DD143185A1 - ONE OR TWO-COMPONENT DIAZOTYPE MATERIAL - Google Patents

Description

The invention relates to diazotype material with novel photosensitive diazonium compounds, which may be one- or two-component material.

Characteristic of the known technical solutions

As is known, photosensitive benzo-diazonium compounds which contain a tertiary amino group in the 4-position to the diazonium group and further substituents in the benzene ring, preferably in the 2- and 5-position, are used for the preparation of diazotype material Photosensitivity, thermal stability and coupling speed of the diazonium compounds are mainly determined by these substituents (review in J. MUlTOEB in G. HAASE (Ed.) Scientific Foundations of Heprography, Hannover 1975, p. 120).

Specifically, the coupling rate of the diazonium compounds is affected by the best of the tertiary nitrogen atom and the other substituents present in the benzene ring. Thus, over lower alkyl groups, longer carbon chains or aralkyl groups on the nitrogen atom, as well as certain heterocyclic moieties in place of the tertiary amino group, such as morpholine or piperidine, increase the coupling rate. Furthermore, longer carbon chains of additional alkoxy groups present in the benzene nucleus cause a

- 2.- All. Coupling (MUlDES, cited above) ·

The so achievable coupling speeds are not sufficient for certain purposes. "Newer photo detectors have strong light sources that allow relatively short exposure times · Due to the low Eupplungsgeschwindigkeit and the long development time, a development in the same device can not be at the speed possible through the exposure maintained.

Furthermore, faster coupling diazonium compounds for Einkoinponentendiazotypiematerialien meaning, because then neutral or weakly acidic solutions can be used instead of the alkaline developer solutions, which are far more resistant than alkaline, but in which the coupling proceeds much slower. · The disadvantage of the low coupling speed can not be compensated by more active coupling components, because then would be too narrow in the color tones.

Efforts are known to increase the coupling speed by varying the substituents on the benzene ring in the 2- and 3-position. For example, it is known from BE-PS 676 820 that in the 3-position to the diazonium group, a trifluoromethyl group substantially increases the coupling speed. However, the photosensitivity of the diazonium compounds is thereby deteriorated. Sine trifluoromethyl group in the 2-position to the diazonium group increases, as known from DE-OS 1572 106 and DE-OS 2149 746, in addition to the coupling speed and the photosensitivity of the benzenediazonium salts. Similar to trifluoromethyl groups, other groups increase the coupling rate. From DE-OS 1572 098 diazonium compounds with fluorinated alkoxy groups and from DE-OS 1930 344 benzenediazonium compounds with cyanoalkoxy groups are known which couple quickly. With these diazonium compounds and conventional azo coupling components such as 2,3-dihydro-3-cynaphthalene and 2-hydroxy-3-naphthoic anilides. in an alkaline aqueous solution or in ammonia vapor

3 -

212 SS3

'are coupled, but 3'edoch no blue or black azo dyes but red to violet dyes.

Object of the invention

The aim of the invention is to produce a diazotype material with short development times, high photosensitivity and thermal stability.

Explanation of the invention of the invention

The object of the invention is to find diazonium compounds which are distinguished by an increased coupling speed compared to conventional compounds These diazonium compounds should form blue or black shades with the conventional azo coupling components.

The object is achieved according to the invention in that a benzenediazonium compound of the general formula Z CH ₉ CH ₀ CH is used as the light-sensitive compound.

in the

Z is hydrogen, an alkyl or hydroxy alkyl group of 1 to 5 carbon atoms, a cycloalkyl or aralkyl group of up to 10 carbon atoms, or the β-cyanoethyl group

E _{1 is} hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, halogens, preferably fluorine or chlorine, a fluorinated alkoxy group having 1 to h carbon atoms

a cyanoalkoxy group having 1 "to 4 carbon atoms, the trifluoromethyl group

E_ is hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, halogens, preferably fluorine or chlorine, a fluorinated alkoxy group having 1 to 4 carbon atoms, a cyanoalkoxy group having 1 to 4 carbon atoms, the trifluoromethyl group

E is hydrogen or halogen, preferably fluorine or chlorine and

X is the anion of the diazonium compound.

The inventively proposed new diazonium compounds have a significantly higher coupling activity over such Diaaoniumverbindungen containing 4-Stell.ung to Diazoniumgruppe an amino group which is substituted in a known manner, or a heterocyclic Best.

The dyes prepared with the claimed diazonium compounds and conventionally used coupling components are remarkably more lightfast than those obtained with the corresponding diazonium compounds substituted in a known manner.

The diazonium compounds are deposited in the usual way in the form of their stable complex or double salts. With the usual stabilizers and additives, such as SuI-f © salicylic acid, phenylacetic acid, thiourea, zinc chloride, etc., they are well tolerated. As carrier materials, as usual, plastic films, paper, transparent paper, transparent paper and glass can be used »

Depending on the choice of substituents, the diazonium compounds can be used for one- or two-component diazotype materials.

5 -

_5_ 212 85

Exemplary embodiments Example 1

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

8 g of 4-IT-ethyl: R-cyanoethylaminobenzenediazonium sulfonate

8β 2,3-dihydrozynaphthalene

3 g of acetoacetanilide

2 g sulfosalicylic acid.

