DE1269478B - Photosensitive layer - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

G03c

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

German class: 57 b -4Θ-? /

Number: 1 269 478

File number: P 12 69 478.9-51

Filing date: September 7, 1963

Open date: May 30, 1968

The invention relates to a photosensitive layer with one or more organic heterocyclic ones Azides and one or more heterocyclic coupling components and optionally a binder.

It is known that certain organic azides are photosensitive and used for the production of printing forms are suitable. Photosensitive layers are used to produce such printing forms of azides and binders, such as albumin, starch Li. Like., applied to the substrate. In the exposure With such a recording material, the exposed parts of the image become hard and insoluble. By removing the non-hardened parts of the image, it is possible to use them as printing forms in this way. Make reversible relief images that can be printed with bold color. According to the British In US Pat. No. 765,909, certain light-sensitive azidobenzimidazoles can also be used for production use of binder-free printing forms.

The disadvantage of the known layers containing organic azides is that the layers obtained with them Images lack the desired high contrast.

The object of the invention is to provide a photosensitive layer that can be used for the production of high-contrast copying images is suitable.

The subject matter of the invention is based on a light sensitive layer with one or more heterocyclic azides and one or more coupling components and optionally one A binder and is characterized in that the layer is an azide of one of the formulas

Photosensitive layer

Applicant:

Eastman Kodak Company,

Rochester, N. Y. (V. St. A.)

Representative:

Dr.-Ing. W. Wolff, H. Bartels,
Dipl.-Chem. Dr. J. Brandes
and Dr.-Ing. M. Held, patent attorneys,
8000 Munich 22, Thierschstr. 8th

Named as inventor:
John Joseph Sagura,
James Albert Van Allen,
Rochester, NY (V. St. A.)

Claimed priority:

V. St. v. America October 1, 1962 (227 561)

or

N-N

where Q is an oxygen, sulfur or selenium atom or a> NR group in which R is a hydrogen atom, an alkyl, aryl, sulfonyl, alkoyl, aroyl, carbalkoxy or carbamyl group, R ¹ and R- each equals a hydrogen atom or an alkyl, alkoxy, aryl or nitro group. A halogen atom or the non-metallic atoms necessary to complete a fused ring are and R ^{; t} is an azido or an alkyl group, R 'is an azido, an alkyl or an amino group. Z equals a - CH group or an = N group and R · " ¹ equals a hydrogen atom or one

Is an alkyl group, and a coupling component of one of the formulas

IO

10

15 16 17

18 19 20 21 2 ~> 23

■ 5

where R "and R ^{7 are} each equal to a hydrogen atom, an alkyl or aryl group. R" and R ^{! l are} each equal to a hydrogen atom, an alkyl, alkoxy, aryl or nitro group or a halogen atom or which are fused to complete one Non-metallic atoms required for the ring are, R " ¹ and R ^{11 are} each equal to a hydrogen atom, an alkyl, alkoxy, aryl or nitro group, a halogen atom, a hydroxy group or an oxygen atom, or the non-metallic atoms required to complete a fused ring Atoms are, W is an oxygen, sulfur or selenium atom, a methylene, imino,

- S -

R ¹² X
- N group

R ^u

in which R ¹ - equals an alkyl group. χ equals an acid anion. R ¹³ is a hydrogen atom or an alkyl group and /; is 1 or 2. means, where at least one of the ortho or para positions to the imino group of the coupling component must be unsubstituted. Suitable azides are, for example:

Name of the azide

-Azidobenzoxazole

! -Azido-1-phenylearbamylbenziinidazole -Azido-1-carbethoxybenzimidazole -azido-1-p-nitrophenylcarbamylbenzimidazole -Azidoacridine

-Methoxy-7-chloro-9-azidoacridine -Azido-1 -p-methoxyphenylearbam \ lbenzimid · azole

