DE3418469A1 - LIGHT-SENSITIVE MIXTURE AND TWO-COMPONENT DIAZOTYPE MATERIAL PRODUCED WITH IT - Google Patents

Abstract

1. A light-sensitive mixture, composed of a diazonium salt, a coupler, a resin binder, a stabilizer, conventional additives and a liquid phase, which comprises a combination of a) at least one p-aminobenzenediazonium hexafluophosphate, b) at least one 4,4-dihydroxy-diphenyl sulfide, if appropriate as a mixture with a further coupler, c) an acid stabilizer in a concentration from zero to 20 per cent by weight, relative to the diazonium salt employed, d) at least one plastic which contains acid groups, has an acid number of at least 100 and is derived from the maleic acid or phthalic acid type, as the resin binder, and e) lower alcohols, glycol ethers, ketones water or mixtures of these solvents.

Description

HOECHST AKTIENGESELLSCHAFl HALLE Branch of Hoechst AG

84 / K 044 May 17, 1984

WLK-Dr.S.-gv

LIGHT-SENSITIVE MIXTURE AND A TWO-COMPONENT DIAZOTYPE MATERIAL MANUFACTURED WITH IT

The invention relates to a photosensitive mixture from diazonium salt, coupler, resin binder, acidic stabilizer, usual additives and a liquid Phase as well as two-component diazotype material produced with it.

It is known to use diazonium salts with coupling components in formulations for two-component diazotype materials to use. The diazonium salts used are in particular those which are derived from p-phenylenediamine.

4-dialkylamino-3-chlorobenzoidiazonium compounds for Use in diazotype materials are known from the literature. They are usually called salts of the Sulfuric acid or tetrafluoroboric acid and as double salts with zinc chloride, cadmium chloride or Tin tetrachloride deposited and in these salt forms for the production of diazotype coating recipes technically used.

The zinc chloride double salt and the tetrafluoborate of the 4-dimethylamino and 4-diethylamino-3-chlorobenzene diazonium compound have been known for a long time (FIAT REPORT 813, p. 797 and 1048) and are due to their relatively high coupling activity preferred for the production of one-component diazotype materials,

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

those with resorcinol and phloroglucinol as coupling components containing, alkaline buffered, aqueous solutions can be developed, used. Because the very good UV absorption of their mono- and polyhydroxybenzene derivatives achievable dyes, these diazo compounds are particularly suitable for the production of one-component diazotype intermediate master materials.

Even faster than the 4-dimethylamino and 4-diethylamino-3-chlorobenzene diazonium compounds couple compounds of the 4-methyl-cyclohexylamine-3-chlorobenzene diazonium salt type (Dutch patent specification 243 429), 4-methyl-cyclohexylamino-2,5-dichloro-benzene diazonium salt (DE-AS 12 90 809) and 4-methyl-cyclohexylamino-5-chloro-2-trifluoromethylbenzenediazonium salt (DE-PS 22 26 532). These diazo compounds are therefore used for the production of one-component diazotype material, the neutral to weakly acidic buffered aqueous solutions containing resorcinol and phloroglucinol can be developed, particularly well suited. Suitable when using a transparent substrate Such a one-component diazotype material is ideal as an intermediate original for production further copies on UV-sensitive materials. These diazo compounds are also preferred as salts of Sulfuric acid, tetrafluoroboric acid or as Double salts made with zinc chloride, cadmium chloride or tin tetrachloride and used as such industrially.

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

4-aminobenzene diazonium compounds with one halogen atom in the 3-position to the diazonium group and 4-aminobenzene diazonium compounds with a halogen atom in the 3-position to the diazonium group and an additional halogen atom, an ether, thioether or trifluoromethyl radical in the 6-position are more light-sensitive, more active on the coupling and more thermally stable than compounds without one of the substituents mentioned. Also absorb Azo dyes made from 4-amino-3-halobenzene diazonium compounds and mono- and / or polyhydroxybenzene derivatives are formed which emit UV radiation much more effective than azo dyes made from 4-aminobenzene diazonium compounds, which have no substituents or an ether or thioether radical in the 3- and / or 6-position. When developing with commercially available Resorcinol and phloroglucinol containing alkaline or neutral to weakly acidic buffered aqueous Solutions one obtains strong dark colorants with a high absorption in the visual and ultraviolet Spectral range.

Because of their relatively high coupling activity, the hydrogen sulfates, tetrafluoroborates and the double salts with zinc chloride, cadmium chloride and tin tetrachloride of the known 4-amino-3-halogenobenzene diazonium compounds for two-component diazotype materials only in combination with coupling components of low activity are used and only if to prevent premature coupling of the unprocessed Diazotype material has a relatively high concentration

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

Tration of acidic stabilizers in the two-component diazotype layer is present. The presence of relatively large amounts of stabilizers, however, often leads to incompatibilities in the coating composition and to the formation of deposits ("exudation") on the layer surface of such diazotype materials under warm, humid storage and development conditions. Exudation in diazotype materials leads to considerable technical disadvantages and is therefore undesirable in practice. In DE-OS 17 72 072 such a two-component diazotype material is described. It contains a zinc chloride double salt of ^: 4-dimethylamino- or 4-diethylamino-chlorobenzene diazonium chloride in combination with 4-morpholino-2,5-dialkylphenol and considerable amounts of acidic stabilizers. This diazotype material is developed with alkaline solutions and can be used very well as an intermediate original material when using transparent paper as the layer support. Despite the high concentration of stabilizer, the shelf life of the unprocessed material is very limited, especially in warm and humid storage conditions, and is not entirely sufficient for practical use. In addition, this diazotype material tends to exude during storage and development.

Under the trade name "Transopaque Film G-2" (Thiokol / Dynachem Corporation) has recently become known a Diazof! Immaterial based on a Benzoldiazonium hexafluophosphate as light-sensitive

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

before connection is established. With this film, after imagewise exposure, light brown copies of high UV and sufficient visual contrast are obtained. The durability of this film in the unprocessed state under warm, humid climatic conditions at 40 ⁰ C and 8o% relative humidity. however not satisfactory. In addition, irreversible damage to the coating occurs during processing under moist and very warm development conditions ("wrinkled structure" due to the formation of bubbles), combined with a complete loss of layer adhesion on the substrate. A diazo copy produced under such development conditions is no longer usable for the application.

It was an object of the invention to provide a light-sensitive Liquid copying varnish in the form of a mixture of diazonium salt, Couplers, resin binders, diazo printing auxiliaries, liquid phase, and optionally acidic stabilizer to provide user self-coating, with the individual components of the liquid copy lacquer or a "semi-finished product" of liquid phase, resin binder, coupler, diazo printing aid and optionally acidic stabilizer separately from the photosensitive diazo compound for self-coating may exist. It was also an object of the invention to provide a light-sensitive two-component diazotype material to create that with a relatively low stabilizer concentration even under difficult conditions can still be kept well in moist and warm storage

HOECHST AKTIENGESELLSCHAFl KALLE Branch of Hoechst AG

and its diazotype layer does not exude on storage and development under extreme conditions and therefore no deposit formation on the surface of the film layer shows. The material should also not be developed in very humid and warm conditions form unwanted bubbles. Intermediate originals produced therefrom should also have a high Have UV and good visual contrast.

