

40.1.3-Diethyl-5 - [(l-methoxy-2 (1 H) -pyridylidene) ethylidene] barbituric acid,

41. 2- (3,3-Dicyanoallylidene) -l-methoxy-1,2-dihydropyridine,

42. 2 - [(l-Methoxy-2 (i H) -pyridylidene) ethylidene] -benzo [b] thiophene-3- (2H) -one-l, l-dioxide,

43. 3-Cyano-5 - [(1-methoxy-2 (1 H) -pyridylidene) ethylidene] -4-phenyl-2 (5H) -furanone.

According to a further embodiment of the invention

contains the image recording material as a crosslinking agent

l-methoxy-2-methylpyridinium-p-toluenesulfonate, l-methoxy-4-methylpyridinium-p-toluenesulfonate, Anhydro-2-methyl-l- (3-sulfopropoxy) pyridi-

nium hydroxide,
l, r-Tetramethylenedioxybis (2-methylpyridi-

nium) dibromide or
1,1 '-TetramethylenedioxybisK-methylpyridinium) dibromide.

For the preparation of an image recording material according to the invention, the usual known ones can be used crosslinkable, reactive group-containing polymers can be used. The responsive Groups can be present in the main chain or the so-called backbone of the polymers be or in side chains of the polymers. Furthermore, the reactive groups can are at the ends of the polymer chains. For the production of the image recording material according to of the invention are generally all the polymers having groups that interact with an aldehyde allow cross-linking, d. H. so-called crosslinkable polymers.

The reactive groups of these polymers can vary from one to another

a) primary amino radicals of the formula - ■ NH ₂ , including amide radicals of the formulas

-C-NH,

Il

-NH-C-NH ₂

b) secondary amino radicals of the formula —NHR, in which R is preferably an alkyl radical with 1 to 8 carbon atoms or an aryl radical of the phenyl or naphthyl series,

c) hydroxyl radicals under acidic conditions, e.g. B. at pH values below about 2,

d) residues with active methylene groups, e.g. firstly ^ -Kctocstcrreste, z. B. acetoacetate residues, or secondly α-cyanoester residues, e.g. B. cyanoaceloxy residues, or thirdly residues with an α-diketone group, for example acetoacetyl or benzoylacetyl residues.

Typical polymers suitable for making the imaging material of the invention are for example:

1. poly (vinyl alcohol / vinyl anthranilate / vinyl succinate),

2. Poly (ethyl acrylate / acrylic acid / 2-acetoacetoxy-

ethyl methacrylate),

3. Polylmethyl acrylate / sodium-O-acryloyloxyl-methylpropane-l-sulfonate / 2-acetoacetoxy- ethyl acrylate),

4. Polyimethyl acrylate / acrylic acid ^ -methacryloyloxyethyl cyanoacetate),

5. poly (1 ^ -dimethyl-S-vinylpyridinium methosulfate / m-methacryloyl-N'-cyanoacetylhydrazine),

6. poly (3-acryloyloxypropane-1-sulfonic acid, Sodium salt / N-methacryjoyl-N'-grycylhydrazine).

7. poly (1 ^ -diinethyl-S-vinylpyridinium methosulfate / 2-aminoethyl methacrylate),

8. Polyacrylamide / N-cyanoacetyl-N'-methacryloylhydrazine),

9. gelatin,

10. Poly (vinyl acetoacetate).

According to a further embodiment of the invention, the image recording material contains a crossover ίο wettable polymer, its reactive group out

(a) primary amino residues, '

(b) secondary amino groups,
(C) Hydroxylreslene and / or

(d) residues with active methylene groups

exist.

According to a further embodiment of the invention, the image recording material contains a crosslinkable material Polymer gelatin or polyvinyl acetoacetate.

The ratio of polymer to crosslinking agent can vary widely. As functional it has proved to use so much wetting agent that after destruction or disintegration of the wetting agent in the Layer at least about 0.1, generally 0.1 to 10 weight percent aldehyde, preferably 1.0 to 7.0 weight percent aldehyde based on the weight of polymer and wetting agent is present.