Azido-1-o-methoxyphenylcarbamylbenzimide azole

4-diazido-6-phenylamino-s-triazine 4,6-triazido-s-triazine

• Azidonaphtho [1,2] oxazole Azidobenzimidazole

Azido-1-carbobutoxymethylearbamylbenz-

imidazole
2-azidobenzothiazole

27 28 29 30 31

Name of the azide

2-azido-1-acetylbenzimidazole

2,4-diazido-6-methylpyrimidine

2-azido-l-carboisopropoxymethylcarbamyl-

benzimidazole

2-azido-1-p-toluenesulfonylbenzimidazole 4-azido-6-chloro-2-methy] pyrimidine 2,4-diazido-6-phenylaminopyrimidine 2-azido-1-trichloroacetylbenzimidazole 2-azido-1-trifluoroacetylbenzimidazole 2-azido-l- (a-carbamyldiethylsuccinato) -benz-

imidazole 2-azido-1 - («- carbamy ldiäthylgl utarato) -benz-

imidazole

2-azido-1-undecylcarbamylbenzimidazole 2-azido-1-carbethoxyundecylcarbamylbenz-

imidazole

2-Azido-1-u-naphthylcarbamylbenzimlazoI 5-Azidotetrazol [a] phthalazine 4-Azido-6-methyl-1,3,3a, 7-tetrazaindene 2-methoxy-6-chloro-9-azidoacridine 2-azido-1- (phenylcarbamido) benzimidazole

Suitable heterocyclic coupling components are:

No.

1 2

10 11 12

16 17 18!

20 ^!

23 ^! 24 25 26 '27 28

Name of the coupling component

Phenothiazine

3-nitrophenothiazine

1-methoxyphenothiazine

l-hydroxyphenothiazine

3-isopropoxyphenothiazine

3,6-dimethylphenothiazine

Dihydrobenzothiazine

S-methylphenothiazine

Benzo [a] phenothiazine

9-methoxybenzo [a] phenothiazine

Benzo [b] phenothiazine

6.11-dioxobenzo [b] phenothiazine

1,6-dimethoxybenzo [b] phenothiazine

Benzo [c] phenothiazine

Dibenzo a.jlphenothiazine Dibenzo a.hjphenothiazine

Benzo [a] phenoselenazine phenoxazine

Benzo [c] phenoxazine Benzo [b] phenoxazine

the dimer of benzo [b] phenoxazine

9-methylbenzo [b] phenoxazine

the dimer of 9-methylbenzo [b] pheno \ azine

9-t-Butylbenzo [b] phenoxazine

the dimer of 9-t-butylbenzo [b] phenoxazine acridane 3-hydroxyacridane N-methyldihydrophenazine

^{The invention achieves that high-contrast copy images} are obtained with light-sensitive layers containing organic azides. Achromatic color print-out, two image forming systems, aeration ⁶ S standing of two or more azides by using \ on with one or more heterocyclic coupling components, or consisting of an azide and two or more heterocyclic coupling components.

be generated. For this purpose, the two color-forming systems should be the same or almost the same photographic Have sensitivities, so that the copied images at all image density levels without a color cast are.

According to one embodiment of the invention, the photosensitive layer contains 2-azidobenzoxazole. Benzo [a] phenothiazine, 2-azido-1-phenylcarbamylbenzimidazole and phenothiazine.

According to a further embodiment of the invention, the photosensitive layer contains 2-azido-1-carbobutoxymethylcarbamylbenzimidazole Benzo [b] phenoxazine and 2-azido-1-phenylcarbamylbenzimidazole.

According to a further embodiment of the invention, the photosensitive layer contains 2-azido-1-phenylcarbamylbenzimidazole. Benzo [b] pheno \ azine and phenothiazine.

According to a further embodiment of the invention, the photosensitive layer contains 2-azido-1-carboisobutoxymethylcarbamylbenzimidazole. Benzo [b] phenoxazine and 2-azido-1-phenylcarbamylbenzimidazole.

According to a further embodiment of the invention, the photosensitive layer contains as a binder Gelatin. Casein, rubber. Polystyrene, a vinyl polymer, a cellulose derivative or a mixture of these polymers.

Solvent mixtures are used to produce the layers used that consists of a low-boiling solvent and one or more higher-boiling solvents such as cyclohexanone. Benzene. Methyl ethyl ketone. Ethylene chloride. toluene and methyl isobutyl ketone. exist, with the low boiling point Solvent e.g. B. acetone can be. The use of higher boiling solvents in an amount of about 10 percent by weight, based on the total mixture, has such an effect. that the drying speeds of the coatings or layers are reduced, so that a a more uniform layer is produced that is free from stains. The addition of benzene and toluene improved also the durability of the inspection knowledge.