The task is through a photosensitive mixture solved the type mentioned, which is characterized by the combination of

a) at least one p-aminobenzene diazonim hexafluophosphate,

b) at least one dihydroxydiphenyl sulfide, if appropriate mixed with another coupler,

c) acidic stabilizer in a concentration of zero to 20 percent by weight, based on the used Diazonium salt,

d) at least one plastic containing acidic groups

substance with an acid number of at least 100, the derived from maleic acid or phthalic acid type as resin binder and

e) lower alcohols, glycol ethers, ketones and water alone or in a mixture as the liquid phase

HOECHST AKT.IENGESELLSCHAFl HALLE branch of Hoechst AG

and by a two-component diazotype material made therewith with a light-sensitive layer made from components a) to d). As p-aminobenzene diazonium hexafluophosphate in particular compounds of the general formula come into question

in which R ^ alkyl with 1 to 6 carbon atoms, Alkenyl with up to 4 carbon atoms or cycloalkyl with up to 8 carbons

material atoms,

^ 2 optionally substituted alkyl with 1 to 18 carbon atoms, alkenyl with up to 4 carbon atoms, cycloalkyl with 6 to 12 carbon atoms, optionally substituted aralkyl of 7 to 12 carbon atoms or

R-] and R £ together with the nitrogen atom, to which they are bound, an optionally substituted 5- to 8-membered heterocyclic radical,

X chlorine or bromine and
Y hydrogen, chlorine or bromine, tri-

fluoromethyl, an ether or thio

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

'Ψ-

ether group

mean is present. As dihydroxy diphenyl sulfide in particular compounds of the general formula come

R3

R ₄

OH

R ₄

in question, optionally in a mixture with at least one coupler of the following general formulas

RS-HNO ₂ S OH

SO2NH-R7

R9-HNCO

SO ₂ N ^

HOHO *

OLO

SO ₂ N.

.R ₁₂

HOECHST AKTIENGESELLSCHAPl HALLE Branch of Hoechst AG

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in which R3 and R4 are identical or different and are hydrogen or alkyl with 1 to 4 carbon atoms, where at least one of the positions o to the OH group is represented by hydrogen is busy

R5 and R6 are identical or different and Hydrogen, carboxyl or optionally substituted by a hydroxyl or amino group Carboxyalkyl or carboxy aryl amide,

R7 and Rß are the same or different and Hydrogen, alkyl, alkenyl, hydroxylalkyl with 1 to 4 carbon atoms, optionally substituted aryl with 6 to 12 carbon atoms,

R9, R- | 0 and R-j 1 are the same or different and hydrogen or an optionally substituted alkyl having 1 to 6 carbon atoms or cycloalkyl of 6 to 12 carbon atoms, aryl or aralkyl of 6 to 12

Carbon atoms or

Rl 0 ^{un <} 3 Rf 1 together with the nitrogen atom to which they are attached, an optionally substituted 5- to 8-membered heterocyclic radical,

R-] 2 hydrogen,

R ^ 3 optionally substituted by alkyl groups Cycloalkyl with up to 8 carbon atoms, aralkyl with up to 10 carbon atoms, optionally substituted aryl or

/ ti

HOECHST AKTIENGESELLSCHAFT. KALLE branch of Hoechst AG

R-] 2 and R] 3 together with the nitrogen atom to which they are bonded, an optionally substituted 5- to 8-membered heterocyclic radical and
Z denote hydrogen, chlorine or bromine are present. Heterocyclic radicals are pyrrolidino, piperidino, piperazino, morpholino, thiomorpholino, He-Harnethylenimino- or heptamethylene

imino residues.
10

The preferred diazonium salt in the mixture is 4-dimethylamino-3-chlorobenzene diazonium hexafluophosphate and the coupler is 2,2'-dimethyl-4,4'-dihydroxy-5,5'-di (tert) butyl diphenyl sulfide and 2,4 -Dihydroxybenzoesäu- ^ re available.

Further preferred mixtures serve as the diazonium salt 4-dimethylamino-3-chlorobenzene diazonium hexafluophosphate and as the coupler 2,2′-dimethyl-4,4′-dihydroxy-5,5′-di (tert.) Butyl diphenyl sulfide, 2,4 Dihydroxybenzoic acid and 2,3-dihydroxynaphthalene-6-sulfonic acid-N (4'-chlorophenyl) -amide, or as the diazonium salt 4-methyl-cyclohexylamine-3-chlorobenzene-diazonium hexafluophosphate and as a coupler 2,2'-dimethyl-4,4 ¹ -d-

hydroxy-5,5-di (tert.) butyl diphenyl sulfide and 1 -hydroxynaphthalene-3-sulfonic acid-N (4'-chlorophenyl) - -amid-8-sulfonic acid-N (n-butyl) amide, or as the diazonium salt 4-diethylamino-2,5-dichlorobenzene diazonium hexafluophosphate, as a coupler 2,2'-dimethyl-4,4'-dihydroxy-5,5'-di (tert.) butyl-diphenyl sulfide and 2,4-dihydroxybenzoic acid, or as a diazonium salt 4-methyl-cyclo-

HOECHST AKTIENGESELLSCHAFl KALLE Branch of Hoechst AG

hexylami.no-3-chloro-2-trifluoromethyl-benzenediazonium hexafluophosphate and, as a coupler, 2,2'-dimethyl-4,4 ^l dihydroxy-5,5'-di (tert.) butyl-diphenyl sulfide and 3,5-dihydroxybenzoic acid .
5

Examples of the p-aminobenzene diazonium hexafluophosphates of the given general formula present in the combination according to the invention are listed in Table A below.
10

Those used in the combination according to the invention p-Aminobenzoldiazonium-hexafluophosphate can from the = corresponding and known p-aminobenzene diazonium hydrogen sulfates or zinc chloride double salts by reaction with commercially available hexafluophosphoric acid (85%) or from their alkali salts in aqueous solution. The hexafluophosphates of the invention are sparingly soluble in water and therefore almost fall out of the reaction solution at room temperature quantitatively. The crystalline, yellow colored precipitate is filtered off, washed with water and im Circulating air drying cabinet dried at 20 to 30 ° C. The p-aminobenzene diazonium hexafluophosphates according to the invention prepared in this way fall in high

Purity and can be used in this quality directly for the production of the photosensitive mixtures or to Coating purposes for two-component diazotype materials can be used.

Examples of those in the combination according to the invention applicable couplers are given in the attached Tables B,

A9

HOECHST AKTIENGESELLSCHAFT. KALLE branch of Hoechst AG

G, D, E and F can be found.

With the couplers of the formula B, yellow dyes are obtained which are only very strong in the visual spectral range absorb weakly, but very strongly in the ultraviolet spectral range between 330 and 450 nm. Because of this absorption behavior, the azo components of the formula B are excellent for the production of Two-component diazotype intermediate master materials suitable. To increase the absorption of these dyes in the visual spectral range, the azo components of formula B to red or blue azo dyes coupling compounds of the formulas C, D, E and F are added. By combining couplers B

¹ ^ with C, D, E or F you get a material that develops into orange-red to brown dyes and absorbs excellently both in the ultraviolet and in the visible spectral range. Such intermediate originals are therefore particularly suitable for the production of further diazo copies and as exposure masks in the photomechanical production of printed circuit boards and integrated circuits in microelectronics. Such an exposure mask is because of its favorable transparency in the visible and uniform

early because of their great absorption in the ultraviolet

Spectral range is particularly advantageous because the template and markings can be precisely positioned on the photosensitive layer of a substrate, for example Drilling on circuit boards, possible and with the 30

Eye becomes easily controllable.