Image recording materials according to the invention are particularly suitable for recording images by exposure to visible light and electron beams. As an advantageous light source for irradiation an image recording material after

Invention, for example, has a 150 watt xenon arc lamp proven that can be set up at a distance of less than about 30 cm, since photochemical cross-linking is sufficiently strong even with relatively low intensity light is. The use of high-intensity light sources is therefore not necessary. When the Electron beam imaging materials of the invention have been found to be useful. To use electron beams with an intensity of about 1 to 100 kV, preferably about 15 kV.

The exposure time is also not critical. It depends somewhat on the amount of crosslinking agent present and the intensity of the radiation source. When using relatively high concentrations of crosslinking agents and strong radiation sources, for example light sources, the exposure time can be very short. The exposure time can be a fraction of a second. On the other hand, however, exposure times can also be used

up to several hours may be required. In most cases, exposure times of 1 second to about 1 hour can be used.

The utility of the image recording materials according to the invention for recording

Images or for the reproduction of images is based on the fact that when the recording materials are exposed, areas can be produced in the exposed areas which are more insoluble than those not exposed districts. If an image is Drawing material according to the invention with a If the originally soluble photosensitive layer is exposed photographically, the photosensitive layer becomes Layer made insoluble in accordance with the image.

2419

The support of the recording material of the invention can consist of one of the usual supports exist for the production of image recording materials be used, d. H. for example from metal supports, e.g., metal plates or metal foils made of e.g. copper, aluminum, zinc and magnesium, or made of paper, glass or foils synthetic polymers, for example from cellulose acetal butyrate, cellulose acetate, polyvinyl acetal, polystyrene, Polycarbonates, polyesters, e.g. B. polyethylene terephthalates ^ and the like Paper, for example a polyethylene-coated paper, consist or of a Polyamide or metal grid or sieve,

The production of the image recording material according to the invention can be carried out by conventional methods. The substrate is expediently coated with a solution or dispersion of the polymer and the nucleus coated in a suitable solvent, followed by the solvent or optionally a solvent mixture is evaporated, the radiation-sensitive layer on the support remains behind. The recording material can then be imagewise exposed to actinic radiation or other sources of energy.

Used to make the imaging material If a light-reflecting substrate is used, it may be advantageous initially on the support a layer or a stratum made of an actinic light absorbing substance apply in order to reduce the reflection of the substrate.

When using water-soluble coating mixtures (polymer and wetting agent), for Applying the radiation-sensitive layer can be used as a solvent water. Using customary organic solvents can be used for coating compositions which are insoluble in water or solvent mixtures or mixtures of organic solvents and water are used will.

The image recording materials according to the invention can be used for photographic reproductions, photomechanical reproductions, lithographic reproductions and for intaglio printing use. For example, the image recording materials of the invention can be use for offset printing, for screen printing, especially silk screen printing, for making Printing templates, lithographic printing forms, relief printing forms and discharge printing forms, d. H. generally the most varied of customary printing forms.

Starting from an image recording material according to the invention, a printing form can be used, for example produce as follows: An image recording material according to the invention, for example with a consisting of a metal plate, is supported by a transparent template with a visible Light exposed, for example through a positive or negative with transparent and non-transparent Districts. When exposed to light, the wetting agent turns into an aldehyde and a dye base split up, whereupon the aldehyde changes the polymer according to the transparent areas of the template cross-linked, with the result that these areas become insoluble, whereas those not exposed Districts retain their original solubility.

The soluble areas can then be removed using a solvent. Those left behind Raised areas can then serve as a resist image, in which case a relief printing form is generated by etching the exposed areas of the substrate. On the other hand, the plate with the insoluble raised areas can also be colored and used as a relief printing form,

The thickness of the photosensitive layer is a direct function of the desired thickness of the Relief image, which in turn depends on the object to be reproduced and especially on the extent of the non-printing districts. Also, in the case of halftone images, that is used Grid is a factor to consider.

It has proven to be useful to use recording materials with a radiation-sensitive layer with a thickness of about 0.001 to 7 mm. For the production of halftone plates in particular recording materials with radiation-sensitive Layers with a thickness of 0.001 to 0.70 mm have proven advantageous. Layers one Thicknesses of about 0.05 to about 1.50 mm have proven to be particularly advantageous when the Imaging material used for the production of printing forms for the printing press should, including for the production of printing forms in which halftone images and line images are to be combined.