The copy-out images can be stabilized by treatment with solvents, soft the extract unreacted portions of the heterocyclic azides from the photosensitive layer while they leave the copy-out image unchanged and do not attack the binding agent. Solvent, which are suitable for this purpose at room temperature are methanol. Ethanol. Butyl acetate and a Mixture of isopropanol and acetone in a ratio of 4: 1. To avoid unreacted azides at increased To remove temperatures, trichlorethylene is used.

example 1

To 25 g of a solution consisting of 10 "cellulose acetate propionate in 2-butanone. 0.5 g of a below-mentioned heterocyclic azide and 0.2 g a heterocyclic coupling component mentioned below was added. After complete solution a paper veneer was coated (2 g 0.09 m-).

Azides completely insoluble in 2-butanone were found in a solution of polystyrene in benzene or Ethylene chloride or dissolved in a methanolic solution of polyvinyl butyral.

The photosensitive layer was copied from a negative exposed to ultraviolet light. The colors of the resulting images are given below:

Heterocyclic
Coupling component Azide Image color blue 1 1 blue 1 1 Blue-gray 1 3 green 1 4th Orange brown 1 5 Brown 6th blue 7th blue 8th Brown 9 Gray 10 blue 11 orange 1 blue 1 Purple 12th blue 1 blue 13th Brown ·> blue T 1 orange 3 1 Brown 3 13th Blue-gray 3 1 Purple 3 1 Purple 4th 1 Purple 5 14th Reddish brown 6th 3 Purple brown 7th 4th Red 8th 15th Purple 9 7th Purple I) O Red 9 16 orange 9 9 Red orange 9 10 Purple 9 1 Gray 9 Gray 9 13th Gray 9 17th Brown 9 1 Dark green 9 1 green 10 1 green 11 Light green 11 10 unsaturated green 9 Dark blue 12th 1 Gray 13th 1 Brown 14th T violet 14th 1 violet 14th 12th Dark purple 14th 1 Purple 15th 18th Brown 16 19th .Brown 17th 16 Brown 18th 2 Purple 18th 1 Purple 18th 12th Gray 18th unsaturated yellow 18th 16 Brown 18th 20th Brown 19th 15th Pale gray 20th 21 * Gray 20th 22nd 20th 20th 20th 20th 20th 20th

continuation

Heterocyclic
Coupling component Azide Image color Gray 20th 13th Gray 20th 17th Gray 20th 23 Gray 20th 24 Gray 20th 25th Gray 20th 26th Yellow-brown 20th 5 Yellow-brown 20th 14th Gray 20th 7th Gray 20th 4th orange 20th 27 unsaturated purple 21 13th Gray 22nd 13th unsaturated purple 23 13th Yellow-brown 24 13th Yellow-brown 25th 13th Brown 26th 1 Brown 26th 13th Red 27 1 Brown 28 1 orange 13th

'5 given: 0.2g 2-azido-1-phenylcarbamylbenzimidazole, 0.2 g 2-azidobenzoxazole, 0.1 g benzo [a] phenothiazine and 0.1 g phenothiazine. Layers made according to the method described in Example 4 produced high-contrast purple images upon exposure.

Example 6

To 60 g of a 10 ⁽⁾ / »by weight solution of polystyrene in ethylene chloride were added: 1.5 g of 2-azido - phenylcarbamylbenzimidazol, 0.1 g of benzo [b] -phenoxazin and 0.1 g phenothiazine. Layers produced therewith led to blue print-out images which were less saturated than those which were obtained when the benzo [b] phenoxazine was omitted.

