DD231146A1 - diazotype - Google Patents

Abstract

The object and the object of providing a diazotype material for recording information containing couplers having a large coupling activity and forming blue-green image dyes with an absorption maximum above 620 mm is achieved by dissolving the diazotype material consisting of diazonium salt, coupler, nickel ( II) salt, stabilizer acid, binders and optionally other photographic additives Blaupruenkuppler of the general formula in which R1, R2, R3 is hydrogen, alkyl, aralkyl, aryl, carboxyl; R4 is hydrogen, halogen, cyano, alkoxy, alkyl, contains.

Description

YEB Filmfabrik Wolfen Wolfen, 4 July 1984

PH 1125 Wa / Hgk

Dipl.-Chem. Heinrich Int. ³ : G 03 C 1/58

Dr. Marx

Prof. Dr. cooper

Prof. Dr. Becker

diazotype

Field of application of the invention

The invention relates to a diazotype material for recording information.

Characteristic of the known technical solutions.

Diazotype materials generally consist of photosensitive diazonium salts which react at the unexposed sites with couplers under the influence of bases to form image dyes.

The absorption maxima of blue image dyes in diazotype materials which use monodiazotized 4-phenylenediamines substituted as diazo components are generally between 580 and 620 nm. Even with the use of diazo components such. B. 4-Methoxybenzendiazoniumsalzen (DD-WP 148 910) or substituted monodiazotierten 2-phenylenediamines are obtained only image dyes whose absorption maxima are below 600 nm. Known blue couplers are substituted 2-naphthols (DE-PS 697 051), hydroxynaphthoic acid amines (DE-AS 1 169 293), 2,3-dihydroxynaphthalenes (DE-PS 922 390) or oxybenzotriazoles (DE-PS 83 869). Blue-green, light stable image dyes with

-7 R ftt-ίΉ 9Π943

an absorption maximum above 620 nm are obtained when heterocyclic hydrazone compounds with an in -Λ as a coupler. Position to the hydrazone heterocyclic nitrogen and simultaneously nickel, copper or cobalt compounds of organic carboxylic acids (DD-WP 206 003) or Ui (II) salts of aromatic sulfonic acids (DD-WP G 03 C / 251 386) are used.

Object of the invention

The aim of the invention is to improve the utility value properties of diazotype materials.

Explanation of the essence of the invention

The known diazotype materials, which have cyan image dyes with an absorption maximum above 620 nm, have low coupling activity.

Therefore, it is an object of the invention to provide a diazotype material containing couplers which have high coupling activity and form blue-gray image dyes having an absorption maximum above 620 nm.

According to the invention the object is achieved by the diazotype material consisting of diazonium salt, coupler, Hglckel- (II) salt, stabilizer acid, binder and optionally other photographic additives, cyan coupler of the general formula

-CH = H-HH

in the

R ₁ , R ₂ , R- are identical or different, hydrogen, alkyl

having 1 to 18 carbon atoms, aralkyl having 7 to 24 carbon atoms, optionally substituted,

Aryl of 6 to 18 carbon atoms, optionally substituted, carboxyl of 2 to 18 carbon atoms

R. hydrogen, halogen, cyano, alkoxy, alkyl

with 1 to 18 carbon atoms

mean, contains.

Blue couplers according to the invention can e.g. B.

3-Benzalhydrazino-4,6-dimethylpyridazine, 3- (p-chlorobenzalhydrazino) -4-> 6-dimethylpyridazine, 3-benzalhydrazino-4,5,6-trimethylpyridazine, 3- (p-chlorobenzalhydrazino) -4i6-diphenylpyridazine.

Substituted monodiazotized 4-phenylenediamines, substituted monodiazotized 2-phenylenediamines, diazotized 4-anilino-cinnamic acid derivatives or stilbene-4-diazonium salts are examples of the diazonium compounds which can be used in the diazotype material.

As Ki (II) salts find the Hickelsalze organic carboxylic acids or aromatic sulfonic acids use. Suitable binders are, for example, cellulose derivatives, vinyl polymers, copolymers of Yinylchlorids and Yinylacetats, polystyrene, copolymers of alkyl acrylates and acrylic acid and polyethylene oxides.

As the support material for the photosensitive layer, there may be used, among others, polymer films, paper, glass or metal.