HOECHST AKTIENGESELLSCHAFl HALLE Branch of Hoechst AG

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The diazotype intermediate originals produced can but can also be used in the printing sector, especially where high UV absorption is required and at the same time visual transparency is advantageous, for example for negative montages in flat and gravure printing.

The exposure masks which can be produced with the combination according to the invention differ in these properties very beneficial of those based on silver. Also, diazo exposure masks are simpler and easier cheaper to manufacture than silver exposure masks.

Those which can be used in the combination according to the invention * 5 couplers are known from the literature. They are connections based on 4,4'-dihydroxy-diphenyl sulfide (DE-OS 15 72 195), dihydroxybenzenes (KOSAR, Light-sensitive Systems, Wiley & Sons, New York (1965), pages 22U to 248) and derivatives of mono- and dihydroxynaphthalenes with one or two sulfonic acid amide radical (s) in the naphthalene ring system (EP-A 0 004 574, EP-A 0 014 982, EP-B 0 017 699).

Those used in the combination according to the invention

acidic stabilizers are already known in the diazotype. However, they are in zero concentrations up to about 20 percent by weight, preferably from 5 to 15 percent by weight, based on the diazonium used

salt, present. These concentrations are opposite 30th

the usual acidic additives little, but still have an excellent stabilizing effect and are partially

HOECHST AKTIENGESELLSCHAFl KALLE Branch of Hoechst AG

even superior to known recipes in terms of stabilization. The preferred connection is 5-sulfosalicylic acid used.

As a resin binder in the invention Combination of acidic group-containing plastics with an acid number of at least 100 are used. they are known from German patent specification 26 52 942 and represent copolymers, such as poly (methyl vinyl ether / maleic anhydride), Poly (methyl vinyl ether / maleic acid) monoethyl ester, monoisopropyl ester, -monobutyl ester or poly (styrene / maleic anhydride).

As the liquid phase for the production of the * 5 igen photosensitive mixtures become such solvents or solvent mixtures used in which the diazonium hexafluophosphates, the couplers, the stabilizers and other auxiliaries commonly used in the diazotype are readily soluble. Suitable solvents are for example lower alcohols such as methanol, ethanol, isropanol, n-butanol and / or glycol ethers such as methyl glycol, Ethyl glycol, propyl glycol, methyl triglycol, butyl triglycol, methoxybutanol, also ketones, such as Acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone and others as well as mixtures of these solvents and water.

Usual additives or diazotype auxiliaries can known to the photosensitive mixture according to the invention Compounds are added, for example zinc chloride to increase contrast, thiourea and Thiourea derivatives and dyes in small quantities

HOECHST AKTIENGESELLSCHAFl KALLE Branch of Hoechst AG

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to stabilize and improve the reason for the break, glycerine, glycerine mono-, glycerine di- and glycerine triacetate as well as urea and alkylated ureas as development accelerators and finely divided silicon dioxide or aluminum oxide to improve the lubricity and prevent air entrapment in the Exposure in a vacuum frame (avoidance of the formation of "Newton rings").

The photosensitive mixture according to the invention can be used in Form of a liquid copy lacquer are made available to the user, with either the individual components or semi-finished liquid phase products, resin binder, coupler, diazo printing aid and stabilizer and photosensitive diazo compound. On the other hand, the photosensitive according to the invention Mixture in the form of a photosensitive layer of components a to d of claim 1 be processed on a layer support, applied as a two-component diazotype material. In these In some cases it can be advantageous if the light-sensitive layer is on at least one layer support surface is upset.

As a support for the two-component diazotype material according to the invention all common opaque and transparent materials, such as coated ones, are suitable or uncoated papers, mineral and metallic substrates such as glass, aluminum, silicon, copper, Iron, etc., plastic films made from cellulose esters, such as cellulose-2 1/2 acetate and cellulose triacetate

HOECHST AKTIENGESELLSCHAFl KALLE Branch of Hoechst AG

Polyesters such as polyethylene terephthalate, which is preferred, made from vinyl polymers such as polyvinyl acetate or Polystyrene, as well as alkene polymers such as polyethylene

or polypropylene.
5

Especially when using plastic foils, mineral ones or metallic substrates, it is advantageous to add a further film-forming material to the photosensitive mixture Add resin binder and apply the modified mixture ("diazotype paint") to the substrate surface to raise. Suitable film-forming resin binders are cellulose ethers, such as ethyl cellulose, cellulose esters, such as cellulose acetate, cellulose acetopropionate, acetobuty type and butyrate, vinyl polymers such as polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, Vinyl acetate copolymers, poly (methyl methacrylate) copolymers of alkyl acrylates and Acrylic acid or polyphenylene oxides as well as ethylene glycol / Isophthalic acid / terephthalic acid terpolymers. Preferably a coated polyethylene terephthalate film is used as the substrate.

Those with the photosensitive mixture according to the invention manufactured two-component diazotype material

Despite the very small stabilizer concentration in the photosensitive layer, they are both under Can be stored well in dry as well as under extremely humid climatic conditions. It also forms

in moist and warm storage and development 30

conditions no coating on the layer surface. Also show up, especially when developing with a lot

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

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humid ammonia gas at high temperatures no vesicular layer lift-offs ("wrinkled structure") from the film base. Otherwise the layer vesicles lead to a complete abolition of the layer adhesion and to a destruction of the information of the diazo copy.

The two-component diazotype material according to the invention differs very clearly and advantageously of the diazo film materials that have been known for a long time on the basis of 4-amino-3-halogen-benzenediazonium tetrafluoborates, -hydrogensulfaten and zinc chloride double salts as well as from the well-known "Transopaque-Film G-2 "with a benzene diazonium hexafluophosphate as the photosensitive compound.

The processing of the two-component diazotype material according to the invention takes place as usual by imagewise contact exposure under a transparent template a light source rich in ultraviolet radiation, for example with a high-pressure mercury lamp or a fluorescent fluorescent lamp. The latent copy is then as usual with moist ammonia gas or by applying an aqueous alkaline solution at normal or elevated temperature.

The following examples are intended to describe the invention in more detail without restricting it thereto.

