DE2057473A1 - Photosensitive copy paste - Google Patents

Description

K 1985 FP-Dr.N.-ur 19.November-197C

Description for registering the

KALLE AKTIENGESELLSCHAFT Wiesbaden-Biebrich

for a patent

Photosensitive copying paste

The invention relates to a photosensitive copying paste which, as essential constituents, at least a condensable aromatic diazonium salt, Contains at least one binder and at least one substance capable of crosslinking and that according to the Exposure to water or predominantly aqueous liquids can be developed. The inventive Copy paste is particularly suitable for the production of screen printing forms.

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Popular screen printing materials include ζ. Β, as a photosensitive substance azido compounds, This However, material cannot be developed in water, but requires organic solvents, in the best case alcohol diluted with water.

Also known are higher molecular weight diazonium compounds that are formed by condensation of diazodiphenylamines with formaldehyde in an acidic condensation medium, and their use for the production of offset printing plates and in combination with water-soluble colloids for the production of screen printing material,

In addition, light-sensitive layers with tanning properties have already been found which, in addition to binders (colloids) and monomeric diazodiphenylamines or diazoamino compounds derived therefrom, contain an addition of at least one aldehyde, preferably formaldehyde (DBP 1 206 308 and 1 447 729).

In the technical application of these copying compounds, which, based on the diazo compound, contain a large, preferably 5-10-fold molar excess of formaldehyde, it was found to be a great disadvantage that

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when the layers dry, large amounts of the toxic and unpleasant smelling formaldehyde are released. To the Coating of the carrier with the formaldehyde-containing coating liquid would therefore have to be the coating and Drying rooms must be provided with intensive ventilation and extraction devices.

The formaldehyde content of the coating solution cannot be essential for the tanning effect without disadvantages be reduced. With equimolar amounts diazo compound and formaldehyde, the crosslinking is sufficient for copying a screen, but not for normal pressure loads. When replacing formaldehyde with glyoxal, the technically second most important aldehyde for this purpose 1/20 to 1/10 of the equimolar amounts give good results, the shelf life of such coating solutions is but worse than the compositions containing formaldehyde.

The object of the invention was to provide a new copy paste to find that does not have the disadvantages of the prior art described.

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The subject of the application is a photosensitive copying paste, which as essential constituents at least a condensable aromatic diazo compound, at least one binder and at least one for Contains crosslinking capable substance which is characterized in that it contains at least one diazonium salt of the general formula I of the attached formula drawing, wherein

^R 1j ^r 2j ^r 3 and R4 are identical or different and

Hydrogen atoms, halogen atoms, alkyl groups with 1 to 2 carbon atoms or alkoxy groups with 1 to 4 carbon atoms,

Y is a single bond or one of the

Groups -0-, -S-, -NH-, -CONH- and

X is the anion of the diazonium salt

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mean, or a diazoamino compound prepared therefrom and at least one compound containing at least one substituent of the formula

- ^CH 3-n

carries what

Z is a halogen atom, a hydroxyl group or an etherified, esterified or acetalized hydroxyl group with 1 to H C atoms and

η is a number from 1 to 3

mean, where Z is a halogen atom when η is greater than 1 is.

The crosslinkable substances described in more detail below show on their own just like the diazo compound practically no tanning effect on the binding agent when exposed

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middle. Surprisingly, however, they show one in combination with the diazo compounds mentioned similar tanning effect to aldehydes, but without the disadvantages associated with them.

The crosslinkable substances used according to the invention can be referred to in the broadest sense as formaldehyde substitutes. This includes not only the methylol compounds, which are formed by the reaction of reactive compounds with formaldehyde and which can possibly be in equilibrium with the starting components. Their derivatives, such as ethers, esters and acetals or hemiacetals, which can also be prepared in ways other than by condensation with formaldehyde and corresponding conversion of the methylol compounds, can also be used. Likewise, the halomethyl compounds formally derived by replacing the hydroxy group by a halogen atom of the methylol compounds are suitable. In addition to these, however, it is also possible to use compounds with dihalogen and trihalomethyl groups. What all such compounds used according to the invention have in common is that they can be used in combination with the above-mentioned Pirj & overbin-

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fertilizer and hardenable binders cause hardening or insolubility of the copying layer on exposure. In the case of multifunctional crosslinking compounds, the effect is of course relatively greater or can be achieved with smaller amounts.

