DD219600A1 - diazotype - Google Patents

Abstract

The task of creating a diazotype material which, after appropriate exposure and development, is distinguished by the formation of dyes having a high extinction in the spectral range of 330-440 nm and a second absorption in the range of 430-550 nm and thus having a high contrast, is solubilized by the diazotype material, consisting of pad, diazonium compound, coupler, binder and optionally further additions a combination of Cyanacetamiden as yellow coupler, which forms a dye having an absorption maximum between 400 and 430 nm with the diazonium compound, and a second coupler or coupler mixture of the general Formula I and / or 2-aminothiazole and / or 2-aminobenzothiazole, wherein R1 is H, phenyl, alkyl; R2 is phenyl, COOH, COR3, alkyl; R3 is alkoxy, amino; R4 is alkyl, alkoxy, halo-SO3H, -SO3, mean, contains. Formula I

Description

diazotype

Field of application of the invention

The invention relates to a diazotype material for information recording '

Characteristic of the known technical solutions

Diazotype materials consist of photosensitive diazonium compounds, which are non-radically capable of reacting with colored couplers either in a coating system or in a developing bath to form colored azo compounds. At the exposed areas is no. More possible coupling (see, inter alia, D. Munder in G. Haase, Ed ,, Wiss. Grundlagen der Reprographie, Hannover 1975, p. 120; M.S. Dinaburg, Photosensitive Diazo Compounds, Focal Press, London - New York, 1964).

The most significant characteristic parameters of diazotype materials are photosensitivity, thermal stability, coupling speed, maximum and minimum density, gradation, spectral behavior and stability of image dyes, the spectral distribution of the after

X fi

t *

Coupling process resulting image Farbs _(tof fe is very important for further demanded by certain diazotype properties such as suitability as an intermediate copy to other photosensitive materials having certain spectral curve of the sensitivity curve and for the visual color impression. These parameters are very largely determined by the choice of the coupler, and , when using multiple couplers, by their concentration ratios to each other.

For certain uses, such as Transopaque films, it is necessary to use diazotype materials that form dyes with a high extinction in the near UV range beginning at the beginning of the visible spectral range (330-440 nm) (D _ax "~ 3.5) and In addition, the material developed should have a secondary absorption between 430-550 nm, which improves the visual recognition during processing and thus the handling and readability in general Furthermore, the dyes should meet the other common requirements for a two-component diazotype material, There are various yellow couplers and other couplers used for the preparation of intermediate copies for diazotype materials, such as acetoacetanilides, resorcinol and derivatives and phenol derivatives, but the dyestuffs formed thereby in the course of their development are known to have excellent fading resistance in the near UV absorption too low absorption. In addition kommoiz.T. Further disadvantages of the couplers such as lack of storage stability in Zvveikomponentenmaterial. Further, cyanoacetamides are known as yellow couplers (eg US Pat. No. 2,537,001, DE-AS 1 793 150, DE-OS 2 746 551). Although dyes are obtained which absorb sufficiently in the near UV range, the materials developed are yellow in color and thus visually detectable in yellow. Processing light.

¹ it is further known that Cyanäcetamide be used in combination with blue couplers such as 2,3-Hydroxynaphthoesäurederivaten (eg DE-OS 2746551, US-FS 3,836,369). These combinations have the disadvantage of the relatively high intrinsic absorption of the UV couplers in the near-UV region, which precludes the use of such materials as zvvic copying: for photosensitive materials having a sensitivity maximum in this field. Also known is a material (DE-A3 1 813 713) containing two couplers, wherein the dye of the one coupler undergoes a hypsochromic shift into the near UV region after development by treatment with a strong acid. However, this color shift is reversible (already partially reversed by ordinary storage), which limits the useful life of such materials, and processing becomes complicated and cumbersome by the additional processing bath or machining.

Object of the invention

The object of the invention is to produce by means of a two-component diazotype material in a simple way copying, which are used as so-called Transopaqus films in the manufacture of printed circuit boards.

Explanation of the essence of the invention

The known diazotype materials do not meet all the requirements that are placed on materials that should be suitable as intermediate copies for printed circuit board production. It is therefore an object of the invention to eit.'iicke a material . In, which is characterized by corresponding exposure and development by the formation of dyes with a high absorbance in the spectral range of 330 - 440 nra, and a second absorption in the range of 430 - 550 nm and thus has a high contrast. .

