DD205549A1 - diazotype - Google Patents

Abstract

The object of providing an information recording diazotype material containing red couplers which give narrow-band and brilliant reds, which are easy to synthesize and have good system compatibility, is solved by using the diazotype material consisting of diazonium salt, coupler, binder, Base and optionally further photographic additives, couplers of the general formula in which R 1, R 2, R 2, H 2, aralkyl, aryl, carboxyl; R deep 3, R deep 4 hydrogen, alkyl, aralkyl, aryl; X & Anion mean, contains.

Description

The invention relates to a diazotype material for information recording.

Characteristic of the known technical solutions

For a variety of applications BiIdfarbstoffe are with an absorption maximum between 500 and 600 nm of importance. Thus, for electrostatic backgrowths of diazotype materials to certain dye-sensitized zinc oxide media, a sufficient back-magnification contrast, ie a sufficient density difference of the image dyes between unexposed and exposed areas of the material, in the spectral range of 500 to 600 nra is needed. Diazotype materials whose image dyes give a neutral gray tone contain blues, yellows, and red couplers that must have a sharp absorption maximum. "Monochrome materials, visual aids, or color proofing media for controlling color proofs for color prints, also become very pure and thus narrow-band red or purple image dyes required. Known red couplers are naphthols, such as β- naphthol (U.S. Patent 3,715,213, U.S. Patent 3,948,661). The known for these types of couplers Azq Hydrazo tautomerism of the image dyes broaden the absorption spectrum strong, so that no pure shades are obtained.

_ ₂ "

Resorcylsäurederivate (DE-AS 1,572,083, US-PS 3,695,885) have a plurality of coupling active centers, which can arise due to differences in the development regime and local reactivity differences of the coupler to the diazonium salts in a solid matrix, both monoazo and bisazo, by their different absorption also lead to a B ^ orandenverbreite tion of the spectrum, pyrazolone couplers (US-PS 3,944,422, US-PS 3,824,101) tend to pre-coupling and thus fogging »urea and guanidine derivatives (US Patent No. 3,653,903 , DE-PS 691 283) give with the commonly used monodiazotierten 4-phenylenediamines image dyes with orange reds, is also known the use of monodiazotierten 2-phenylenediamines in conjunction with naphthol-AS-couplers (DD-WP G 03 C / 230 853) , with this combination no blue tones and thus in conjunction with conventional Rotkupplern no gray tones can be realized.

Object of the invention

The aim of the invention is to improve the performance characteristics of diazotype materials.

Explanation of the essence of the invention

The known red-drawing diazotype materials do not meet the requirement to produce image dyes with singly producible couplers, which deliver brilliant red or purple tones through their narrow absorption band. It is therefore an object of the invention to provide red couplers that provide narrow-band and brilliant red or purple tones, are easy to synthesize and have good system compatibility. According to the invention the object is achieved by the diazotype material consisting of diazonium salts coupler, binder, pad and optionally other photographic additives, couplers of the general formula ^

N-N-R.

R.-C CR, ^Λ

4 \ / ύ

R

υ a / ο / -

in the

R, R _{2 are the} same or different, hydrogen, alkyl of 1 to 18 carbon atoms, aralkyl of 7 to 24 carbon atoms, optionally substituted, aryl of 6 to 18 carbon atoms, optionally substituted, carboxyl of 2 to 18 carbon atoms;

R, R need be the same or different, are hydrogen, alkyl having 1 to 18 carbon atoms, aralkyl having 7 to 24 carbon atoms, aryl having 6 to 13 carbon atoms, wherein either R, or R is hydrogen _R

x "anion

mean, contains.

As the anion, all known ones, e.g. Chloride, toluenesulfonate, hydrogen sulfate, perchlorate possible.

The preparation of the couplers is carried out in a known manner by alkylation of substituted 1,2,4-triazoles, the substituted 1,2,4-triazoles, e.g. by condensation of hydrazines !! be obtained with formic acid.