For developing the exposed image recording materials, i. H. to wash out the soluble Districts, the usual known solvents can be used, which have a good solvent action on the unexposed areas and the hardened areas, the substrate material and optionally present antihalation layers or so-called adhesive layers for improvement the adhesion of the radiation-sensitive layer to the substrate is not affected.

A particular advantage of the image recording materials according to the invention is that they can be irradiated with a wide variety of energy sources, for which it is only necessary that a such crosslinking agent is selected which is opposite to the radiation source used in the individual case is sensitive. For example, image recording materials can be produced, which by Appropriate choice of the crosslinking agent (s) ensures maximum light absorption over a wide range Have the range of the visible spectrum, so that the recording material can be exposed to various radiation sources.

The image recording materials of the invention can be used for printing purposes other than those described for example also for the production of jewelry plates, plaques or for the production of ornamental ones Effects are used, as well as for the production of templates and stencils for automatically working engraving, embossing and punching machines, also for the production of molds, Stamp matrices, name stamps as well as folders and documents for the blind, for embossing plates as well finally for the production of printed circuits.

The coating compounds used to produce the radiation-sensitive layer can finally also be used as fast-curing coating compositions z. B. be applied to the substrate

used to produce soundtracks on films.

The following examples are intended to illustrate the invention in more detail.

Example I.

A mixture consisting of gelatin and the crosslinking agent No. 24 was in a layer thickness of 6 μ on a polyethylene terephthalate carrier applied. The concentration of the crosslinking agent was such that from this if completely destroyed, 3 percent by weight of aldehyde, based on the weight of crosslinking agent and polymer.

The recording material was then exposed through a slide with a 140 watt UV lamp, which was placed 7.60 cm from the imaging material. After exposure the recording material was washed with water. The unexposed ones were thereby Districts washed off, and an image consisting of the exposed hardened image areas remained.

Equally favorable results were obtained when instead of crosslinking agent no Crosslinking agent # 12, 25, 26, 27, 29, 32 or 33 were used.

Example 2

The procedure described in Example 1 was repeated except that several Concentrations of crosslinking agent No. 24 were used to show the dependence of the crosslinking effect on the concentration of the crosslinking agent.

Each image recording material was swollen by immersing it in water for 3 minutes. The extent of swelling or the percentage swelling is an indication of the degree of crosslinking, a slight swelling is an indication of a relatively strong cross-linking. the The results obtained are summarized in Table I below.

Table I.

45

connection
No. % Aldehyde based
on dry
binder % Swelling Without
24
24
24 G
1
2
6th 580
302
265
85

Example 3

The procedure described in Example 1 was repeated except that in place of of the crosslinking agent No. 24, the crosslinking agent No. 32 was used, and that further in place of Gelatin was used as the polymer polyvinylaceloacetate. After the exposed recording material was washed with water, a relief image became more excellent Maintain quality.

Example 4

This example illustrates the preparation of a lithographic printing plate.

For this purpose, the crosslinking agent No. 24 was mixed with gelatin in such a way that the concentration of crosslinking agent with complete destruction 6% formaldehyde, based on the dry weight the gelatin, produced. The coating mass was applied to an anodized substrate Aluminum applied in a thickness of 0.005 cm.

The recording material was then exposed for 15 minutes through an original with a 140 watt UV lamp (Hanovia type). The exposed plate was then washed for 10 minutes with 3O ⁰ C warm water and then dried. The developed printing form was then clamped in a lithographic printing press and used for printing. Copies of excellent quality were obtained.

Example 5

This example shows the use of a picture recording material according to the invention in the context of a simple transfer process.

First of all, an image recording material was produced by being made from a film support a fluorinated hydrocarbon (Teflon) a layer of gelatin and so much of the crosslinking agent No. 24 was applied that theoretically 6% formaldehyde could form. The layer thickness of the layer was 0.010 cm. The dry recording material was then wetted through a negative in the manner described. The exposed recording material was then immersed in a warm silver nitrate-urea solution. Thereupon the recording material brought into contact with a copy sheet (Verifax copy sheet) and again from the Sheet separated. The image transferred onto the copy sheet was then given the following in a developer Composition developed:

Water, about 50 ^° C. 500 ml

p-methylaminophenol sulfate 3.0 g

Sodium sulfite, dehydrated 45.0 g

Hydroquinone 12.0 g

Sodium carbonate, monohydrate .... 80.0 g

Potassium bromide 2.0 g

Made up to 1.0 1 with water

An excellent reproduction of the original was obtained.