The 3ildfarbstoffe must have sufficient light stability, especially in the near UV range possess. In the developed state, the material must not cause any disturbing intrinsic absorption. Furthermore, the material should be easy and uncomplicated to process and possess sufficient storage stability.

According to the invention the object is achieved by the Diazotypiematerial, consisting of pad, diazonium compound, coupler, binder and optionally further additives sire combination of Cyanacetaraidenals yellow coupler, -which with the Diazoniuraverbindung forms a dye having an absorption maximum between 400 and 430 nm _/ and a second coupler or Kupplergejnisch the general formula

H ₂ C- (JR

O = C N V

and or

CH ₃ -CO-CH ₂ -CO-MH- /. '''' - ^τΐ

and or .

2-aminothiazol

and or

2-aminobenzothiazole

in which . ,

H, phenyl, substituted phenyl, alkyl; Phenyl, substituted phenyl, COOH, COR, alkyl of 1 to 3 carbon atoms;

R. Alkoxy, amino;

R ⁴ alkyl, alkoxy, halogen -SO ₃ H, -SQ mean, contains.

The molar ratio between yellow and second couplers is 5: 1 to 70: 1, which, because the second coupler has been selected so that its coupling speed is greater than that of the yellow coupler, is still sufficient for a sufficiently high optical density of the dye from the second coupler , The molar ratio of coupler to diazonium salt is variable, but a significant coupler excess proves to be beneficial.

Cyanacetamides according to the invention are compounds of the general formula

, , CN-CH ₂ -CO-R ¹ ''.

1

wherein R is dialkylamino, benzylaiaino, alkylamino, substituted arylamino, anilino, a nitrogen-containing heterocycle such as e.g. Morpholino, piperidino, pyrrolidino

mean.

Particularly suitable diazonium compounds are of the monodiazotised p-phenylenediamine type, especially dX- 2,5-dialkoxy-substituted compounds.

As anions to the diazonium cation preferably find such complex anions application, the cation thermally

- Stabilize '2- -''2-, such as SF. , ZnCl ₀ , HSO. , SbCl ,. , CdBr ₄ ~, SnCIg ". Suitable stabilizers are organically highly soluble, low-volatile acids such as 4-Tdluensulfonsäure and SuIfosalizylsäure. Suitable binders are -any film formable, forming a transparent matrix, swellable little with water permeable possible polymers suitable, such as Cellulose derivatives, vinyl polymers and copolymers of vinyl chloride and vinyl acetate.

Support materials for the photosensitive layer may i.a. Be polymer films and glass. As other additives, plasticizers (e.g., diethyl phthalate, dibutyl phthalate, tricresyl phosphate), image dye stablizers (e.g., hydroquinone dialkyl ethers, hindered phenols, aromatic amines) or antifoggants (e.g., stilbene derivatives) may be incorporated.

    ·. ''. - s -

For the preparation of the casting solution d.i.e components are introduced into the solution of a 'binder, wherein when Zusämmehgeben diazo component and coupler sufficient acidity must be present to prevent the pre-coupling. Suitable solvents are e.g. the easily volatilizable lower aliphatic alcohols, ketones and chlorinated hydrocarbons or mixtures thereof. The diazotyping solution is prepared by the known methods, e.g. that dipping or Anspülwalzenverfahren applied to the UnteVlage. The useful layer thicknesses are in the range 5-10. The diazotype materials according to the invention are distinguished by the strong absorption of the image dyes in the range of 330-440 nm (Dx3.5) as well as a secondary absorption in the range 430-550 nm. They have a high contrast (especially in the near UV range), are sufficiently stable in light and have no disturbing intrinsic absorptions, The materials are uncomplicated processable and have sufficient storage stability as other common Zvveikomponentendiazotypiematerialien, making them particularly as intermediate copies for materials with a high photosensitivity in the near UV range (eg photoresists, photoresists) suitable. Especially when the developed diazotype layers are used in yellow light, the good visual evaluability of the images on the basis of the formulation according to the invention is advantageous-for the effect *

embodiments example 1

In 1000 ml of a 10% cellulose acetate solution in methylene chloride / methanol

17.3 g of 2,5-Oiethoxy-4-raorpholinobenzendiazoniuratetrafluoroborat

14.8 g of cyanoacetic acid morpholide

0.6 g of 1-phenyl-3-methyl-pyrazolone (5)

6 g of p-toluenesulfonic acid * ·.