Rotoproteins of the invention are, for example, 1-benzyl-4-benzylideneamino-1,2, 4-triazolyl chloride, 1-methyl-4-benzylideneamino-1,2, 4,4'-triazole-4'-toluenesulphate. Benzyl 4-diethylamino-1,2,4-triazolium chloride, 1-benzyl-4- (4'-dimethylamino) -benzalamino-1,2,4-triazolein chloride, 1,4-dibenzyl-1, 2,4-triazolium methosulfate , 1,3-dimethyl-4-araino-l, 2,4-1-riazolium tosylate, l-benzoyl-4-methyl-l, 2,4-t riazolium chloride. The red couplers are mixed to prepare the Diazotypiegießlösungen with one or more diazonium salts, stabilizer acid, optionally one or more other couplers and optionally other photographic additives, such as inhibitors in usual quantities in the diazotype, and then in a polymer solution or in a solvent solved. The casting solution is then either applied to a support or rinsed in a support.

υ 3 / ü / - 4 -

The resulting diazotype materials according to the invention are distinguished by brilliant red or purple hues. The red couplers are economical and easy to produce, show a good Systeraverträglichkeit and only slightly prone to pre-coupling.

Suitable diazonium salts are monodiazotized 4-phenylenediasnines, which optionally carry further substituents. Stabilizers used are salicylic acid, 4-toluenesulfonic acid, citric acid or tartaric acid. Additional couplers may be any known, e.g. Acetoacetatenine and cyanoacetic acid derivatives as yellow couplers, 2-hydroxy-3-naphthoic acid amides and 2,3-dihydroxynaphthalenes as blue couplers,

As binders, for example, cellulose derivatives, copolymers of vinyl chloride and vinyl acetate, copolymers of alkyl acrylates and acrylic acid, polyethylene oxides can be used. Furthermore, the material may still contain photographic additives, e.g. Plasticizers (dialkyl phthalate), development accelerators (zinc chloride), fading inhibitors (sterisbh hindered phenols and aromatic amines), and antifoggants (stilbene derivatives). Carrier materials for the photosensitive layer may be polymeric films, paper, translucent paper, glass or metal.

Ausfünruncjsbeispiel Example I In 1,000 ml of a 7.5% cellulose acetate solution in methylene chloride / methanol, which is molded to 10 to 15 m Polyethylenterephthalatunterlage and gives a transparent film, the following diazo system is introduced:

10 g of 1-benzyl-4-benzylideneamino-1, 2,4-triazolium chloride 8 g of 2,5-diethoxy-4-morpholinobenzendiazonium tetrafluoro-

borate 2 g of 4-toluenesulfonic acid

^ i * »Ί Λ Γ?

ιλ U 9 7

After image-wise exposure to the light of a mercury-vapor lamp and development by ammonia, a brilliant red positive image of the original is obtained. The absorption maximum of the red image dye is 534 nra.

Example 2

In 1000 ml of a 0.2% solution of cellulosic acetate in acetone / methanol, which is rinsed to a cellulose acetate pad at a speed of 6 m / min and, after drying, gives a transparent film such that the photographic system is immersed in the pad until 10 is diffused, the following diazo system is introduced:

28 g of l-methyl-4-ethyl-1, 2,4-triazolium-4-toluenesulfonate 25 g of 4-diethylaminobenzonediazoniuratetrachlorozincate 5 g of sulfosalicylic acid

After imagewise exposure to the light of a mercury vapor lamp and development by bathing in an aqueous solution of sodium carbonate and ammonium chloride at a pH of 9.5 gives a brilliant purple positive image of the original, the absorption maximum of the purple image dye is 555 nm.

Example 3

In 1000 ml of a 7.5% Polyvinylacetalbutyrallösung in

2 methylene chloride / methanol, which is cast on 10 to 15 m polyethylene terephthalate underlay and gives a transparent film, the following diazo system is introduced:

12 g of 1-benzyl-4- (4'-methoxy) -benzylideneamino-1, 2,4-

T riazolium tetrafluoroborate 10 g of 4-diethylaminobenzene diazosulphonate 1 g of citric acid

L ^ U 3 / Ό / - β -

After image-wise exposure to light of the wavelength range of 420 to 460 nm and development by ammonia, a brilliant, purple negative image of the original is obtained.

The absorption maximum space of the purple image dye is 540 na. The image is fixed by intensive second exposure with the full emission spectrum of a mercury vapor lamp.

