DE1283091B - Photosensitive layer - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN # 87XW PATENTAMT Int. Cl .:

G 03 c

EDITORIAL

C07d

German class: 57 b-1/72

12 ρ-1/30, 3.4 / 01.6; 12q-24, 26

Number: 1283091

File number: P 12 83 091.0-51 (H 52379)

Filing date: April 16, 1964

Opening day: November 14, 1968

The invention relates to a photosensitive layer for copying out with 0.1 to 10 parts by weight of one Activator of the formula

R ¹ COOH

wherein R ¹ is an aryl or alkaryl group, of the formula

R ² CO - A

wherein R ² is an aryl, —NH-aryl or _{—CH 2} —CO — NR3 aryl group, R ³ is H, an alkyl, aralkyl, aryl or —CO —R ¹ group. R ¹ is H. an alkyl, aralkyl or aryl group and A is an alkyl, alkaryl or aryl group. or the formula

Q C = O

where Q equals those required to complete a heterocyclic 5- or 6-membered ring Atoms is. and with one part by weight of a leuco compound.

It is known to copy out photosensitive layers with at least one activator and one to use oxidizable leuco base. It has also been proposed to use a triphenylmethane dye to be used as a leuco base and the photosensitivity of the photographic recording material especially against ultraviolet light by adding certain aldehydes. To improve esters and ketones.

Disadvantages of these already known or proposed photographic recording materials is. that they still do not have satisfactory sensitivity to visual and ultraviolet Own light.

The object of the invention is. to specify light-sensitive layers that are copied out directly and which have an improved Have sensitivity to visible and ultraviolet light.

The object of the invention is based on a light-sensitive layer for copying out with 0.1 to 10 parts by weight of an activator of the formula

R ¹ COOH

jj ^ where R ¹ is an aryl or alkaryl group. - 'of the formula

R ² CO - A

wherein R- equals an aryl-. - NH-aryl or ~ * - CH ₂ - CO - NR ^{; 5} -aryf group, R ^{; i} is H, -i an alkvl-. Aralkvl-. Arvl or CO-R ¹ light-sensitive layer

Applicant:

Horizons Incorporated,

Cleveland, Ohio (V. St. A.)

Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys, 6000 Frankfurt, Große Eschenheimer Str. 39

Named as inventor:

Robert H. Sprague, Chelmsford, Mass .; John A. Stewart, Parma, Ohio; James M. Lewis, Cleveland, Ohio (V. St. A.)

Claimed priority:

V. St. v. America April 17, 1963 (273 569)

Group. R ¹ is H. an alkyl, aralkyl or aryl group and A is an alkyl, alkaryl or aryl group. or the formula

C = O

where Q is the number of atoms required to complete a heterocyclic 5- or 6-membered ring. and with one part by weight of a leuco compound and is characterized in that, as the leuco compound, it is a compound of the formula

R ⁵

R ⁵

509 637 / 12-1

contains where R ^{5 is the} same or different and is H, an alkyl group with 1 to 2 C atoms, an aryl group, R ^e is H, an alkyl group with 1 to 2 C atoms, an aryl group or a C6H5N (R ⁵ ) 2 group and Z is O, S, Se or NH.

The leuco compounds that can be used in the context of the invention are color-forming, colorless compounds of the above formulas, which are already used for photosensitive Layers proposed leukotriarylmethane dyes are very similar to each other this, however, by one or more bridging heteroatoms differentiate.

According to the invention, preferred leuco compounds are xanthenes, since with them in terms of photosensitivity exceptionally good results can be achieved. Preferred leuco compounds are the following xanthenes are used:

20th

3,6-bis (dimethylamino) -9- (p-dimethylamino-

phenyl) -xanthene,
3,6-bis (diethylamino) -9- (p-dimethylamino-

phenyl) -xanthene,
3,6-bis (diethylamino) -9- (p-diethylamino-

phenyl) -xanthene,
3,6-bis (dimethylamino) -9- (p-dimethylamino-

phenyl) thioxanthene.

According to one embodiment of the invention, the layer preferably contains a xanthene as the leuco compound 3,6-bis (diaikyIamino) -9- (p-dialkylaminophenyl) -xanthene.