Example 6

This example describes the production of a dye stain with simultaneous curing of the polymer. First, a gelatin-silver halide emulsion was prepared with Crosslinking Agent No. 26, the concentration of the crosslinking agent being chosen so that a 100% reaction the formation of 3% propionaldehyde sulfonic acid was to be expected. After applying the emulsion on The emulsion layer was a layer support using a 150 watt xenon arc lamp through a mask exposed. The recording material was not more than 2.54 cm from the opening of the Removed from the lamp housing. During the 95 minute exposure, the test template became cooled with a stream of nitrogen. The test strip

a size of 4.45 cm ² was then hardened in a pre-hardener bath containing 2% amber aldehyde for 1 minute and then with flowing distilled water at 26 ° C for 15 minutes.

washes. The test square was then ufschllimmen with a solution / on methylene blue eingefUrbl obtained by incorporating ωη 1 g methylene blue in IO ml of water and 10 minutes \ and filtration was made. The dye was stained in the exposed areas. The test square was then allowed to stand in distilled water at room temperature overnight. The dye could not be extracted from the exposed areas,

Example 7

A layer of polyvinylticctoacetate was placed on a polyester support with a size of 11.5 x 16.5 cm and No. 33 crosslinking agent is applied. The concentration of the crosslinking agent was increased chosen so that, based on the dry polymer, the formation of 6% amber aldehyde was expected.

The layer produced was then exposed through the layer support. One served as a template Glass plate with a layer applied thereon with a step wedge pattern.

The exposure time was 5 hours and 5 minutes. The reason for the long exposure time was that the original and recording material at 2500 to 2700A together have an optical density of over 8.0.

The exposed layer was then immersed in a 10% solution of the tetrasodium salt for 10 to 15 seconds colored by 1,8-dihydroxy-2- (6,8-disulfonaphthyl-2-azo) -3,6-disulfonaphthalene and then Washed for a total of 20 minutes with running water at first 30 and then 33 ° C. One Coloring was done preferably in the exposed areas, corresponding stain effect.

Example 8

The procedure described in Example 7 was repeated except this time as a crosslinking agent the compound no. 32 and as a dye the tetrasodium salt of 1,5-disulfomethylamino-SJ-disulfo- ^ S-dihydroxyanthraquinone has been used. Correspondingly favorable results as described in Example 7 were obtained.

45 Example 9

This example illustrates electron beam recording.

There were three different recording materials by coating substrates with Coating compositions made from gelatin and crosslinking agents No. 24, 32 or 33. the The concentration of crosslinking agent was chosen in each case so that by splitting up the crosslinking agent theoretically 6% aldehyde, based on the dry binder, were formed.

The recording materials were then in a series of tests in stages electron beams from 15 kV exposed.

The test strips were then washed with water and checked for the hardening effect that had occurred examined. Hardened areas had emerged in all of the strips.

To illustrate the staining effect, the exposed strips were bathed in a dye solution of the composition given in Example 7. Coloring began primarily in areas exposed to the Aen. The strips were

then left in distilled water overnight. The heated dye was not removed.

Manufacture of photosensitive crosslinking agents <

No protection is claimed here for the manufacturing processes specified below.

1. Preparation of compound no.24 (Method A)

A mixture of 10.9 g of 2-picoline N-oxide and 27.9 g of methyl p-toluenesulfonate was heated on the steam bath with constant stirring until an exothermic reaction began. After completion of the supply of external heat, the temperature rose to a maximum of about 120 ⁰ C. The mixture was then cooled, diluted with 200 ml of acetone and quenched. The deposited precipitate was filtered off and washed with acetone. The yield of reaction product was 23.2 g, corresponding to 79% of theory. The melting point of the compound was 113 to 114 ° C.

2. Preparation of Compound No. 28 (Method B)

10.9 g of 2-picoline N-oxide and 18.8 g of benzyl bromide were dissolved in 25 ml of acetone and the solution was refluxed for 10 minutes. After dilution with 150 ml of acetone, the solution was cooled. The deposited precipitate was filtered off and washed with acetone. The yield of reaction product was 19.0 g, corresponding to 68% of theory. The melting point was 113 to 114 ^° C.