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

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Beis piel 1

From a stock solution of the composition given below 18 paint samples of 50 g each are taken:

Acetone 1360 g

Methanol 345 g

n-butanol 50 g

Methyl glycol 50 g

Cellulose acetopropionate (Cellit ^R PR 500/180 g PR 800)

PolyCmethylvinyl / maleic anhydride) 15 g (Gantrez ^R AN 119)

In 9 of these paint samples (A) are each

75 mg of 5-sulf © salicylic acid and

600 mg of A'-dimethylamino-S-chlorobenzene diazonium hexafluophosphate (MG: 327.5)

and in the remaining 9 master paint samples (B) as comparison samples, respectively

75 mg of 5-sulfosalicylic acid and

490 mg of 4-dimethylamino-3-chlorobenzene diazonium tetrafluoborate (MG: 269)

solved.
30th

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

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The diazo lacquer samples produced in this way are designated A1, Α2 ... A9 and B1, B2 ... B9. Then be in the diazolack sample pairs A1 / B1, A2 / B2 ... A9 / B9 in each case 1.83 χ 10 "^ mol of the following coupling compounds entered and dissolved with mechanical stirring:

A1 / B1: 660 mg 2,2'-dimethyl-4,4'-dihydroxy-5,5'-di-

(Tert.) butyl diphenyl sulfide, MW: 358 10

A2 / B2: 360 mg 2,4-dihydroxybenzoic acid-hydroxyethylamide, MG: 197

A3 / B3: 280 mg 2,4-dihydroxybenzoic acid amide, MW: 152 15

A4 / B4: 500 mg of 4-bromo-3,5-dihydroxybenzoic acid amide, MW: 276

A5 / B5: 280 mg 2,4-dihydroxybenzoic acid, MW: 153 20

A6 / B6: 280 mg 3,5-dihydroxybenzoic acid, MW: 153

A7 / B7: 870 mg 1-hydroxynaphthalene-3-sulfonic acid-N (4'-chlorophenyl) -amide-8-sulfonic acid-N (n-butyl) amide, MG: 479

A8 / B8: 820 mg of 2-hydroxy-3-naphthoic acid-N (4'methyl-

phenyl) amide-6-sulfonic acid N (4'-methylphenyl) amide, MW: 446
30th

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A9 / B9: 640 mg 2, S-dihydroxynaphthalene-6-sulfonic acid-N (4'-chlorophenyl) -amide, MG: 350

From each sample, a corresponding solution is HII-fe of a 10 cm wide die coater of 0.16 mm gap width on a provided with a conventional adhesive layer crystal-clear polyethylene terephthalate film of 125 m thickness applied and the liquid Diazolackschicht in a convection oven dried for 1 minute at 90 ⁰ C. The diazo film samples obtained in this way are referred to as A1, A2 ... A9 and B1, B2 ... B9, corresponding to the diazo lacquer samples. The layer weight of each sample is 8 to 9 g / m ² .

For a comparative test of the durability, a section of each film sample is placed under a UV-impermeable The original is half covered and placed in a commercially available diazo film duplicator (Kalle Ozafiche 066) completely exposed and then developed with moist ammonia gas, which in the exposed Film section the minimum density of the film background and in the unexposed film section the maximum density of the solid is achieved.

The film samples A1 and B1 develop yellow in the unexposed film section, the film samples A2 to A6 and B2 to B6 to red and the film samples A7 to A9 and B7 to B9 to dark purple tones. The exposed Section of each film sample is colorless.

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Another section of each film sample becomes more 24 hours in a climate of 55 ° C and 65% relative Stored in moisture and then exposed and developed as described above. The film background densities achieved here were measured and compared to the film background densities of the corresponding unstored diazo film samples compared.

The measurement of the optical densities was carried out with a "Macbeth-Quantalog Densitometer TD 205", the Kodak filter Wratten No. 106 (D _{vis #} ) for the visual spectral range and the Schott filter UG4 (D _ÜV ) for the ultraviolet spectral range. was used. The results are shown in Table 1.

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Movie
sample Unstored ⁰ UV ⁰ ViS Stored Movie
background 5 ⁰ ViS 0.08 0.04 ⁰ UV almost colorless A1 0.03 0.10 0.08 0.10 light yellow B1 0.04 0.06 0.04 0.42 colorless A2 0.03 0.08 0.42 0.09 red-brown 10 B2 0.03 0.08 0.04 0.71 colorless A3 0.03 0.10 0.31 0.09 bright red B3 0.03 0.08 0.04 0.61 colorless A4 0.03 0.07 0.72 0.09 red-brown B4 0.03 0.06 0.04 1.00 colorless 15th A5 0.04 0.08 0.14 0.08 yellow-brown B5 0.04 0.09 0.04 0.46 colorless A6 0.03 0.06 0.38 0.08 Red B6 0.03 0.14 0.04 0.63 colorless A7 0.04 0.16 1.24 0.16 dark purple 20th B7 0.04 0.35 0.06 0.50 colorless A8 0.04 0.38 1.44 0.41 dark purple B8 0.04 0.08 0.10 0.92 pale pink A9 0.04 0.08 0.96 0.14 dark purple B9 0.04 0.45 25th

In the case of film samples A1 to A9, the film background has changed after storage under forced conditions practically unchanged, i.e. no pre-coupling occurred during storage. In the film samples B1 up to B9 the film background has been among the same

SO

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However, storage conditions have changed significantly, i.e. strong pre-coupling during storage. While the Film samples A1 to A9 can still be processed properly after storage, film samples B1 to B9 are listed under under the same storage conditions have become completely unusable in some cases.

The results show very clearly the superiority of the benzene diazonium hexafluophosphates over the general ones Formula in combination with the coupling components compared to the corresponding known Benzoldiazonium- tetrafluoborates. Similar results are obtained if, instead of the ^ —dimethylamino-S-chlorobenzene diaconium tetrafluoborate (B1 to B9) the corresponding A-dimethylamino-S-chlorobenzene diazonium hydrogen sulfate or the ^ dimethylamino-S-chloro-benzene diazonium chloride-ZnCl2 double salt used.

The diazo lacquer solutions A1 to A9 are protected from light Stable for at least 24 hours at room temperature. While the diazo lacquers of the comparative solutions B1 to B9 under these conditions due to dye formation in the solution (pre-coupling) have largely become unusable.

Example 2

A stock solution of the composition given below is divided into 12 paint samples of 50 g each.

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680 G 170 G 22nd G 22nd G 90 G

acetone
Methanol
n-butanol
Methyl glycol
Cellulose acetopropionate

PolyCmethylvinyl / maleic anhydride) 5-sulfosalicylic acid 1.7 g

2,2'-Dimethyl-4,4'-dihydroxy-5,5'-di (tert) -butyl-diphenyl sulfide 13.1 g

Each of these 12 paint samples (C) is ^{sensitized with 1.83 χ 10 -3} mol of the following diazonium salts:

C1: 600 mg 4-dimethylamino-3-chlorobenzene diazonium hexafluophosphate, MG: 328

D1: 490 mg 4-dimethylamino-3-chlorobenzene diazonium tetrafluoborate, MG: 269

C2: 710 mg of 4-diethylamino-2,5-dichloro-benzene diazonium

hexafluophosphate, MW 390

D2: 640 mg 4-diethylamino-2,5-dichlorobenzene diazonium chloride (ZnCl ₂ double salt), MW: 349

C3: 730 mg 4-MethyI-cyclohexylamine-3-chlorobenzene-

diazonium hexafluophosphate, MW 369

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D3: 760 rag A-methyl-cyclohexylamino-S-chlorobenzene diazonium chloride (ZnCl ^ double salt), MG:

413

C4: 850 mg of 4-methyl-cyclohexylamino-2-trifluoromethyl-5-chlorobenzoldiazoniuinhexafluophosphate, MG: 464

D4: 960 mg of 4-methyl-cyclohexylamino-2-trifluoromethyl-S-chlorobenzene diazonium chloride (ZnC ^ -Dop-

pelsalz), MG: 524

C5: 770 mg 4-dimethylamino-2- (4'-methylphenyl) mercapto-5-chlorobenzene diazonium hexafluophosphate, MG: 418

D5: 680 mg of 4-dimethylamino-2- (4'-methylphenyl) -mercapto-5-chlorobenzene Iazonium hydrogen sulfate, MW 370

C6: 830 mg 4-dimethylamino-2- (4 ¹ -chlorphenoxy) -5-chlorobenzene diazonium hexafluophosphate, MG:

D6: 760 mg of 4-dimethylamino-2- (4'-chlorophenoxy) -5-chlorobenzene diazonium chloride (ZnC ^ double salt),

MG: 413

Those made with the diazonium hexafluophosphates Diazo lacquer samples are with C1 to C6, those with the diazonium hydrogen sulfates and -ZnCl2 double salts with D1

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

- -26 -

to D6. As described in Example 1, a diazo film sample is produced from each diazo lacquer sample. The layer weight of the diazo film samples is 8 to 9 g / m ² .