The reason for the effectiveness of the methylol compounds and their derivatives can be found in a transaldolization or transhydroxymethylation reaction can be seen as described by Olsen, z. B. Liebigs Ann. Chem. 651; 102 (1962), with products that arise analogously to the substances of the asymmetrical Three-carbon condensations such as those from Hellmann in Liebigs Ann. Chem. 632; 73 (1960) and 656; 53, 70 (1962). A partner would be the hydrogen atom on nitrogen of diazodiphenylamine.

Crosslinking with substances containing activated halogen atoms is known as nucleophilic substitution. Of the many halogen compounds which can be used as crosslinkers, however, are within the scope of this invention only the halomethyl compounds of interest. Of the

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Effect of nitrohalogen aromatics, e.g. B. 2,4-Dinitro-1,5-difluorobenzene, and especially of monofunctional representatives such as 4-nitrochlorobenzene is too low.

Two different groups effective according to the invention can also be present in one molecule, such as, for example, im N-methylol chloroacetamide. Becomes the chloromethyl group halogenated even further, as in N-methylol-dichloroacetamide and trichloroacetamide, the tanning effect decreases on exposure to light.

In addition, the layers can also contain substances that further increase the crosslinking at the exposed areas. This can be done by releasing acid, as when adding tetrabromomethane, with the formation of hydrobromic acid. The methylol compounds or their derivatives can also be one or

contain several such groups which are themselves photosensitive like the azido group or polymerizable are like the acrylic group (or are already polymerized like the polyacrylic derivatives) or curable like the Epoxy group or reversibly crosslinkable like the disulfide group. In addition, the layers can contain other photosensitive compounds with a crosslinking action contained in a smaller amount.

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In detail, the formaldehyde substitutes used according to the invention can include the following classes of substances belong.

I acid amide-N-methylol compounds

II C methylol compounds

III acetals

IV derivatives of methylol compounds.

I. N-Methylol Compounds of Primary Carboxamides

Monomethylol urea Dimethylol urea N-methylol acetamide N-methylol propionic acid amide N-methylol chloroacetamide N-methylol dichloroacetamide N-methylol trichloroacetamide N, N * -Dimethylol-oxamide N, N ^f -dirnethylol-malonamide N, N · -Dimethylol-suc cinamid Trimethylol-citramid.

Dimethylol-sebacic acid diamide N-methylol-acrylamide N-methylol polyacrylamide

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- ίο -

N-methylol compounds of secondary acid amides

Dimethylol-ethylene urea Dimethylol-dihydroxy-ethylene urea Dimethylol propylene urea Trimethylol melamine Tetramethylol melamine Pentamethylol melamine 1,3-dimethylol-5-methyl-1,3,5-triazinon-2 1,3-Dimethylol-5-allyl-1,3,5-triazinon-2 1,3-dimethylol-5-butyl-1,3,5-triazinon-2 1,2-Di- [1,3-dimethylol-1,3,5-triazinon- (2) -5-yl] -ethane N-methylol-N-methyl-acetamide N-methylol-acetanilide N-methylol-phthalimide N-methylol-pyrrolidone tetramethylol-hydrazodicarboxamide Tetramethylol acetylenediurea

N-methylol compounds of primary acid amides aromatic carboxylic acids and sulfonic acids

N-methylol-benzamide

N-methylol salicylamide N-methylol-2-cyano-benzamide

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N-methylol-cinnamic acid amide N-methylol nicotinic acid amide NjN'-dimethylol-terephthalic acid diamide N-methylol-4-azido-benzamide (pp. 160-161 ° C) N-methylol-4-azido-cinnamic acid amide N-methylol-toluenesulfonic acid amide Ν, Ν'-dimethylol-benzene-m-disulfonic acid amide N-methylol-C 1-4 azido-benzenesulfonyl) urea

II. C-methylol compounds Glycolic acid

Glycolic acid amide

Dihydroxyacetone

Anhydroenneoheptosis

2,4,6-trimethylol-phenol 2,6-dimethylol-4-methyl-anisole 2,6-dimethylol-p-cresol 1-4 -dihydroxymethyl- 1-4-diisopropylbenzene 2,2-bis- (4-hydroxy -3,5-dihydroxymethyl-pheny1) -propane 3,3'-dihydroxymethyl-4, ^{1 l} -dihydroxy-diphenylsulfone

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III. Acetals of methylol compounds

2,2,4,4-tetramethylol-pentanone-3-bisformal 2,2,4, ^4-i-pentanol tetramethylol-3-bisformal Polyvinylhydroxymethyläther 5-hydroxymethyl-l, 3-dioxolan-2-dioxolane Methy1-1,3 Ascorbic acid diformal