As stated earlier, it is sensitive to light Layer an activator present. A colorless, organic compound with a keto group is used as the activator - optionally within a carboxyl group - used. The amounts of Activators can vary from 10 ': 1 to 1:10 parts by weight per part by weight of leuco compound.

The manufacture of photographic recording materials the photosensitive layer according to the invention can be carried out in a manner known per se. To the photosensitivity of photosensitive layers according to the present invention, the following methods were used used:

A mixture of 2 ecm each of acetone and a 10% solution of polystyrene in benzene. Herein those given in Table I below were given Amounts by weight of 3,6-bis (dimethylamino) -9- (p-dimethylaminophenyl) -xanthene and an listed activator dissolved. The coating liquid thus obtained was coated on a support Made of polyethylene glycol terephthalic acid ester, 0.038 mm thick, applied and allowed to air dry calmly.

The other method used only a mixture of benzene and acetone as the solvent used for the specified amounts of the leuco compound and the activator and with this solution treated with a filter paper.

The exposure of the first-mentioned light-sensitive material was either with a 500 watt photo lamp through a silver step wedge made for 5 minutes with a 30 cm from the photosensitive material remote lamp or with a sensitometer through a suitable daylight filter.

The exposure of the photosensitive Filter paper was also with a reflector photolamp through a step wedge at a distance of 30 cm with an exposure time of 30 seconds.

In order to fix the produced color image, a stable, practically usable image to produce, two methods known per se are used. In one process the was exposed Material two or more times for 15 seconds with a mixture of 1 part acetone and 4 parts Rinsed petroleum ether. In the other method, the exposed material was on for 4 minutes Heated to 125 ° C.

The fixed material was again totally exposed for 5 minutes with a photolamp. The evaluation of the exposed recording materials was made by the density and the number the steps visible in the resulting image were read after fixation. The evaluation of the photosensitized filter paper was done by determining the density behind a Green filter of a densitometer.

The results obtained with the exposures with the photolamp are shown in Table I.

Table I.
Leuco compound: 50 mg of 3,6-bis- (dimethylamino) -9- (p-dimethylaminophenyl) -xanthene

No, Activator weight
mg Type of fixation Exposure
Time
Minutes number
of the steps Gross
density Densities of
layer
carrier +
veil Nelto-
density 1 Benzoic acid 50 warmth 5 19th 1.55 . 0.36 1.19 2 α-naphthoic acid 50 solvent 5 21 1.57 0.25 1.32 warmth 5 21 2.57 0.33 2.24 3 1-hydroxy 50 solvent 5 21 2.12 0.25 1.87 2-naphthoic acid 4th 3-hydroxy solvent 5 21 2.46 0.15 2.31 2-naphthoic acid 5 2-mercaptobenzoe 50 solvent 5 21 2.02 0.23 1.79 acid (thiosalicylic acid)