The same procedure as in Example 1 is used to test the durability of the film samples for comparison. The film samples C1 up to C6 and D1 to D6 develop into yellow to brownish yellow hues in the unexposed film section.

The results of the film samples stored under forced conditions compared to the corresponding Fresh comparative samples that have not been stored are summarized in Table 2.

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

Film rehearsal

Unstored

Stored

C1 ^D vis ^D UV ^D vis ⁰ UV Movie 5 D1 0.03 0.05 0.04 0.08 background C2 0.03 0.08 0.06 1.26 colorless 0.03 0.06 0.04 0.12 yellow D2 very weak 10 C3 0.04 0.14 0.06 0.82 yellow D3 0.03 0.06 0.04 0.08 yellow C4 0.03 0.09 0.04 0.16 colorless 0.03 0.10 0.05 0.18 pale yellow D4 very weak 15th C5 0.03 0.10 0.06 0.46 yellow D5 0.04 0.10 0.04 0.11 yellow C6 0.05 0.16 0.07 0.17 colorless D6 0.03 0.07 0.04 0.07 pale pink 0.04 0.10 0.05 0.16 colorless 20th pale yellow

After the storage of the film samples C1 to C6, the film background did not change or only changed very slightly, i.e. there was practically no pre-clutch. In the case of film samples D1 to D6, the film background has changed partly significantly changed under the same storage conditions, i.e. there is a strong pre-clutch registered during storage. While the film samples C1 to C6 after the under forced conditions

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

storage carried out, the duplication results are still flawless deliver, the film samples D1 to D6 can only be processed with considerable loss of quality.

Similar results are obtained if, instead of 2,2'-dimethyl-4,4-dihydroxy-5,5'-di (tert) butyl diphenyl sulfide Equimolar amounts by weight of other listed diphenyl sulfide coupling compounds are used will.

The measurement results from Table 2 also show in this series of tests the clear superiority of the benzene diazonium hexafluophosphates compared to the corresponding known Benzoldiazoniumtetrafluoboraten, hydrogen sulfates and benzene diazonium chlorides (ZnC ^ double salts) .

Example 3

A polyethylene terephthalate film 125 m thick, provided with an adhesive layer, is subbed on the Surface sensitized with a coating composition of the following composition.

25th acetone 67.5 G Methanol 17.5 G n-butanol 4.0 G Methyl glycol 4.0 G Cellulose acetopropionate 7.0 G 30th Poly (methy! Vinyl / maleic anhydride) 0.75 G

Yo

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

- a-9 -

5-sulfosalicylic acid. 0.15 g 2,2'-dimethyl-4,4'dihydroxy-5,5'-di (tert) -

butyl diphenyl sulfide 1.0 g

2,4-dihydroxybenzoic acid 0.1 g 4-dimethylamine »-3-chlorobenzoldiazonium-

hexafluophosphate 1.70 g

Coating and drying are carried out as described in Example 1. The layer weight is 7.6 g / m.

A section of the produced film sample (E) is exposed under a transparent line template and then the latent copy is developed with moist ammonia gas (Kalle Ozafiche 066). A positive copy of the original is obtained with orange-red lines on a colorless transparent film background. Due to its high contrast in the ultraviolet spectral range < ^D UG4, max ^{: 2} > ⁸ > ^D UG4, min ^: °> ⁰⁸ >, this copy is ideally suited as an intermediate original film for making further copies on UV-sensitive materials. Because of the favorable contrast in the visible spectral range (D _{ÜV 106> max} : 0.6, D _{ÜV] Q6> min : 0.04), such an intermediate original film} is also ideally suited as an exposure mask in the photomechanical production of printed circuit boards and integrated circuits in the Microelectronics. Because of its favorable visual transparency and, at the same time, high UV absorption, such an intermediate original film is clearly superior to the usual silver film masks in many areas of application.

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

A second section of the unprocessed film sample (E) is, as described in Example 1, exposed, developed and the optical densities in the film background measured.

Another section of the unprocessed film sample (E) is ^{stored for 24 hours at 60 °} C. and 80% relative humidity and then processed as described above and the optical densities in the film background are measured. If, instead of 4-dimethylamino-3-chlorobenzene diazonium hexafluophosphate, the equimolar amount by weight of the commercially available 4-dimethylaTnino-3-chlorobenzene diazonium tetrafluoborate (= 1.4 g) is used, a film sample (F) is obtained which is considerable under the storage conditions given above is less durable.

Is then used when using 4-dimethylamino-3-chlorobenzene diazonium tetrafluoborate the proportion of 5-sulphosalicylic acid in the diazo lacquer coating compound Increased by 0.20 g and also added 0.30 g of tartaric acid as an acidic stabilizer, the pre-coupling can can be significantly reduced. The disadvantage of the film sample (G) produced in this way is that on storage of the unprocessed film material and during its development under warm, humid conditions (40 ° C / 80% relative Humidity of the unprocessed film and approx. 70 ° / 80% relative humidity during development) a clearly visible coating forms on the layer surface ("exudation").

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

The results of this series of tests are summarized in Table 3.

Table 3

5 Movie ⁰ ViS 04 Unstored D. vis Stored sample 0, 04 ⁰ UV 0 , 04 ⁰ UV 0 E 0, 04 0.08 0 , 26 0.13 F. 0, 0.08 0 , 15 2.06 G 0.08 1.20 surface surface

If the coating compound is still 0.01 g of the coupler 2-Hydroxy-3-naphthoic acid-N (4'-methylphenyl) -amide-6-sulfonic acid-N (4'-methylphenyl) -amide or 0.01 g of the coupler 2,3-dihydroxynaphthalene-6-sulfonic acid-N (4'-chlorophenyl) -amide added, you get film materials with equally good copying and storage results.

After imagewise exposure and development with moist ammonia gas, both film materials are obtained Copies of the original with brown lines on a colorless transparent background.

Example 4
A poly-

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

- 3-2 -

ethylene terephthalate film of 125 μm thickness is applied to both Pages sensitized with a coating compound of the following composition:

acetone 67.5 G Methanol 17.5 G n-butanol 4.0 G Methyl glycol 4.0 G Cellulose acetopropionate 7.0 G Poly (methyl vinyl / maleic anhydride) 0.75 G 5-sulfosalicy! Acid 0.075 G

butyl diphenyl sulfide 0.66 g

1-Hydroxynaphthalene-3-sulfonic acid-N (4'-chlorophenyl) -amide-8-sulfonic acid- (n) butylamide 0.10 g of 4-methyl-cyclohexylamino-3-chlorobenzene diazonium hexafluophosphate 0.73 g

Coating and drying is carried out as described in Example 1. The layer weight on each side of the film is 7.5 g / m.