IV. Further derivatives of methylol compounds

N-methylol chloroacetamide Chloroacetamido-chloromethane methylenebis-chloroacetamide Bis-chloroacetyl hydrazine Bis-chloroacety1-ethylenediamine Bis-chloroacetyl-tetramethylenediamine Bis-chloroacetyl-3,5-phenylenediamine-1-carboxylic acid benzamido-bromomethane N- (benzoxymethyl) methacrylamide 1,3,5-tri-β-chloropropionyl-hexahydro-1,3,5-triazine Methylene-bis-ß-chloropropionamide phthalimido-chloromethane ß-chloropropionamide

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N-methylol-ß-chloropropionamide

B-acetoxy-propionamide

N-methylol-2,3-dibromo-propionamide U-methylol-β-acetoxy-propionamide 4 ₃ 4 * -Dimethoxymethyl-diphenyl ether 4j4'-diacetoxymethyl-diphenyl ether N-acetoxymethyl-phenylacetaniide

Trismethoxymethyl-dipJaenylather-Geinisch Polymethacrylamide N-methylol methyl ether Tetramethoxymethyl acetylenediliar Tetramethoxymethyl hydrazodicarboxamide Glycidoxymethyl melamine

N, N ^f -dimethylol-dithio-diacetamide trischloromethyl-diphenyl ether mixture

The diazonium salts used in the copying compositions according to the invention in combination with the crosslinking compounds contain, in addition to the benzene nucleus, which carries the diazonium group, another benzene nucleus a condensation reaction with formaldehyde or the formaldehyde substitutes used according to the invention can attack. The good cure of the invention

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Copy mass at the image areas is probably due to the fact that both the binder and the photosensitive diazonium compound in the crosslinking reaction are included. As mentioned above, the two benzene nuclei are the diazonium compounds linked by a single bond or an -NH-, -0-, -S- or -CONH- group. Particularly active and therefore preferred are the compounds which contain an —NH group contain, i.e. 4-diazo-diphenylamine and its derivatives. All diazonium compounds used according to the invention can carry substituents in both benzene rings, in particular alkoxy groups with 1 to 4 carbon atoms, preferably methoxy and ethoxy groups, alkyl groups with 1 or 2 carbon atoms, halogen atoms, especially chlorine and bromine, and the like. More.

Examples of suitable diazonium compounds are: 2,3 ', S-trimethoxydiphenyl ^ -diazonium chloride, 2,4', 5-triethoxydiphenyl-4-diazonium chloride, 4-phenylmercapto-2-chloro-5-methoxy-benzene diazonium chloride, 4 - [4- (3-methylphenoxy) phenoxy] -2,5-dimethoxy-benzenediazonium sulfate, 4- (4-methoxyphenylmercapto) -2,5-diethoxy-benzenediazonium chloride, 2,5-diethoxy-4-phenoxy-benzenediazonium chloride , 4- (3,5-Dimethoxy-benzoylamino) -2,5-diethoxy-benzenediazonium hexafluorophosphate, diphenylamine-4-diazonium sulfate and the 4-diazonium salts of the following diphenylamine derivatives: 209822/0811

3-methoxy-diphenylamine, 2-methoxy-diphenylamine, 2 ^f -methoxy-diphenylamine, Jj'-methoxy-diphenylamine, 3-methyldiphenylamine, 3-ethyl-diphenylamine, 4'-methyl-diphenylamine, 3-ethoxy-diphenylamine, 3 -Butoxy-diphenylamine, 3-ß-hydroxy-ethoxy-diphenylamine, 2'-methoxy-5'-methyldiphenylamine, 3-methoxy-6-methyl-diphenylamine, 3'-chlorodiphenylamine, 4'-n-butoxy-diphenylamine, 3 , 4 · -Dimethoxydiphenylamine, 4'-Broni-diphenylamine.

Diphenylamine-4- and 3-methyl-diphenylamine-4-, the 3-alkoxydiphenylamine-4-diazonium salts are particularly preferred with 1-3 carbon atoms in the alkoxy group, especially the 3-methoxydiphenylamine-4-diazonium salt.

Numerous binders can be used for the preparation of the photosensitive copying paste; she do not necessarily have to be water-soluble; in many cases it is sufficient if they are preferred by the Developer used to be swollen. Development with water or aqueous developers is possible when using z. B. of polyvinyl alcohol, partially acetylated polyvinyl alcohol or partially hydrolyzed polyvinyl acetate, polyacrylic acid, methyl--

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cellulose, hydroxyethyl cellulose, gelatin, casein and other natural colloids. Polyvinyl alcohol is preferred, the incompletely saponified polyvinyl acetates are particularly preferred. It is possible and in many Cases appropriate to use plasticizers, e.g. B. tricresyl phosphate or dibutyl phthalate, and antifoam agents, ζ. Β. Silicone oils or polyglycols, and preservatives such as sorbic acid as well as dyes and wetting agents to be added.