3. Establishing compound no. 22

5.90 g of compound no. 24 and 2.98 g of ethyl isoformanilide in 5 ml of dimethylformamide were heated on the steam bath for _{2 hours.} The mixture was then diluted with 50 ml of acetone and quenched. The resulting yellow precipitate was filtered off and washed with acetone. The yield was 3.3 g, corresponding to 41% of theory. The melting point of the compound was 172 to 173 ° C.

4. Establishing compound no. 1

3-ethyl-1'-methoxy oxa-2'-pyridocarbocyanine perchlorate

= CH-CH = <

/ X

1Y

OCH,

2.22 g of l-methoxy-2-methylpyridinium-p-toluenesulfonate, 2.17 g of 2 - / <- acetanilidovinyl-3-ethylbenzoxazolium iodide and 1.4 ml of triethylamine in 20 ml of ethanol were heated to reflux temperature for 2 minutes. Then a solution of 0.61 g of sodium perchlorate in hot methanol was added. To the reaction product separated out on cooling. It was filtered off and washed with ethanol. The yield of reaction product was 1.50 g, corresponding to 77% of theory. The melting point the compound was at 146 to 147 ° C.

5, making compound no, 3 3'-Ä (liyI-l-mothoxy-2-pyridathitJpyaninjodicl

6. Establishing compound no, 6 3'-ethyl-1-methoxy-2-pyridolhiacarbocyunin iodide

OCH

4.44 g of l-methoxy-2-methylpyridinium-p-toluenesulfonate, 4.00 g of 3-ethyl-2-phenyltniobenzothiazoliumjoclid and 2.8 ml of triithylamine were refluxed for 10 seconds in 20 ml of ethanol. After quenching, the precipitated precipitate was filtered off and washed with ethanol. The yield of reaction product was 1.55 g, corresponding to 30% of theory. The melting point of the compound was 159 to 16O ⁰ C.

IO 2.22 g l-Mcthoxy-2-mcthylpyridinium p-toluenesulfonate, 2.25 g of 2- / i-acetanilidovinyl-3-ä'thylbcnzothiazoliumjodid and 1.4 ml Triiithylamin were heated in 20 ml of ethanol at reflux for 2 minutes . The mixture was then quenched and the resulting precipitate was filtered off and washed with ethanol. The bulge was 1.27 g, corresponding to 50% of theory. The melting point of the compound was 115 ° C.

7. Preparation of Compound No. 10 3'-Ethyl-1-methoxy-2-pyridothiadicarbocyanine perchioral

- CH = CH - CH == CH - CH OCH ₃

ClO ₄ ⁰

3.54 g of l-methoxy-2-methylpyridinium-p-toluenesulfonal, 4.76 g of 2- (4-acetanilido-1,3-butadienyl) -3-ethylbenzothiazolium iodide and 1.8 ml of triethylamine were added to 20 ml of dimethylformamide for 2 minutes Stirred at room temperature. The mixture was then diluted with 400 ml of ether. The ethereal layer was then decanted off, whereupon the oily residue was dissolved in 50 ml of methanol. Thereupon was a solution of sodium perchlorate in methanol was added to the solution obtained. The mixture was cooled, whereupon the deposited precipitate was filtered off and washed with methanol. The yield of reaction product was 0.95 g, corresponding to 22% of theory.

20 ml of ethanol heated to reflux temperature for 2 minutes. The resulting solution was then cooled, whereupon a solution of 1.15 g of picric acid in ethanol was added. After cooling, the deposited precipitate was filtered off and washed with ethanol washed. The yield of reaction product was 1.12 g, corresponding to 40% of theory.