A section of the film sample produced in this way is exposed under a silver film original and the latent The copy was then developed in a commercially available continuous flow device with moist ammonia gas. Man receives a positive copy of the original with brown lines and a colorless transparent film background. Because The favorable visual transparency of the brown lines makes such a film particularly suitable

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

- 33 -

Exposure mask in the photomechanical production of printed circuit boards and integrated circuits in the Microelectronics.

The shelf life of the unprocessed film material above (film material H) is significantly better than that of a film material I, in which instead of 4-methylcyclohexylamino-S-chlorobenzene diazonium hexafluophosphate Equimolar amounts by weight of the corresponding ZnC ^ double salt are used.

Tabel 4th ⁰ ViS 5 06 Unstored D. Stored VLS D. UV 2 Movie O, 06 ⁰ UV 0 , 06 0 ,1 8th 15th sample O, 0.12 0 , 11 0 J H 0.12 I. 20th example

A glass plate is sensitized on one side with a coating compound of the following composition:

Acetone 67.5 g

Methanol 17.5 g

n-butanol 4.0 g

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

4.0 G 7.0 G 0.75 G 0.15 G 0.66 G 0.20 G

Methyl glycol
Cellulose acetopropionate
Poly (methyl vinyl / maleic anhydride) 5-sulfosalicylic acid

2,2'-Dimethyl-4,4'-dihydroxy-5,5'-di (tert) -butyl-diphenyl sulfide
2,4-dihydroxybenzoic acid amide
4-diethylamino-2,5-dichlorobenzene diazonium hexafluophosphate 1.42 g

Coating and drying is carried out as described in Example 1. The layer weight is 7.6 g / m. Exposed is placed under a silver film template with a 5 kW xenon pulsed lamp until the yellow film layer not covered by the original is completely faded is. The latent copy is then placed in a sealed container with ammonia gas Room temperature developed. A positive copy of the original is obtained with red lines on a colorless transparent sheet Background, which is excellent as a template material for the manufacture of printed circuit boards and integrated circuits in a photomechanical way.

The shelf life of the unprocessed Diazofilm glass plate K is very good. Is 4-diethylamino-2,5-dichlorobenzoldiazonium hexafluophosphate replaced by the molar weight of the corresponding ZnCl · ■> double salt, then the longer term is no such material

3 (j rials L over 24 hours at!> B "C and b5 % relative humidity significantly worse.

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

- 25 -

Tabel_ 5 K 5 ⁰ ViS 03 Unstored ■ ⁰ ViS 06 Stored UV Movie (Glass) ⁰ UV D. sample L. 0, 04 O, 08 .12 (Glass) 0.07 0 0, O, .34 0.14 0

Similar good results are obtained if instead of 4-diethylamino-2,5-dichloro-benzene diazonium hexafluophosphate equimolar amounts by weight of 4-methylcyclohexylamino-3-chloro-2-trifluoromethyl-benzene- diazonium hexafluophosphate can be used.

Example 6

A 75 μm thick polyethylene terephthalate film coated on both sides with cellulose acetopropionate containing silicon dioxide and aluminum oxide as finely divided pigments is sensitized on one side with a solution of the following composition and the applied solution is dried:
25th

Isopropanol 80 ml

Acetone 12 ml

n-butanol 4 ml

Formic acid (85%) 4 ml

Water 8 ml

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

- .36 -

Poly (methyl vinyl ether / maleic acid) monoisopropyl ester (Gantrez ^R ES-335) 1500 mg

5-sulfosalicylic acid 125 mg

butyl diphenyl sulfide 1880 mg

3,5-dihydroxybenzoic acid 180 mg 4-Bromo-3,5-dihydroxybenzoic acid-N (2'-di-

methylaminophenyl) amide 60 mg 4-dimethylamino-3-chlorobenzene diazonium

hexafluophosphate 1000 mg

After imagewise exposure of the diazotype material M produced in this way under a pencil drawing and subsequent development with moist ammonia gas, a positive copy of the original is obtained with brown lines on a colorless transparent background. The shelf life of the unprocessed material under the forced conditions described is significantly better than when using equimolar amounts by weight of the corresponding 4-dimethylamino-3-chlorobenzene diazonium tetrafluoborate (film sample N). Similar Good results are achieved when using a transparent paper coated on both sides with cellulose acetobutyrate as a support for the light-sensitive diazotype layer.

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

Tabel 5 M. 6th D. 7th Unstored D. UV Stored ^D UV Movie N
0 0 0 , 18 (24 hours 55 ° C / 65% r.h.) 0.22 sample example 0 vis 0 , 18 ^D vis 1.28 , 10 0.10 , 09 0.30

6 paint samples of 100 mg each are taken from the stock paint solution of the composition given below removed:

Acetone 20 methanol n-butanol methyl glycol cellulose acetopropionate

Poly (methyl vinyl / maleic anhydride
2,2'-dimethyl-4,4'-dihydroxy-5,5'-di (tert) -

butyl diphenyl sulfide 2,4-dihydroxybenzoic acid

In 3 of these paint samples (0) are each
a) 1700 mg of 4-dimethylamino-3-chlorobenzene diazonium

hexafluophosphate (sample 0 3) and

675 G 175 G 40 G 40 G 70 G 7.5 G 10 G 1 G

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

a) plus 150 mg 5-sulfosalicylic acid (sample 0 1) and

a) plus 37.5 mg of 5-sulfosalicylic acid (sample 02) entered and dissolved.

In each of the remaining 3 paint samples (P) b) 1400 mg ^ dimethylamino-S-chlorobenzene diazonium tetrafluoborate (Sample P 3) and

b) plus 150 mg 5-sulfosalicylic acid (sample P 1) and b) plus 37.5 mg 5-sulfosalicylic acid (sample P 2) registered and solved.

As in Example 1, a diazo film sample is produced from each of the paint samples produced in this way and numbered 0 1 to 0 3 or P 1 to P 3 corresponding to the paint samples.

The layer weight of each diazo film sample is 8 to 9 g / m ² .

For comparative testing of the shelf life of the unprocessed diazo film samples 0 1 to 0 3 and P 1 to P 3 proceed as in example 1.

In the durability test, the one on a benzene diazonium hexafluophosphate based diazo film known under the trade name "Transopaque Film G-2" (Thiokol / Dynachem Corp.) was included as a comparison.

Develop the diazo film patterns 0 1 to 0 3 and P 1 to P 3 in the unexposed section of the film

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

orange-red hues, the "Transopaque Film G-2" too a light brown shade.

The results of the stored under forced conditions Film samples 0 1 to 0 3 and P 1 to P 3 and a film sample of "Transopaque Film G-2" were compared for the corresponding freshly prepared comparative samples in Table 7.

Table 7

Film rehearsal

Unstored

VlS

Stored
(96 hours 40 "C / 80% RH)

FiIm-D.