continuation

No. Activator weight
mg Type of fixation Exposure
Time
Minutes number
of the steps Gross
density Densities of
layer
carrier +
veil net
density 6th Phenylacetic acid 50 warmth 5 18th 1.85 . 0.34 1.51 solvent 5 21 1.45 0.25 1.20 7th Naphthylacetic acid 50 solvent 5 21 2.00 0.15 1.85 δ 2,4-dichlorophenoxyl 50 solvent 5 21 2.60 0.29 2.31 acetic acid (Comparison without Leuco compound) 9 • 2 mercapto 50 solvent 5 21 2.22 0.13 2.09 1-naphthylacetic acid 10 Tribromoacetophenone 50 solvent 2 21 3.00 0.21 2.79 (with 100 mg Leuco connection) 11 p-nitroacetanilide 100 warmth 5 8th 0.48 0.28 0.20 12th Phenylacetanilide 100 warmth 5 11 0.72 0.28 0.44 13th «,«, «- Trichloroacet- 100 warmth 5 11 1.30 0.28 1.02 anilide 14th l-aceto-2-naphthol 15th warmth 5 21 1.77 0.78 0.99 solvent 5 21 1.31 0.30 1.01 15th Acetoacetanilide 100 warmth 5 . 12th 0.87 0.28 0.59 16 Acetoacet-2-chloro 70 warmth 5 12th 1.61 0.20 1.41 anilide 17th Acetoacet ^^ - dichloro- 100 warmth 5 10 1.19 0.32 0.87 anilide 18th Acetoacet-2,5-dichlor- 100 warmth 5 6th 0.77 0.48 0.29 N-benzoylanilide (Comparison without Leuco compound) 19th Acetoacet ^^ - dichloro- 100 solvent 5 9 0.60 0.16 0.44 N- (m-nitrobenzoyl) - anilide 20th Acetoacet - ^. S-dichloro- 100 warmth 5 18th 2.36 0.18 2.18 N-butyrylanilide 21 Monobenzoylaceto 100 warmth 5 12th 1.16 0.44 0.72 4.3 <3'-dichloro benzidide 22nd Monobenzoylacet- 50 warmth 5 • 13 0.95 0.35 0.60 benzidide 23 Acetoacet-2-chloro 100 warmth 5 17th 1.77 0.24 1.53 N-butyrylanilide 24 / i-naphthoylaceto- 50 warmth 5 11 2.25 0.35 1.90 mini solvent 5 13th 1.49 0.13 1.36 25th Phenylisoxazolone 100 warmth 5 11 2.20 0.17 2.03 26th 3-methyl-i-phenyI- 50 warmth 5 14th 2.17 0.20 1.97 5-pyrazolone 27 1,3-diphenyl-5-pyr- 50 solvent 5 11 0.55 0.07 0.48 azolone (comparison without leuco link) 28 Benzothiazolone 100 warmth 5, 12th 2.32 0.45 1.87 (with 100 mg Leuco compound)

The results obtained with the sensitometer exposures are shown in Table II.

7th Exposure line
• minutes 1,283,091 8th Gross density Densities of
Layer support + veil 30th 0.56 0.26 30th Table II 0.62 0.25 Mix no.
(as in Table I) 30th Number of stages 0.63 0.11 1 30th 9 0.52 0.08 2 10 14th 0.90 0.16 3 60 14th 1.31 0.51 4th 60 12th 0.74 0.22 5 30th 15th 0.65 0.11 6th 60 11 1.64 0.24 30th 12th 0.91 0.11 7th 30th 11 0.91 0.20 8th - 15th ~ - 9 30th 12th 0.50 0.16 10 ■■ —- 15th 11 to 15 120 ■ - 0.76 0.25 16 30th 9 0.55 0.18 17 to 24 30th - " 0.72 0.05 25th 60 9 0.76 0.28 26th 14th 27 11 28 9

The photographic recording materials with the photosensitive layers according to the invention like other light-sensitive materials, should be cool, dark and in a relatively dry place Environment.

The invention achieves that a photographic recording material which can be copied out directly has an improved photosensitivity and allows stable, practically usable To make pictures.

Claims (2)

Patent claims: 1. Light-sensitive layer for copying with 0.1 to 10 parts by weight of an activator the formula R ¹ COOH wherein R ¹ is an aryl or alkaryl group. the formula R-'CO -A wherein R ² equals an aryl, - NH-aryl or - CH ₂ - CO - NR ³ aryl group. R ^:) equals H. to an alkyl, arykyl aryl or - CO - R 'group. R ¹ is H. an alkyl, aralkyl or aryl group and A is an alkyl. Is alkaryl or aryl group. or the formula Q c = where Q equals those required to complete a heterocyclic 5- or 6-membered ring Atoms is. and with one part by weight of a leuco compound. characterized, that as a leuco compound it is a compound of the formula R "\ R ⁵ R ⁵ contains where R ^{1 is the} same or different and is H. an alkyl group with I to 2 carbon atoms, an aryl group. R "is H. an alkyl group with 1 to 2 carbon atoms, an aryl group or a CfiH .-, (R") -'- group and Z is OS Sc or NH. 2. Layer according to claim 1, characterized in that it is a xanthene as the leuco compound. preferably 3.6-bis (Dialk \ Tamino) -9- (p-dialkylaminophenyl) -xanthene contains.