5 g of diethyl phthalate

dissolved and potted on subbed polyethylene terephthalate underlay. The obtained transparent film with a layer thickness of 6, UEi is developed after appropriate exposure to the diazo developing device ODE 1 (VEB Carl Zeiss Dena). Is obtained at the non-exposed Bildteilenein reddish brown dye image having a main absorption maximum from 410 to 430 nm (D _χ> 3.8) a high absorption in the near UV range (D2. 2.5) and between 450 and 500 nm. Comparative film without l-phenyl-3-methyl-pyr azolone (5) forms only a yellow dye image and no high dye absorption between 450 and 500 nm.

Be i s ρ i e 1 2 ~

In 1000 ml of a 10% cellulose acetate solution in methylene chloride / methanol

13.3 g of 2,5-diethoxy-4-morpholinobenzendiazonium. tetrafluoroborate cyanoacetic acid o-toluidide 1,3-diphenylpyrazolone (5) p-toluene sulphonic acid, oibutyl phthalate "

dissolved and potted on subbed polyethylene terephthalate. The obtained transparent film with a layer thickness of 5 μm is exposed and developed according to Example 1 ». A red-brown dye image is obtained with a similar absorption curve as the film in Example 1.

example

Example 2, but instead of 0.8 g of 1,3-diphenylpyrazolone (5), 0.65 g of acetoacetic acid p-anisidide are used. After exposure and development according to Example 1, a yellow-brown dye image with a similar absorption in the near UV region as the film of the case, game 1 and a relative to Example 1 slightly hypsochromic shifted secondary absorption.

 ' - 8th -

16 S 0.8 G 6.2 G '5 G

Examples

.Vie example 2 ,. only * instead of 0.8 g of 1,3-Qiphenyipyrazolon (5) 0.5 g of 2-aminobenzothiazole be used. After exposure and development according to Example 1, a yellow-brown dye image with a similar absorption curve as the film of Example 3 is obtained.

Example '5'.

IVie Example I ₁ only 0.7 g of 1-phenyl-3-carboxylic acid pyrazolone (5) are used instead of 0.6 g of 1-phenyl-3-ethylpyrazolone (S). After exposure and development according to example 1, a red-brown dye image is obtained with a similar absorption curve to that in Example 1. '\'

Example 6

Like Example 1, instead of 17.3 g of 2,5-diethoxy-4-morpholinobenzendiazoniumtetrafluoroborai: 19.5 g of 2,5-dibutoxy-4-morpholinobenzendiazoniuratetrafluoroborat be used. After exposure and development according to Example 1, a red-brown dye image with a similar absorption curve as the film in Example 1 is obtained.

Example 7

As Example 2, only instead of 18.3 g of 2,5-Oiethoxy-4-morpholinobenzendiazoniumtetrafluoroborat 14.2 g of 4-Piperidinobenzendiazoniumtetrafluoroborat be used. After exposure and development according to Example 1, a red-brown dye image with a similar absorption curve as the film in Example 1 is obtained.

Claims (3)

r f i η dun g s η s ρ r u c h. Diazotype material, .A consisting of pad, diazonium compound, coupler, binder and optionally further additives, characterized by a coupler combination of a cyanacetamide as a yellow coupler, which forms a dye having an absorption maximum between 400 and 430 ηm with the diazonium compound, and a second coupler or coupler mixture of the general formulas 2 and or and / or and / or in which R ¹ "· R ² • 2 ι O = C II l · - CH ₃ -CG-CH ₂ -CO-NH- 2-Arainothiazol 2-aminobenzothiazole H, phenyl, substituted phenyl, alkyl; Phenyl, substituted phenyl, COOH, COR * ³ , alkyl with 1 to 3. carbon atoms, · Alkoxy, amino; Alkyl, alkoxy, halogen, -SO ₃ H, -SO ₃ ' mean.