VlS

η background ^D UV

O 1 0.03 0, 06 0.06 0.18 pale yellow P 1 0.04 0, 06 0.12 0.54 yellow-brown O 2 0.04 0, 07 0.06 0.20 pale yellow P 2 0.04 0, 06 0.12 0.54 yellow-brown O 3 0.04 O, 07 0.05 0.20 pale yellow P 3 0.04 0, 06 0.14 0.58 yellow-brown Trans opaque Movie G-2 0.04 0, 10 0.20 0.60 red-brown

After storage, the film background for film samples 0 1 to 0 3 changed only slightly, i.e.

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

- -tit -

there was very little pre-coupling during storage.

In the film patterns P 1 to P 3, the film background, however, has changed dramatically under the same storage conditions, ie it entered a very distinct pilot clutch during storage, particularly in the ultraviolet region (Dyy) ^»au ^ * ^ ^he" Transopaque film G- 2 ″ behaves similarly unfavorably as the film samples P 1 to P 3.

The film samples P 1 to P 3 and the "Transopaque Film G-2" are unsatisfactory under warm, humid storage conditions durable, while the film samples according to the invention hold up significantly better under these storage conditions.

Example 8

To assess the behavior during development with very humid ammonia gas at high development temperatures the filram patterns O 1 to O 3 from Example 7 tested in comparison to the well-known "Transopaque Film G-2".

The test specimens developed to full tone were assessed. Each film pattern was developed with a defined one Amount of aqueous ammonia solution (28%) at temperatures between 95 and 100 "C. The residence time of each film sample in the development tester 10 and 30 seconds.

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

- Ape -

The results after development are shown in Table 8.

Tabel 8th Layer vesicles 30 sec. Layer adhesion Well Layer aspect Movie 10 sec. no template no very Well Orange red, 0 1 no smooth no very Well Orange red, 0 2 no smooth no very Orange red, 0 3 smooth bad Trans very opaque very many very light brown, Movie G-2 many wrinkled ("Wrinkle structure")

The results show very impressively that the film patterns 0 1 to 0 3 can be processed without any problems even under very extreme development conditions, while in the case of the comparative sample under the same development conditions it was irreversible, clearly There is a visible change in the film layer and a complete loss of layer adhesion.

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

Because of their very large latitude for development, the diazo film patterns according to the invention are known The material is clearly superior and can therefore be used on all commercially available development devices - even under very extreme development conditions - can be processed without layer and adhesion defects.

The optical density values given in the working examples were obtained with a “Macbeth densitometer TD 205”, _{the Kodak filter “Wratten 106” for the visual spectral range (D vis} ) and the Schott filter “UG” for the ultraviolet spectral range (Dyy) 4 "was used.

so

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

84 / K tables

May 17, 1984 WLK-Dr.S.-gv

Table A.

General formula:

No.

N ₂ PF ₆

1 -CH ₃ -CH ₃ Cl H 2 -CH ₃ -CH ₃ Br H 3 -CH ₃ -CH ₃ Cl Cl 4th -CH ₃ -CH _a Cl -CF ₃ 5 -CH ₃ -CH ₃ Br -CF ₃ 6th -CH ₃ -CH ₃ Cl CH ₃ _ / p \ _ _s _

-CH *

-CH-:

8th -C ₂ H ₅ -C ₂ H ₅ Cl 9 " ^C 2H ₅ -C ₂ H ₅ Cl 10 -C ₂ H ₅ -C ₂ H ₅ Cl 11th -C ₂ H ₅ -C ₂ H ₅ Cl

Cl -CF

Si

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

84 / K 044 -S-

Continuation Table A No.

Ri

12th -C ₂ H ₅ ZH ₅ Cl 13th -C ₂ H ₅ -C ₂ H ₅ Cl 14th -C ₃ H ₇ -C ₃ H ₇ Cl 15th -C ₄ H ₉ -C ₄ H ₉ Cl 16 -C ₄ H ₉ " ^C 4H ₉ Cl 17th -CH ₂ -CH = CH ₂ -CH ₂ -CH = CH ₂ Cl 18th -CH ₃ -C ₃ H ₇ Cl 19th -CH ₃ -C ₄ H ₉ Cl 20th -CHo -CicHoo Cl

21
22nd
23
24

25th

27

-CH ₃
-CH ₃
-CH ₃
-CH ₃

-CHo

-CH ₂ CH ₂ -

26 -CH-:

-CH ₃

CH '

Cl Cl Br Cl

CH ₃ O-

H H

Cl Cl

HH -CF ₃

-CF ₃ H

Cl

-CF-:

-CF-:

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

84 / K 044 - ^ S -

Table A continued

No. R ₁

28 -CH.

29 -CH.

30th

31 -CH.

32 -CH.

33 -CHr

34 -CH ₂ -CH-CH ₂

35 -CH ₃

36

R-:

8th I.

M2 '

-CH ₂ -

Cl

- ^CH 2 <O> ^cl

(CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₃ C1- Cl

-CFc

CFc

Cl

Cl

S3

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

84 / K 044

Table A continued

No.

37

38

CH ₃ YHY CH ₃

39

Cl

20th 40 \ ^ ~ Ν 41 H 25th 42 H
S. 43 H

CF ₃

Cl

HOKCHS 'Γ Λ KTTKN C K F- Γ. T, T, S Γ H AFT HALLE Branch of Hoechst AG

84 / K

Pro_rtse t ■ zung_ Tab_e 11 e__A

No. R ₁

44 45

46

H ι

CF,

Cl CF.

48

49

50

CH.

CHo I ^J

CO

Cl

SS

341

HOECHST AKTIENGESELLSCHAFT. KALLE branch of Hoechst AG

84 / K

- jfr -

Table A continued

No,

COCH3

52

<CH2> 6

6)

53

-CF ₃

Table B.

General formula:

HO-

R ₄

-S-

R ₄

-OH

No.

A3.

HHH
CH ₃

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

84 / K 044 - 7 -

For tse tzun g Table B

No.

R /

4 5 6 7

CH ₃

CH ₃

CHo

< ^CH 3) ₂ CH (CH ₃ ) ₃ C CH ₃

(CH ₃ ) ₂ CH (CH ₃ ) ₃ C

Table C.

General formula:

No.

1 H -COOH H 2 H -CONH ₂ H 3 H -CONH ₂ Cl 4th H -CONH ₂ Br 5 H -CONHCH ₂ CH ₂ OH H

-CONH- (O,

341

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

84 / K

Continuation of Table C No.

Rc

-CONH-

N (CH ₃ ) ₂

12th

-CONH-I

N (C ₂ H ₅ ) ₂

9 -COOH H 10 -CONH ₂ H 11th -CONHCH ₂ CH ₂ OH H

Table D.

General formula:

No.

1 2

R ₈ -HNO ₂ S OH

-SO ₂ NHR ₇

Rc

H -C ₄ H ₉ H
-C ₄ H ₉

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

84 / K 044 - $ -

£ o_rt s_e_tz ung_Ta b el_l§L JD No. Rc

3

-CH ₂ CH ₂ OH

-CH ₃

-C ₄ H

₄ H ₉

Table E.