Claims (6)

Patent claims: 1. Photosensitive layer with one or more organic heterocyclic azides as well as one or more heterocyclic coupling components and optionally a binding agent, characterized in that that the layer is an azide of one of the formulas Example 2 A coating solution was prepared consisting of 50 g of cellulose acetate, 17 g of 2-azido-1-carbobutoxymethylcarbamylbenzimidazole, 1.5 g of 2-azido-1-phenylcarbamylbenzimidazole, 1.0 g of benzo [b] phenoxazine and 200 g of acetone. The clear solution was coated onto a baryta-coated paper substrate using a hopper loader to give a coating of 1.6 g / 0.09 m ² (based on dry solids) and dried. By exposing these photosensitive layers to ultraviolet light through a negative master copy, a positive image was obtained which was almost neutral gray at all degrees of density. B e i s ρ i e 1 3 To 60 g of a 10 ^ll ₍₎ solution of cellulose acetate propionate in 2-butanone, 3 g of 2-azido-1 -carboisobutoxymethylcarbamylbenzimidazol. 0.4 g of 2-azido-1-phenylcarbamylbenzimidazole and 0.25 g of benzo [b] phenoxazine were added. Light-sensitive layers produced with it gave neutral gray images at all degrees of density. Example 4 To 25 g of a 10% solution of a vinyl chloride-vinyl acetate copolymer in 2-butanone was 0.5 g of 2-azido-1-phenylcarbamylbenzimidazole, 0.2 g Phenothiazine and 0.2 g benzo [c] phenothiazine are given. This mixture was made into a barite Paper brought, dried and using ultraviolet light through a negative halftone master copy exposed. The image color obtained was shifted to green compared to the image color, which is obtained without benzo [c] phenolhiazine. B e i s ρ i e 1 5 To 25 g of a 10% solution of a vinyl chloride-vinyl acetate copolymer in butanone were R ⁴ CN ₃ -R ³ Z N N, or Ν — Ν wherein Q equals an oxygen, sulfur or selenium atom or a> NR group. in which R is a hydrogen atom, an alkyl, aryl, sulfonyl, alkoyl, aroyl, carbalkoxy or carbamyl group, R ¹ and R ^{2 are} each a hydrogen atom or an alkyl, alkoxy, aryl or nitro group are a halogen atom or the non-metallic atoms necessary to complete a fused ring, and ^R;! equals an azido or an alkyl group, R 'equals an azido, an alkyl or an amino group, Z equals a = CH group or a = N group and R ³ is a hydrogen atom or an alkyl group. and a coupling component of one of the formulas wherein R "and R" each represent a hydrogen atom, an alkyl or aryl group. R ^s and R "are each equal to a hydrogen atom, an alkyl, alkoxy, aryl or nitro group or a halogen atom or the non-metallic atoms necessary to complete a fused ring. R" ¹ and R "each equal to a hydrogen atom, one Alkyl, alkoxy, aryl or nitro group, a halogen atom, a hydroxyl group or an oxygen atom or which are the non-metallic atoms necessary to complete a fused ring. 10 - s - or selenium atom, a methylene, imino - N group
or I R ¹² X- R ¹³ in which R ¹² is an alkyl group, X- " is an acid anion. R ¹³ is a hydrogen atom or an alkyl group and η is 1 or 2, where at least one of the ortho or para positions to the imino group of the coupling component must be unsubstituted . contains. 2. Photosensitive layer according to claim 1, characterized in that it contains 2-azidobenzoxazole, Benzo [a] phenothiazine, 2-azido-1-phenylcarbamylbenzimidazole and contains phenothiazine. 3. Photosensitive layer according to claim 1, characterized in that it contains 2-azido-l-carbobutoxymethylcarbamylbenzimidazole, Benzo [b] phenoxazine and 2-azido-1-phenylcarbamylbenzimidazole contains. 4. Photosensitive layer according to claim 1, characterized in that it contains 2-azido-l-phenylcarbamylbenzimidazole, Contains benzo [b] phenoxazine and phenothiazine. 5. Photosensitive layer according to claim 1, characterized in that it contains 2-azido-l-carboisobutoxymethylcarbamylbenzimidazole, Benzo [b] phenoxazine and 2-azido-1-phenylcarbamylbenzimidazole contains. 6. Photosensitive layer according to claim 1, characterized in that it is used as a binder Gelatin, casein, rubber, polystyrene, a vinyl polymer, a cellulose derivative or a Contains mixture of these polymers. 809 557/418 5.68 ® Bundesdruckerei Berlin