Example 4

In 1000 ml of a 7.5% cellulose propionate solution in

Methylene chloride / methanol, which is cast on 10 to 15 ra transparent paper and gives a transparent film, one introduces the following diazo system:

4.0 g of 1-isopropyl-3-methyl-4-benzylideneamino-1, 2,4-

t riazolium perchlorate

3.0 g of acetoacetbenzylamide

7.5 g of 2-hydroxy-3-naphthoic acid 2-methoxy-5'-nitroanilide

9.5 g of 4-diethylaminobenzobenzonium tetrafluoroborate

2.0 g of 4-toluenesulfonic acid

4.0 g of thiourea

After image-wise exposure to the light of a mercury-vapor lamp and development by dry ammonia gas under an ammonia pressure of 20 at, raan obtains an approximately neutral-gray image of the original.

Example 5

Example 4, but instead of 2-hydroxy-3-nsphthoesäure-2-methoxy-5 * -nitroanilicL an equimolar amount of phloroglycine. After image-wise contact exposure of a microfilm template of the reproduction scale 1:42 and development by ammonia, a brown positive image of the microfilm master is obtained. The diazo copy can be readily electrophotographically re-enlarged on eosin-sensitized zinc oxide re-enlarging paper *.

Example 6 i _: . _v

In 10 ml of a 7.5% polyvinyl alcohol solution in water, which is poured onto a 600 cn subbed glass and after 8 hours drying at room temperature gives a transparent film, the following diazo system is introduced:

70 mg of l-benzyl-4-benzylideneamino-l, 2,4-t riazoliumhydregen-

Sulfate 60 mg of 4,4 N-ethyl-N-cyanoethylaminobenzendiazoniurahydrogen-

sulfate 50 mg oxalic acid

After imagewise exposure to the light of a mercury-vapor lamp and development in a moist ammonia atmosphere at 313 K, a brilliant red image of the original is obtained. The absorption maximum is 530 nm.

Example 7

In Table 1 are further varied couplers in a standard diazo system consisting of:

8 g of 2,5-diethoxy-4-niophenolbenzendiazonium tetrafluoro-

borate and Ig 4-toluenesulfonic acid in 1 l of 7.5% cellulose acetate solution in methsol / methylene chloride, in the amount of 10 g.

After imagewise exposure and development, one obtains positive images of the original on a transparent background.

g ^ TW *** S ^ BT

-B-

Table 1

Coupler ^ ax of the image color

Substance / nm

l-benzyl-4- (4-methylbenzylideneamino) -l, 2,4-t ria-

zolium chloride 540

l-ethyl-4-ethyl-1 _f 2- _f 4-triazo-chloride 545

1-Benzyl-4- (4'-methoxybenzylidenarainc) -! ; 2. , 4-t ria

zolium chloride 547

I-3enzyl-4-amino-l, 2,4-triazolium chloride 555

i-Benzyl-4- (4-methoxy-2'-methylbenzylideneamine) -

1,2,4-triazolium chloride '555

l-Benzyl-4- (4'-Dimethylaminobenzylidenaminc ^ -

1,2,4-triazolyl chloride 570

1-Benzyl-4- (4'-diethylarainobenzylideneamine) -1, 2,4-

triazolium chloride 576

l-3enzyl-4-benzyl-l, 2, 4-triazolium chloride 570

Claims (1)

O / rfindungsanspruch Diazotype material consisting of diazonium salt, coupler, binder, substrate and optionally other photographic additives, g e! <E η π ζ e i c h η e t characterized in that the material couplers of the general formula Φ
NNR. H ίι ¹ ν e
¹ Vx / ^R 3 N ' ^R 2 in the R ₁ J-Rp, same or different, represents hydrogen, alkyl of 1 to 18 carbon atoms, aralkyl of 7 to 24 carbon atoms, optionally substituted. Aryl of 6 to 18 carbon atoms, optionally substituted, carboxyl of 2 to 18 carbon atoms; · R 1, R 2 are the same or different, hydrogen, or alkyl of 1 to 18 carbon atoms, aralkyl of 7 to 24 carbon atoms, Aryl of 6 to 18 carbon atoms'; in which always either R-, or R ^ vv're rstdf f must be - j> 4 X ~ anion
mean, contains.