Sulfosalicylic acid, 4-toluenesulfonic acid, citric acid or tartaric acid are used as stabilizer acid.

To prepare a casting solution, the cyan couplers according to the invention with a suitable diazonium salt, Ulckel (II) salt, stabilizer acid and optionally other photographic additives, such as. As plasticizers, inhibitors, other couplers of other types, mixed and dissolved in a polymer solution. This casting solution is applied to a substrate. The resulting diazotype materials according to the invention are characterized by a high coupling activity and, in the basic development step, give metal-complexed formazan dyes whose absorption maxima are bathoehromeric than 620 nm and which have good fastness to light.

Exemplary embodiments Synthesis example

Preparation of 3-Benzalhydrazino-4,6-dimethylpyridazine

a) 4-amino-1,2,4-triazole

475 g of 33% hydrazine hydrate are placed in a beaker and 106 g of formic acid are added with vigorous stirring. The reaction solution is then heated until a temperature of 20O ⁰ C is reached. This temperature is maintained for 3 minutes. Thereafter, the solution is cooled to 80 C and 33 ial ethanol are added. The 4-amino-1,2,4-triazole precipitates in white! Blemishes. After filtering off with suction, it is washed with ether and dried in an excipient.

Pp .: 77 - 7S ⁰ C

Yield: 125 g (65% c.L. Th.)

b) 6,8-dimethyl-5-triazolo-T, 3-yl-pyridazine

84 g (Hol) of 4-amino-1,2,4-triazole, 100 g (1 mol) of acetylacetone, 80 ml of xylene and 0.1 g of 4-toluenesulfonic acid are boiled on a water separator until the end of the water separation. After cooling, 50 ml of petroleum ether or gasoline 80/110 are added. The precipitate is filtered off and recrystallized from a little dioxane.

Mp .: 123 to 124 ⁰ C

Yield: 140 g (95 % of theory )

c) Quaternization of 6,8-dimethyl-5-triazolo -, 257-pyridazine 14.8 g (0.1 mol) of GjS-dimethyl-S-triazolo- ^ f ^^ - pyridazine are treated with 12.6 g ( 0.1 mol) of benzyl chloride in 20 ml of acetonitrile refluxed for 2 hours. The solvent is distilled off in vacuo and the residue is recrystallized from ethanol / acetone.

Pp .: 198-200 ⁰ C

Yield: 20 g (80 % of theory )

d) 3 - (/ 3-Pormyl-ZO -benzylhydrazino) -4,6-dimethylpyridazine 13.7 g (0.05 mol) of the quaternization product from c) are dissolved in 50 ml of water. Then 7.0 g (0.05 mol) KpCO- are added and the mixture held for 15 minutes at 70 ⁰ C. The separated brown oil solidifies under cooling to yellowish crystals, which are recrystallized from water.

Pp .: 124 - 127 ⁰ C

Yield: 9.2 g (72 % of theory )

e) 3- β- Benzylhydrazine.o-4 * 6-dimethylpridazine

5.0 g (0.02 mol) of 3 - (/ 3-formyl- / 3-benzylhydrazino) -4,6-dimethylpyridazine are boiled with 10.0 g of concentrated hydrochloric acid for 2 minutes. Upon cooling, the dihydrochloride precipitates as a white precipitate.

M.p .: 210-215 ° C. (dec.) Yield: 5.0 g (85 % of theory )

5.0 g of the dihydrochloride are dissolved in 10 ml of water and exactly neutralized with 1 N sodium hydroxide solution. The conspicuous yellow oil crystallizes upon cooling and can be recrystallized from gasoline / benzene.

Mp .: 109-112 ⁰ C

Yield: 3.2 g (85 % of theory )

f) 3-Benzalhydrazino-4,6-dimethylpyridazine

2.3 g (0.01 mol) of 3- / 3-benzylhydrazino-4,6-dimethylpyridazine are dissolved in 50 ml of water and adjusted to pH 9-10 with 0.1 N sodium hydroxide solution. With frequent shaking (stirring) allowed to stand for 2 days in the air. The precipitated crystals are removed by evaporation and recrystallized from ethanol.