The diazo compound used is obtained by diazotizing the nitrosation product of IT-cyanoethyl-IT-ethylaniline after catalytic reduction (Raney - Hi / Ho) in a mixture of 20 parts of glacial acetic acid and one part of sulfuric acid by isoamyl nitrite and precipitated by ether. By development at 40 C under constant UIL atmosphere, the maximum color density is reached after 26 s.

In Example 1 for 4-IT-Oyanethyl-iT-etliylaminobenzoldiazoniumsulfat the equimolar amount of 4-LT, IT ~ Diethylaminobenzoldiazonium tetrafluoroborat used, this time extended by about »20 to 32 s.

Example 2

In 1000 ml of a 7.5% polyvinyl alcohol solution in water,

which is cast in 10 to 15 in area and gives a transparent film, a diazo system of the following composition is introduced;

8 g of 4-hydroxyethyl-IT-cyanoethylaminobenzenediazonium

sulfate

10 g of R-SaIs 2 g of oxalic acid

; ^: - '_ ₆ _ 21' Z 05 ^. -

The diazonium compound used is obtained analogously to Example 1 from U-hydroxy-ir-cyanoethylaniline.

By developing at 40 ⁰ C under a constant Mo atmosphere 90 % of the maximum Far.bdichte are reached after 32 s. If 4-H-hydroxy-ir-ethylaminobenzenediazoniuitetrafluoroborat used, this time is extended to 39 s.

Example 3

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

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

8 g of 4-IT-cyanoethyl-1-ethyl-3-methylbenzenediazonium

sulfate

6 g of haphthol-AS-0L 2 g of resorcinol 2 g of cyanoacetic anilide 2 g of 4-toluenesulfonic acid

The diazonium compound was prepared analogously to Example 1 via the nitrosation of 2-methyl-ll-cyanoethyl-N-ethylaniline.

If, instead of the above diazonium compound, an equimolar amount of 4-pyrrolidino-3-methylbenzene-diiron compound is obtained, a diazotype material is obtained which couples more slowly and develops significantly less lightfast azo dyes.

Example 4

In 1000 ml of a 7.5 , cellulose propionate solution in methyl

lenchloride / methanol, which is cast on a 10 to 15 m surface and gives a transparent film, a diazo system of the following composition is introduced:

1 2 85

9 g of 2,5-diethoxy-4-L ^T , F-dicyanethylamine; above; 3-diazonium

sulfate

8 g of 2,3-dihydroxvnaphthalene 3 g of acetoacetbenaylamide 2 g of sulfosalicylic acid

Bas Kltrierungsprodukt of hydroquinone diethyl ether is catalytically reduced (Raney-Ifi / ^)> oyanethyliert and further processed according to Example 1 ·

If an equimolar amount of 2,5,5-diethoxy-4-morpholinebenzenediazonium compound is used instead of the above diasonium compound, the result is a diazotype material which couples more slowly and develops significantly γ / less lightfast azo dyes.

Example 5

In 1000 ml of a 7 _? 5% cellulose acetate solution in methylene chloride / methanol, which is cast on a 10 to 15 m surface and gives a transparent PiIm, a diazo system of the following Zusassiensetzung is introduced:

8 g of 4-If, ST-dicyanethyl-amino-2-propylbenzenediazonium

sulphate 2.g sulfosalicylic acid.

The Diasoniumverbindung used erliält man from 3-propyl-ΙΓ, ΙΓ-dicyanethylaniline analogous to Example 1.

Developing by the humid method at a constant pH> 8, phloroglucin and 2-hydro: sy-3-naphthoic acid ethanolamide give rise to 90 % of the maximum color density after 20 s. If, instead of the above Diasoniumverbindung an equimolar amount of 4-13 ", li-diethylamino-3-propylbenzoldiazoniumverbindung, so the development time is extended by more than 20 fo to 26 s.

-S

R ₁ R ₂

SOjH

NO,

C hj

Cl

OCH ₃

T-butoxy / ^ -Br

-Cl

OC H ₃ -CH ₃

-H

Y:

NO ₂

ij

Cl

CHj

OCHj

NO ₂ ΖΛ -OCH ₃ H T Chg Cl Π -Cl ^CHs / xl ~ H OCH, l £ i - NO ₂

-OCH ₅

-CH ₃

-Cl

-H

-NO,

LD ··

Z:

He

OCH ₅

Cl

NO ₂

C ₂ H ₅

III THERMAL STABILITY 2 CLUTCH

Xj LIGHT SENSITIVITY COLOR INTENSITY OF COLOR TOFFICITY OF PAINTING

Claims (1)

Z is hydrogen, an alkyl or hydroxyalkyl group with 1 to 5 carbon atoms, a cycloalkyl or aralkyl group having up to 10 carbon atoms or the
beta-cyanoethyl R. hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,
Halogens, preferably fluorine or chlorine, a fluorinated alkoxy group having 1 to 4 carbon atoms, a cyanoalkoxy group having 1 to 4 carbon atoms, the trifluoro. methyl group Ep is hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to β carbon atoms, Halogens, preferably fluorine or chlorine, a fluorinated alkoxy group having 1 to 4 carbon atoms, a cyanoalkoxy group having 1 "to 4 carbon atoms, the trifluoromethyl group Ε «hydrogen or halogen, preferably fluorine or chlorine and X denotes the anion of the diazonium compound "contains "751 / I Λ il S ./ι