To a certain extent, which is determined by the developability of the layer with the aqueous developer, it is possible to add binders which are insoluble or sparingly soluble in water in a form which has been dissolved or swollen with solvents or in a dispersed form. Suitable additives are fillers, such as diatomaceous earth, alumina and plastics such as polyamides or phenolic resins, and vinyl polymers such as polyvinyl acetate, polystyrene or poly-vinylidene chloride ψ. Polyvinyl acetate in the form is preferred

an aqueous dispersion, particularly preferred are those internally plasticized by copolymerization Types of dispersion that make the addition of plasticizers superfluous.

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All materials customary for the four printing processes can be used as carriers for the copying compounds according to the invention in question. For the preferred application of the copy paste For screen printing, fabrics and perforated flat structures made of plastics such as polyamide or polyester are used and metals such as steel or bronze are used. For flat printing, the foils pretreated as usual, z. B. made of paper, aluminum or brass-chrome, for the Gravure plates or cylinders made of copper and for letterpress plates or cylinder segments, e.g. B. made of zinc or magnesium is used. Depending on the requirements placed on the layer during development, possibly etching, and the printing process or the possibly necessary redecoatability, the type and amount of binding agent, the dilution of the Copy paste, the amount of crosslinkable substance, the pH value, the layer weight, the drying, the exposure time and the type of development as well as possibly Tempering processes for post-curing after development can be adapted to the desired purpose in a known manner. If necessary, smaller amounts of solvents, acids and salts can also be added to the developer.

The photosensitive ones according to the invention are preferred Copy paste for the production of screen printing material which can be developed with pure water and which can be used for the

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Printing with solvent-based as well as with aqueous screen printing inks, e.g. B. used for textile printing can be. The screen printing material according to the invention is particularly preferred for solvent ink screen printing.

The copying compound according to the invention can be in liquid form as a solution or dispersion, in particular as a screen printing varnish, but also as a copying varnish, e.g. B. for the production of copied circuits, commercially exploited. It can also be marketed as a presensitized copy material on an appropriate carrier for screen printing, planographic printing, gravure printing, letterpress printing. In order to achieve a particularly long shelf life, it can be sold and stored for screen printing in two components, the screen printing emulsion, which contains binding agent, diazo compound and possibly other additives, and the hardener solution or dispersion, which contains the crosslinking substance. In this case, both components are mixed by the consumer in the usual screen printing manner immediately before coating the carrier.

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The use of the additives according to the invention not only makes screen printing materials unpleasant replacing smelling and toxic formaldehyde, but with the same amount of light-sensitive Substance compared to copier layers with diazo condensates also given the option, depending on The type and amount of the crosslinking methylol compounds or their derivatives determine the tanning effect to control and after the development also, z. B. by heating to reinforce. Also can by setting a weakly acidic pH, e.g. B. by adding ammonium acetate, one more than Sufficient shelf life of the finished copy paste and the pre-coated screen printing material is achieved will. Without the additives according to the invention, the photosensitive copying paste is under normal storage conditions Can be stored for months, in the refrigerator for over a year. Overall, the invention is the Production of very variable good. Copy layers that are more convenient to process are easier to achieve than with the previously known aqueous developable diazo tanning layers.

The invention is explained in more detail by the following examples. All percentages are percentages by weight, if nothing other is indicated. Parts by weight (by weight) and parts by volume (by weight) are related to each other in the ratio of g to ecm.

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example 1

A screen printing fabric made of polyamide is coated with a copying solution by knife-coating, which by dissolving from 25 Gt. Hydroxyethyl cellulose, 3 pbw. Diphenylamine 4-diazonium sulfate and 8 Vt. a 2 / Sigen solution of dimethylol propylene urea in a total of 200 Vt.

fc water is produced. After the sieve has dried

with a hair dryer or a circulating air drying cabinet at 30 - 50 ° C is under a positive template with UV light from an 18 ampere two-phase carbon arc lamp is exposed for 5 minutes and the exposed screen is passed through Hosed down with tap water in the unexposed areas. The screen printing form produced in this way is strong enough and can be used for printing. Without the addition of the methylol compound, one holds under sieve manufactured under the same conditions

"Development does not develop and is completely stripped.

The copier solution can be stored at 42 ° C at least two weeks; thereafter the crosslinking falls off at the exposed areas of the layer.