Mp .: 166 - 167 ⁰ C

Yield: 1.36 g (90% of theory)

Application Example 1

The following diazo system is introduced into 1000 ml of a 7.5% strength cellulose acetate solution in methylene chloride / methanol, which is cast on a 10-15 m surface and gives a transparent film.

8S 2,5-Diethoxy-4-morpholinobenzendiazonium tetrafluorobenzoate

7 g of 3-benzalhydrazino-4,6-dimethylpyridazine 10 g of 4-toluenesulfonic acid

12 g of nickel butyrate

Hach Aufbelichtung a template and development in a humid HH - atmosphere at about 6O ⁰ C to obtain a cyan, positive image of the original. The absorption maximum of the blue-green image dye is 646 mn. The coupling speed is twice as high as in previously known cyan systems.

Application Example 2

The following diazo system is introduced into 1000 ml of a 7.5% cellulose acetate solution in methylene chloride / methanol, which is cast on a 10-15 m surface and gives a transparent PiIm:

8 g of 4-H ", H-Diethylaminobenzendiazoniumtetrafluoroborat 7 g of 3-Benzalhydrazino-4» 6-dimethylpyridazine

10 g of 4-toluenesulfonic acid 12 g of nickel propionate

Exposure and development are analogous to application example 1. The absorption maximum of the blue-green image dye is 667 nm. The very high extinction (> 2.2) is reached after a short development time.

Application Example 3

In 1000 ml of a 7.5% cellulose acetate solution in methylene

chloride / methanol, which is cast on 10-15 m surface and gives a transparent film, the following diazo system is introduced:

8 g 4 ^f diethylamino-oil-cyano-stilbene-4-diazonium tetrafluoroborate

7 g of 3-benzalhydrazino-4,6-d: methylpyridazine 10 g of 4-toluenesulfonic acid

12 g of nickel butyrate

Exposure and development are carried out analogously to application example 1. The absorption maximum of the cyan image dye is 690 nm. This very light-stable image dye is obtained after a short development time. The coupling speed is about three times as high as in previously known cyan systems.

Application Example 4

In 1000 ml of a 7.5% cellulose acetate solution in methylene

Chloride / methanol, which is cast on 10-15 m surface and ergifc.t a transparent PiIm, the following diazo system is introduced:

8 g of 2,5-diethoxy-4-morpholinobenzendiazonium

tetrafluoroborate

7 g of 3-benzalhydrazino-4,6-dimethylpyridazine

2 g acetoacetanilide 12 g 4-toluenesulfonic acid 12 g Uickteltosylat

Exposure and development are similar to application example 1. The absorption maximum of the cyan dye is 646 nm. Acetoacetanilide also forms a yellow dye with the diazonium salt having an absorption maximum of 440 nm, which significantly improves the duplicating properties of this material.

Application Example 5

In 1000 ml of a solution of methylene chloride / methanol, a diazo system according to Application Example 1 is used.

introduced. The solution is poured onto a 15-18 m paper surface. After imagewise exposure to the light of a mercury vapor lamp and development by dry ammonia gas under an ammonia pressure of 20 atms, a dark blue image on a light yellow background is obtained.

Application Example 6

According to Application Example 1 further systems are investigated, wherein the substituent R of the inventive cyan coupler and the hickel (II) salts are varied. The results are summarized in Table 1,

Table 1

complexing

7 { max

2-Cl Hickelpropionat 627 2-Cl Hickelbutyrat 627 4-Cl nickel propionate 640 4-Cl Uickelbutyrat 640 4-Cl Hickeltosylat 640 4-CH ₃ Hickelbutyrat 651 4-OCH ₃ Nickelpivalinat 658 4-0CH ₀ Mckelpropionat 658

- 10 -

Claims (1)

invention claim Diazotype material consisting of diazonium salt, coupler, nickel (II) salt, stabilizer acid, binder and optionally other photographic additives, characterized in that the material cyan coupler of the general formula / \ -CH = U-EB
^R 4 in the R 1, R ₂ , R ₄ , identical or different, denote hydrogen, alkyl having 1 to 18 carbon atoms, aralkyl having 7 to 24 carbon atoms, optionally substituted, Aryl having 6 to 18 carbon atoms, optionally substituted,
Carboxyl with 2 to 18 carbon atoms R, hydrogen, halogen, cyano, alkoxy, alkyl of 1 to 18 carbon atoms mean, contains.