9. Establishing compound no. 12

3'-ethyl-1-methoxy-4 ', 5 ^/ -benzo-2-pyridothiacarbocyanine perchlorate

8. Preparation of compound no.11

1'-methoxy-1,3,3-trimethylindo-2'-pyridocarbocyanine picrate

45

CH = CH-CH

CH ₃

CH = CH-CH

OCH,

COO °

O, N

55

60

NO,

2.22 g of l-methoxy-2-methylpyridinium-p-toluenesulfonate, 2.23 g of 2- / i-acetanilidovinyl-1,3,3-trimethyl-3H-indolium iodide and 1.4 ml of triethylamine were in

OCH ₃

2.22 g of l-methoxy-2-methylpyridinium-p-toluene-sulfonate, 2.57 g of 2- / f-anilinovinyl-1-ethylnaphtho [1,2-d] -thiazolium-p-toluenesulfonate and 1.4 ml of triethylamine in 25 ml of acetic anhydride were added with stirring Heated to 40 ° C for 5 minutes. A small amount of undissolved compounds was filtered off II whereupon the filtrate was diluted with excess ether. The ethereal layer was then decanted off, whereupon the residue was dissolved in 25 ml of methanol. Then a solution of 0.61 g Sodium perchlorate in methanol was added. After cooling, the deposited precipitate became filtered off and washed with methanol. The yield of the reaction product was 1.48 g, correspondingly 65% of theory.

Following the procedures described in Preparation Examples 1 to 9, those in the following were obtained Compounds listed in Tables II and III.

The two following tables show the manufacturing methods used in detail, the yields achieved and the melting points of the compounds obtained.

Table!!

Manufacturing example connection
No. Between-
connection no. (Reak 25th method
according to the example solvent 80 ° C) Ä Yield in% M.p. ' C 10 2 27 25th 6th Ä M. 43 dec. 11th 4th 27 29 5 A. DF / EA ² ) 33 dec. 12th 5 28 5 Ä 18th 125 to 130 13th 7th 27 6th Ä 89 dec. 14th 8th 26th 6th M ¹ ) 45 128 to 131 15th 9 28 4th M. 45 125 16 13th 27 9 EA 81 dec. (without NaClO ₄ ) 17th 14th 29 6th M. 38 143 18th 15th 29 5 M. 47 dec. 19th 16 29 6th M. 63 138 to 139 20th 18th 24 9 EA 35 127 to 128 ion temperature 21 19th 5 20th 186 to 187 22nd 20th 4th 58 128 23 21 11th 40 dec.

') Reaction mixture, diluted with acetone, to precipitate the dye. ² ) Reaction temperature 25 ° C, without addition of NaClO ₄ .

A = ethyl alcohol.

M = methyl alcohol.

EA = acetic anhydride.

DF = dimethylformamide.

Table III

Hcr- Connection base Alkylating agents method solvent Out M.p.'C positional manic prey example No. 4-picoline-N-oxide Methyl p-toluene sulfonate A. % 153 to 154 24 25th 2-picoline-N-oxide 1,3-propane sultone B. acetone 97 202 to 203 25th 26th 2-picoline-N-oxide Triethyloxonium B. CHCl ₃ 95 53 to 57 26th 27 tetrafluoroborate 80 Quinaldine N-oxide Triethyloxonium B. CH ₂ Cl ₂ 115 to 117 27 29 tetrafluoroborate 90 Pyridine-N-oxide 1,2-dibromoethane A. - 170 to 171 28 30th Pyridine-N-oxide 1,3-dibromopropane A. - 81 151 to 153 29 31 2-picoline-N-oxide 1,4-dibromobutane A. - 100 153 to 154 30th 32 4-picoline-N-oxide 1,4-dibromobutane B. CH ₃ CN 88 109 to 111 31 33 Pyridine-N-oxide 1,4-dibromobutane A. 39 172 32 34 Pyridine-N-oxide 1,5-dibromopentane A. ._ 91 115 to 117 33 35 88

34. Establishing compound no.

1,3-diethy 1-5 - [(1-methoxy-2 (1H) -pyridylidene) ethylidene] -2-thiobarbituric acid

Oc υ CH - CH = <> = S

OCH,

C ₂ H,

99 g 2-Ii- anilinovinyl -1-methoxypyridinium p-töluenesulfonate, 2.00 g U-diethyl-2-thiobarbitur-

acid and 20 ml of acetic anhydride were stirred together, whereupon 5 ml of triethylamine were added became. The mixture was then stirred for a few minutes until everything had dissolved. The solution was then inoculated by using a seed crystal, obtained by diluting a small amount of the reaction mixture with excess Ether, was added. The mixture was then chilled for a few hours. The unusual one The dye was filtered off and washed first with methanol and then with ether. The yield at pure dye was 1.48 g. corresponding to 44% of theory. The melting point of the compound was at 171 to 172 ° C dec.