Example 2

To an aqueous screen printing emulsion, which in 1000 Vt. 180 Gt. Polyvinyl alcohol (2 % vinyl acetate units, K value 50), 60 Vt. Dibutyl phthalate as a plasticizer,

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2057Α73

90 Gt. contains finely powdered polyvinyl acetate and 15 parts by weight * diphenylamine-4-diazonium sulfate, a hardener solution is added which contains 15 % N-methylol-chloroacetamide, 0.8 % free formaldehyde and 1.5 % methyl violet. When 15 % hardener solution is added, a sieve is obtained which, with an exposure time that is about a third shorter, shows the same crosslinking as a sieve to which 10 % was added.

Screens made in the same way and tested from an emulsion containing 12 % hydroxyethyl cellulose, 12 % of a 50% polyvinyl acetate dispersion, 6 % dibutyl phthalate and 1.5 % 3-methoxydiphenylamine-4-diazonium sulfate in water are precoated for five weeks at room temperature storable and normally applicable. They are acetone-proof, and the layer delimitation of the developed sieves crosses the mesh, so does not show the so-called sawtooth effect. In a printing test with the Maratex water color from Marabu, Tamm / Württemberg, the screen was still completely in order after 30,000 squeegee strokes.

Example 3

With 100 Gt. the screen printing emulsion described in Example 5, but with 1.5 % 3-methoxy-diphenylamine-4-

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diazonium sulfate as a light-sensitive substance, will be 2 Gt. 2,4,6-trimethylolphenol, in a little water dissolved, stirred. This copying solution is used to create a fine-mesh polyester fabric for screen printing stencils coated, dried with warm air and exposed. The exposed screen and a corresponding screen, made without the addition of the methylol compound are developed with cold water. The comparison screen shows the shortest exposure time sufficient for the desired screen printing form no hardening and is stripped.

Example 4

To the screen printing emulsion mentioned in Example 1, 4 % methylenebis-chloroacetamide is added in finely powdered form and stirred intensively with it. Then it is stained with crystal) violet. This copying solution can be used to produce a screen printing stencil in the usual way. By heating after the development, the screen is not only dried, but z. B. at 100 ° C within 15 minutes, the copy layer also solidified significantly.

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Example 5

To 100 Gt. an aqueous screen printing emulsion, which contains about 40 % polyvinyl acetate dispersion (50 #ig), 20 % of a polyvinyl alcohol solution with a viscosity of about 45,000 cp, obtained by stirring polyvinyl alcohol with 12 % vinyl acetate units and the K value in an open vessel for 7 hours at 80 - 85 ° C, contains 4 % dibutyl phthalate, 0.3 % ammonium acetate and 1.5 % diphenylamine-4-diazonium sulfate, a solution of 5 pbw. Ν, Ν'-dimethylol-terephthalamide given in methylglycol. A perlon screen coated therewith is exposed for 4 minutes under a 5000 watt xenon point light copier lamp (COP χ P 5000 from Pa. Staub, Neu Isenburg) at a distance of 100 cm and developed with water to form a printable screen. A comparison screen without the addition of the hardener is not developed image-wise by water, but rather stripped of the coating.

Example 6

An aqueous screen printing emulsion containing 10 % hydroxyethyl cellulose, 5 % polyvinyl acetate, 3 % dibutyl phthalate, 1 % finely divided silica and 1 % diphenylamine-4-

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contains diazonium sulfate, 1 % dimethyloldihydroxyethyleneurea and 4 % tetrabromomethane are added and this copying solution is stirred intensively. By coating a screen with this solution, drying with cold air, exposure under a positive template and developing with a sharp water jet, a screen printing stencil is obtained from which many prints are also made in textile printing with water inks

can be produced. The addition of tetrabromomethane increases the crosslinking density.

example J

In the screen printing emulsion mentioned in Example 1, 5 % bis-chloroacetyl-tetramethylenediamine are finely divided by stirring. A screen coated with this copying solution satisfies simple requirements for screen prints which - as is usually the case - can only be produced in small numbers. Heating after developing will make the screen much stronger.