General formula:

NSO

CONH-R

No. 1 2

3 30

-CH ₂ CH ₂ OH

H H H

HOECHST AKTIENGESELLSCHAFT KALLE Branch of Hoechst AG

84 / K 04-4

-KT-

Continuation of Table E No. 5

6 10

Rc

Q)

(CH ₂ J ₃ -HHQ

10

-C ₄ H ₉

H H H H

Table F

General formula

HO

SO ₂ N ^R 12

No.

12th

1 H 2 H 3 H

13th

CH ₃

(CH ₂ ) 2 "CH ₃

Cl

HOECHST AKTIENGESELLSCHAFT KALLE branch of Hoechst AG

84 / K

Table F continued

No.

5 4 H 5 H 6th H 0
7th H

15th

10

CH

CH ₃

OCH-:

^CF 3

CH

^υη 3 OC ₂ H ₅

C ₂ H ₅

CH (CH ₃ ) ₂

N (C ₂ H ₅ ) ₂

Claims (14)

HOECHST AKTIENGESELLSCHAF1 KALLE Branch of Hoechst AG 84 / K 044 - A8 - May 17, 1984 WLK-Dr.S.-gv PATENT CLAIMS 1. Photosensitive mixture of diazonium salt, coupler, resin binder, stabilizer, customary additives and liquid phase, characterized by the combination of a) at least one p-aminobenzene diazonium hexafluophosphate, b) at least one dihydroxydiphenyl sulfide, if appropriate mixed with another coupler, c) acidic stabilizer in a concentration of zero to 20 percent by weight, based on the used Diazonium salt, d) at least one plastic containing acidic groups with an acid number of at least 100, the derived from maleic acid or phthalic acid type as resin binder and e) lower alcohols, glycol ethers, ketones and water alone or in a mixture as the liquid phase. 2. Mixture according to claim 1, characterized in that that as p-aminobenzene diazonium hexafluophosphate a Compound of the general formula HOECHST AKTIENGESELLSCHAFl HALLE Branch of Hoechst AG 84 / K 044 in which R ^ alkyl has 1 to 6 carbon atoms, Alkenyl with up to 4 carbon atoms ^ ⁰ or cycloalkyl with up to 8 carbons material atoms, & 2 optionally substituted alkyl with 1 to 18 carbon atoms, alkenyl with up to 4 carbon atoms, Cycloalkyl of 6 to 12 carbon atoms, optionally substituted aralkyl with 7 to 12 carbon atoms or Ri and R? along with the nitrogen-20 atom to which they are bound, one optionally substituted 5- to 8-membered heterocyclic radical, X chlorine or bromine and Y is hydrogen, chlorine or bromine, trifluoromethyl, an ether or thioether group
mean is present. 3. Mixture according to claim 1, characterized in that that as a dihydroxy-diphenyl sulfide a compound of general formula 3418489 HOECHST AKTIENGESELLSCHAFl
KALLE branch of Hoechst AG 84 / K 044 R ₄ optionally in a mixture with at least one coupler of the general formulas 10 RS-HNO ₂ S OH SO2NH-R7 20th R9-HNCO so ₂ n; 1 "* 13 30th in which R3 and R _{4 are} identical or different and Hydrogen or alkyl having 1 to 4 carbon atoms, at least one of the for HOECHST AKTIENGESELLSCHAFl KALLE Branch of Hoechst AG 84 / K 044 -M- OH group o-position is occupied by hydrogen,
R5 and Rg are identical or different and are hydrogen, carboxyl, carleonamide or optionally by a hydroxy or amino group-substituted carboxyalkyl or carboxyarylamide,
R7 and Rg are identical or different and are hydrogen, alkyl, alkenyl, hydroxylalkyl with 1 to 4 carbon atoms, given if substituted aryl with 6 to 12 carbon atoms,
R9, R-] 0 ^{and <} 3 & 11 are identical or different and are hydrogen or an optionally substituted alkyl having 1 to 6 carbon atoms or cycloalkyl with 6 to 12 carbon atoms, aryl or aralkyl with 6 to 12 Carbon atoms or R- | 0 and R-] 1 together with the nitrogen atom to which they are attached, an optionally substituted 5- to 8-membered heterocyclic radical,
Rj 2 hydrogen, R- | 3 optionally substituted by alkyl groups tuted cycloalkyl with up to 8 carbon atoms, aralkyl with up to 10 carbon atoms, optionally substituted aryl or R- | 2 ^and Rl 3 together with the nitrogen atom to which they are attached, optionally one HOECHST AKTIENGESELLSCHAFa KALLE Branch of Hoechst AG 84 / K 044 substituted 5- to 8-membered heterocyclic radical and
Z hydrogen, chlorine or bromine mean are present.
5 4. Mixture according to claim 1, characterized in that the diazonium salt is 4-dimethylamino-3-chlorobenzene diazonium hexafluophosphate and as a coupler 2,2'-dimethy1-4,4'-dihydroxy ~ 5,5'-di (tert) butyl-dipheny1-sulfide and 2,4-dihydroxybenzoic acid are present, 5. Mixture according to claim 1, characterized in that that the diazonium salt is 4-dimethylamino-3-chlorobenzene diazonium hexafluophosphate and as a coupler 2,2'-dimethyl-4,4'-dihydroxy-5,5'-di (tert.) butyl-diphenyl sulfide, 2,4-dihydroxybenzoic acid and 2,3-dihydroxynaphthalene-6-sulfonic acid-N (4'-chlorophenyl) -amide available. 6. Mixture according to claim 1, characterized in that that the diazonium salt is 4-methyl-cyclohexylamino-3-chlorobenzene diazonium hexafluophosphate and as a coupler 2,2'-dimethyl-4,4'-dihydroxy-5-5'-di (tert) butyl-diphenyl-sulfide and 1-hydroxynaphthalene-3-sulfonic acid-N (4'-chlorophenyl) amide-8-sulfonic acid-N (n-butyl) amide available. 7. Mixture according to claim 1, characterized in that the diazonium salt is 4-diethylamino-2,5-dichlorobenzene diazonium hexafluophosphate and as a coupler 2,2'-di- HOECHST AKTIENGESELLSCHAFa KALLE Branch of Hoechst AG 84 / K 044 - kß - methyl 4,4 ¹ -dihydroxy-5,5'-di (tert) butyl diphenyl sulfide and 2,4-dihydroxybenzoic acid are present. 8. Mixture according to claim 1, characterized in that that the diazonium salt A-methyl-cyclohexylamino-S-chloro-2-trifluoromethyl-benzenediazonium-hexafluophosphate and the coupler 2,2'-dimethy1-4,4 '"dihydroxy-5,5" -di (tert) -butyl-diphenyl sulfide and 3,5-dihydroxybenzoic acid are present.
10 9. Mixture according to claim 1, characterized in that that the resin binder is a mixture of cellulose acyl ester and a copolymer of maleic acid derivatives and alkene compounds are present. 10. Two-component diazotype material made of a layer support and a light-sensitive layer the components a to d of claim 1. 11. Diazotype material according to claim 10 with a polyester film as a substrate. 12. Diazotype material according to claim 10 having a lacquered polyethylene terephthalate film as a layer carrier ger. 13. Diazotype material according to claim 10 with a Glass base as a layer carrier. HOECHST AKTIENGESELLSCHAFI KALLE Branch of Hoechst AG 84 / K 044 - 49 - 14. Diazotype material according to claims 10 to 13 with a photosensitive layer on at least one support surface.