209 628/242

2419

Compounds 39 to 43 were prepared in the manner described in Preparation Example 38. The yields obtained and the melting points of the compounds are shown in the table IV.

Table IV

Heating
example Connection no. yield
% M.p. C 39 39 47 75.5 40 40 25th 154 to 155 41 41 73 dec. 42 42 79 169 to 170 43 43 88 133.4

25th

Claims (6)

Patent claims: 1. Image recording material, consisting of a layer support and at least one thereon applied light crosslinkable layer with (I) ₁ a crosslinkable polymer whose radicals capable of crosslinking are reactive with aldehydes, and (2) a photosensitive crosslinking agent for the polymer, which when exposed to Light decays and its decay products cause cross-linking of the polymer, characterized in that it is a crosslinking agent with a residue OR contains one of the following formulas ^ R « OR 40 45 II III ^x N · '■ OR R, R ₄ NOR ₅ -N 2X-IV OR in which Z denotes the one to complete an optionally substituted 5- or 6-membered. heterocyclic ring required atoms. R is an optionally substituted alkyl. Aryl or acyl radical, R, an optionally substituted methine or polymethine group with a terminal heterocyclic ring customary for cyanine dyes, an optionally substituted alkyl radical. an anilinovinyl residue. an optionally substituted aryl radical, a hydrogen atom, an aldehyde radical, an optionally substituted styryl radical or an acyl radical. R ₂ and R ₃ each represent a hydrogen atom or an optionally substituted alkyl or aryl radical. R _{5 is} an alkylene or alkyleneoxy radical having 1 to 8 carbon atoms in the alkylene chain or a radical of the formula -t CH ₂ ) T- R _iirt CH ₂ V-Or- where s and t are each a number from 1 to 8.K = O or 1 and R, _{o is} an arylene radical. R _{8 is} an optionally substituted methine or polymethine group with a terminal heterocyclic ring customary for merocyanine dyes, an optionally substituted allylidene radical or an aldehyde radical, Q ₂ and Q _{9 are} the atoms required to complete a 5- or 6-membered heterocyclic ring and X is an acid anion . 2. Image recording material according to claim 1, characterized in that it contains a crosslinking agent of one of the following formulas: Q, CH-CH-ij-r-N-R, X -Q- NR ₃ X L = L- χβ RO-N = L-L in which R denotes an optionally substituted aryl, alkyl or acyl radical, R ₂ denotes an optionally present alkyl or aryl radical of the meaning already given, R ₃ denotes an optionally substituted alkyl, alkenyl, aryl or alkoxy radical, Q ₁ , Q ₂ , Q ₃ and Q ₇ the atoms required to complete 5- or 6-membered, heterocyclic rings, L an optionally substituted methine group, D, E and J each a hydrogen atom or an alkyl or aryl radical, X ⁰ an acid anion, G an anilino or aryl radical , g = 1 or 2, m = 1, 2 or 3 and η = 1, 2, 3 or 4. 3. Image recording material according to claim 1, characterized in that it contains a crosslinking agent of the specified formulas, in which Q ₁ , Q ₂ , Q ₃ and Q ₇ represent the atoms required to complete pyridine or quinoline rings. 4. Image recording material according to claim 1, characterized in that it is used as a crosslinking agent contains: l-methoxy-2-methylpyridinium-p-toluenesulfonate, .- Qr-- CH = CH l-methoxy-4-methylpyridinium-p-toluenesulfonate, Anhydro-2-methyl-1 - (3-sulfopropoxy) pyridinium hydroxide, l, l'-tetramethylenedioxybis (2-methylpyridinium) dibromide or 1,1 '-Tetramelhylenedioxybis (4-methylpyridinium) dibromide. 5. Image recording material according to claim 1, characterized in that it is a crosslinkable Polymer contains whose reactive groups (a) primary amino residues, (b) secondary amino groups, (c) hydroxyl radicals and / or (d) residues with active methylene groups exist. 6. Image recording material according to claim 1, characterized in that it is crosslinkable Contains polymer gelatin or polyvinylacetoacetai.