Example 8

To 100 Gt. an aqueous screen printing emulsion, which

45 % polyvinyl acetate dispersion (Mowilith DM 1),

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45 % of the polyvinyl alcohol solution described in Example 5, 0.2 % ammonium acetate and 1.6 % diphenylamine-4-diazonium sulfate, 6 pbw in ethylene glycol monomethyl ether. a chloromethylated one
Diphenyl ether (CMDPO from DOW Chemical Co.) was added. This substance has a degree of chloromethylation of 2.8 and the following isomer distribution: 2.4 '1.9 %', 4.4 '8.6 % i 2.2', 4 «17 % i 2.4.4 ' 74 % and 2.2 ', 4.4'<2 %. The active crosslinking substance is finely distributed through intensive stirring, a sieve made from it is completely smooth. After 4 minutes
Exposure under the xenon lamp can quickly develop the screen image-wise with warm water.
This screen printing stencil is very resistant and elastic. The sieve cannot be used without the addition of the hardener.

Example 9

If the chloromethyl compound used in Example 8 is reacted quantitatively (Cl detection negative) with methanol to give the corresponding methoxymethyldiphenyl ether (methoxy content found 28.9 %) , an oily substance is obtained which is also active in crosslinking.

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In the screen printing emulsion described in Example 5, 8 % of the oil, dissolved in ethylene glycol monomethyl ether, is finely divided. A smooth sieve is obtained which can be cleaned with a water jet after 4 minutes
Exposure under the xenon lamp is developed imagewise. Without the addition, you will not get a screen printing stencil under otherwise identical conditions.

Example 10

In the screen printing emulsion described in Example 8, but which contains 1.8 S ^ 3-methoxy-diphenylamine-4-diazonium sulfate as the diazonium compound, 5 %
Ν, Ν'-Dimethylol-sebacic acid diamide finely dispersed
stirred in and rubbed with it. This dispersion is colored with crystal violet for a recognizable uniform coating of metal surfaces and additionally after dilution with the same amount of water
filtered through cotton wool. This is done by skidding
a plate made of mechanically brushed aluminum
coated. After drying with cold air and leaving to stand overnight, exposure is carried out under a negative original and developed by rinsing with water, the water jet must not be too sharp

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be. After development, the layer, which is initially still sensitive to friction, is dried and then dried for 10 minutes heated to 240 ° C and thus solidified the layer for long runs. Hydrophilizing the non-image parts and the annealed image areas are colored as usual in offset technology.

Example 11

5% 2,2,4,4-tetramethylol-3-pentanol-bisformal are stirred into the screen printing emulsion described in Example 2. For better distribution, the substance can be dissolved in acetone beforehand. A screen is coated with this copying solution, dried, exposed and developed. In the case of the shortest possible exposure time for such a screen printing stencil, the crosslinking is not sufficient in the case of a comparison screen which is produced without the additive. Similar results are obtained when 2,2,4,4-tetramethylolpentanone-3-bisformal is used as hardener.

Example 12

50 Vt. a solution containing 20 g of Luviskol K 90 and 10 g of Luviskol VA 60 (both polyvinylpyrrolidones from BASF, Ludwigshafen) in 100 ml of ethylene glycol monomethyl ether

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contains, are mixed with 50 Vt. of the polyvinyl acetate dispersion Mowilith DM 1 H, 2 pbw. 3-methoxy-diphenylamine-4-diazonium sulfate and 30 pbw. a solution of polyvinyl alcohol (12 % vinyl acetate content, K value 75) thickened to a viscosity of 50,000 cp. To 100 Gt. this screen printing emulsion is a solution of 4 pbw. N-methylol-4-azido-cinnamic acid amide and 6 parts by weight. 2,6-Dimethylol-p-cresol ψ given and finely divided. A screen is coated with it, dried with cold air, exposed for 2 minutes under a negative original and developed with cold water. Without the additives, the screen cannot be used as a printing stencil under the same manufacturing conditions.

The N-methylol-4-azido-cinnamic acid amide used (mp 132 ° C from methanol, analysis: found 55.7 % Cj 5.1 % H; 25.4 % N; calculated 55.0 % C; 4.6 % H; 25.7 % N) is prepared as usual from 4 ~ azido-cinnamic acid amide (p. 158 ° C from ethanol, analysis: found 57.1 ίί C; 5.3 Η; 29.3 % N; calculated 57 , 5 % C; 4.2 % H; 29.8 % N) obtained by condensation of 4-azido-benzaldehyde with malonic acid monoamide analogously to JACS 70; 2568 (1948) is easily accessible.

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Example 15

The screen printing emulsion described in Example 2 are 6 pbw as hardener. Dimethylolurea added. at this hardener is for the goodness of the screen printing stencil Compliance with certain conditions is particularly important, since dimethylolurea hardens easily or small amounts result in a relatively large crosslinking effect. If the amount of hardener used is significantly increased, the Shelf life decreases significantly, if it is reduced further, optimal hardening is not achieved.

Example 14

In the screen printing emulsion of Example 13, the urea derivative used is the equivalent amount of 1,3-dimethylol-5-allyl-1,3,5-triazinon-2 used, but a three-fold excess can also be used. That developed Sieve is clearly solidified by heating to 100 ° C.

Example 15

With 100 Gt. of the emulsion described in Example 8 are 2 pbw. the diazoamino compound prepared from 3-methoxy-diphenylamine-4-diazonium sulfate and diisobutylamine, dissolved in 10 pbv. Ethylene glycol monomethyl ether, stirred. 8 Gt as hardener. Tris- (ß-chloropropionyl) -hexahydro-1,3,5-triazine. After intense

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Stirring, this copying solution is used to coat a sieve, dried with cold air and exposed imagewise for 10 minutes under the xenon lamp Developing with running water is post-hardened by heating to 100 ° C. Without the hardener additive the screen printing form is easily swellable in water and P can be removed mechanically very quickly.

Example 16

A screen printing emulsion consisting of 50 Gt. the internally plasticized polyvinyl acetate dispersion Mowilith DM 2 HB, 50 pbw. of the polyvinyl alcohol solution used in Example 12 and 2 pbw. 3-Methoxy-diphenylamine-4-diazonium sulfate is stirred with the solution of 7 g of 4,4 · diacetoxymethyl-diphenyl ether in ethylene glycol monomethyl ether. A screen is coated with it, dried with cold air, exposed for 4 minutes and developed with a water jet. A stable, smooth screen printing stencil is obtained; a comparison screen without the addition of hardener is unusable.

Example 17

For example in 2 used Emulsion 2% N-methylol-2-cyanobenzamide and optionally finely mixed.

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A screen made with this solution is for normal pressure loads with solvent screen printing inks just usable, a comparison screen without the hardener, however, not because the layer during development swells and dissolves.

Example 18

In 100 Gt. the screen printing emulsion described in Example 5 an ethanol solution of 6 pbw. NjN'-dimethylol-m-benzene-disulfonic acid amide stirred in. A sieve coated therewith is dried with cold air and exposed for 3 minutes under the xenon lamp and developed by hosing down with warm water. A very stable screen printing stencil is obtained.

Example 19

A saturated solution of 10 pbw. 2,2-di- (4-hydroxy-3,5-dihydroxymethyl-phenyl) -propane in acetone is 100 pbw. the emulsion described in Example 8 intense mixed and coated a sieve with it. This is dried quickly with warm air and 6 minutes exposed under a positive original with a 5000 watt xenon lamp. You get after the development

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with cold water one preferred for solvent ink screen printing suitable template. The copier solution can be used for at least two weeks.

Example 20

10% of 2-methyl-1,3-dioxolane are added to the emulsion described in Example 6 and distributed uniformly. A sieve made with it is exposed for 5 minutes under the carbon arc lamp. A usable screen printing stencil is obtained.

Example 21

An aqueous solution of 5 pbw. Ν, Ν'-dimethylol-dithiodiacetamide becomes 100 pbw. the emulsion described in Example 8 stirred> diluted with water 1: 1 and applied by spin coating to a carrier, which consists of a 30. _u thick copper skin-clad insulating material made of glass fiber reinforced epoxy resin compound. It is dried with cold air, exposed for 9 minutes under a negative line original with the xenon lamp, carefully developed with cold water and, if necessary, accelerated by wiping over the development. By brushing over with aqueous methyl violet

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Solution, the image areas are colored and at the same time the copy is precisely checked. Afterward the layer is further solidified by drying and heating to 100 - 130 ° C. She is firm enough in order to withstand the etching of the copper with ferric chloride on the exposed parts. You get one like that Raised shape made of copper on plastic, which, depending on the template, is used as a circuit board or for printing can be.

Example 22

50 Gt. the emulsion described in Example 8, mixed with 50 pbw. a 25 # solution of polyvinylpyrrolidone (Molecular weight about 700,000) in ethylene glycol monomethyl ether and 1.9 pbw. Diphenylamine-4-diazonium sulfate, are with an aqueous solution of 8 pbw. Tetramethylol hydrazodicarboxamide stirred.

With this copying solution can also be a resistant Make a screen printing stencil.

Example 23

U% N-methylol polyacrylamide is added to the screen printing emulsion of Example 2. With this copy solution a

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Sieve coated, dried with cold air, exposed for 5 minutes under a carbon arc lamp, developed with water and dried. The screen printing stencil obtained is suitable for large print runs.

Example 24

5 Gt. N-methylol-phthalimide are in ethylene glycol monoethyl ether solved and at 100 Gt. given the emulsion described in Example 5. With this copy solution a fabric for screen printing is coated by squeegee coating on both sides, dried with a hair dryer and under exposed a positive original with a 5000 watt xenon lamp. The unexposed image areas of the screen can be easily dissolved with running water, but the exposed areas are very resistant. Without The addition of the hardener dissolves the comparison screen during development. With the as described At least 1000 textile prints can be made.

Example 25

For the emulsion described in Example 16, but which contains 1.2 pbw. 2,5,4'-triethoxy-diphenyl-4-diazonium chloride as photosensitive Substance per 100 Gt. contains, becomes a

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aqueous-alcoholic solution of 0.5 pbw the in the following given methylol compound described. A A sieve coated with it and dried with cold air is exposed for three minutes under the xenon lamp and developed with water. A well networked screen printing stencil is obtained; a comparison sieve without however, the additive is quickly and completely stripped.

To produce the hardener, the commercially available 4-amino-benzenesulfonylurea is first found via the diazo compound to form 4-azido-benzenesulfonylurea (from methanol decomposition point 178-118 ° C., analysis calculated: 29.1 % N; 13.3 % S, found: 29 , 4 % N; 13.1 % S) implemented. This light-sensitive urea derivative is briefly heated in a soda-alkaline solution with excess formaldehyde, buffered with ammonium acetate and the light yellow solution is slowly cooled. The crosslinking-active 4-azido-benzenesulfonylurea-N-methylol compound is obtained as a granular white powder, is washed with water, dried and stored at room temperature until it is used as described.

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Example 26

The photosensitive compound of the emulsion described in Example 16 is 2,5-dimethoxydiphenyl ether-4-diazonium chloride as zinc chloride double salt and as hardener solution to 50 Vt. 5 Vt. given a 10 # solution of dimethylolurea. A screen made with it is more than sufficiently hardened after just 3 minutes of exposure Comparative sieve without the methylol compound, however, not at all.

Example 27

The procedure is as in Example 26. However, 2,5,4'-triethoxydiphenyl sulfide-4-diazonium chloride is used as the sensitizer and exposure is 4 minutes. The screen printing stencil obtained is excellent Edge sharpness.

Example 28

To 100 Vt. of the emulsion described in Example 5 are 3 pbw. 4- (2-methoxy-5-ethoxy-benzoyl-amino -) - 2,5-diethoxy-phenyl-diazonium chloride and 10 Vt. 10 # Dimethylo! Urea solution given. A

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a sieve coated therewith is exposed for 4 minutes and developed with running water. A good screen printing stencil is obtained.

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Claims (7)

2057A73 Claims lly light-sensitive copying paste which contains as essential components at least one condensable aromatic diazo compound, at least one binder and at least one substance capable of crosslinking, characterized in that it contains at least one diazonium salt of the general formula wherein R ₂ , R ^ and R ^ are the same or different and are hydrogen atoms, halogen atoms, alkyl groups with 1 to 2 carbon atoms or alkoxy groups with 1 to 4 Carbon atoms,
209822/081 1 Y is a single bond or one of the Groups -0-, -S-, -NH-, -CONH- and X the anion of the diazonium salt means, or a diazoamino compound prepared therefrom and contains at least one compound that contains at least one, Substituents of the formula - ^0H 3-n ^Z n carries what Z is a halogen atom, a hydroxyl group or an etherified, esterified or acetalized one Hydroxy group with 1 to 4 carbon atoms and η is a number from 1 to 3 where Z is a halogen atom when η is greater than 1. 209822/0811 2. copying paste according to claim 1, characterized in that it is a diazonium salt of the general formula I, in which Y is an -NH- group. 3. copying compound according to claim 1 or 2, characterized in that it is one for crosslinking capable compound containing at least one substituent of the formula carries, which is on the nitrogen atom of a primary or secondary acid amide. 4. copy paste according to claim 1 or 2, characterized in that it contains a compound capable of crosslinking, the at least one Substituents of the formula -CH, carries, which is on an aromatic carbon atom of a phenol or a phenol ether. 2 09822/0811 - ki - 5. copying paste according to claim 1, characterized in that it is in the form of an aqueous Solution or dispersion is present. 6. copy paste according to claim 1, characterized in that it is in the form of a solid photosensitive layer is present on a support. 7. copying paste according to claim 6, characterized in that the carrier is a screen printing carrier. (Jf 209822/0811 Formula I. To the KALLE AKTIENGESELLSCHAFT patent application K 1985, Wiesbaden-Biebrich, from November 20, 1970 on: "Light-sensitive copying compound" 209822/0811