DE2065914A1 - Dry positive working photoresist compsn. - contg. curable hydroxy or amino substd. polymer and light-sensitive bis-diazonium salt - Google Patents

Abstract

Flexible thermoplastic light-sensitive curable compsn. yielding positive images consists of a curable synthetic or natural polymer (I) with recurring OH or amino gps. and a light-sensitive bifunctional cpd. (II) effecting cure on treatment with basic substances. The improvement comprises the use of a bis-diazonium salt as (II), having a cation of the Formula +N triple bond N-R- (XR)q N-=N+ (in which q = 0 or 1. R is an aromatic hydrocarbon polynuclear quinone or heterocyclic ring of aromatic character, linked at its cyclic C atoms. X is alkylene with min. 2C, arylene, azo or sulphone and, if q = 1, X can also be an alylenedioxy or arylenedioxy gp. and R is aroyl or arylsulphonyl). (II) has an inorg. anion. This positive-working photoresist material can be used and transferred dry and has satisfactory thermal stability. A typical (I) is the Zn chloride salt of 1,4-butylene-(4,4'- tetradiazonium) dibenzate. E.g. 0.5 g this cpd. was incorporated in a photoresist coating based on poly(methyl methacryle/-hydroxyethyl methacrylate) for a Cu-plated glass fibre-reinforced epoxide resin panel. Exposure for 2 min through a process negative with C arc lamp, treatment with NH3 vapour.

Description

5 Cologne ι. April 1, 1976

DEiCHMAMNMZ-Uj Λ '.' MU »'.- ¹ - ¹ " ^ ": · ¹ F

EGG. DuPont de Nemours and Company, Wilmington 19 393, Delaware, U.S.A.

Flexible, thermoplastic, photosensitive mass for the production of positive records

When using light-sensitive materials for the production of relief-like records, e.g. in the field the photoresists, it is known to use recording materials in the form of polymer coatings on carrier materials, like metal plates. In the case of imagewise exposure, the recording materials are usually used made insoluble in the exposed areas. These areas are then used in the subsequent development of the Plates not washed out with solvents. The masses usually used for this purpose are usually brought as liquids or they require in addition to treatment with liquid developer at least a further, usually several process steps running in liquid form. Raising awareness in the liquid Polymers present in the mass is usually made through the use of light-sensitive azides, jichromates or cinnamon acid esters.

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ÖAO ORIGINAL

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In the Uo-PSeη 3 469 932 and 3 4l8 295 are materials described for the production of photoresists. which no Require awareness or application methods, dje in run off in liquid form. These include dry photopolymerizable Material layers that contain ethylenically unsaturated compounds with moderate adhesive strength a temporary layer support and can be covered with a protective film, which has a lower adhesion has opposite the photopolymerizable layer. The materials work negatively, i.e. the unexposed areas are washed out during development.

In some cases it is desirable to be dry photosensitive Use masses for the production of relief-like records, especially in the unexposed areas become insoluble, so that a positive-working recording material is present. Such masses should be in the photosensitive form be sufficiently thermostable, the process of transferring the photosensitive material layer, which is usually carried out with the application of heat to survive from the temporary carrier to the permanent carrier undamaged.

US Pat. No. 3,274,166 discloses compositions based on hydrocarbon polymers known, which in the presence of polydiazo compounds, such as bis-diazonium salts, can be modified by heating or irradiation with ultra-violet light, v. whereby the vulcanization is more natural and synthetic rubber compounds are in the foreground The bis-diazonium salts used for these purposes are not thermally stable.

From GB-PS 1 113 759 light-sensitive, photographic recording layers are known, the light-sensitive, contain polymeric diazo group-containing compounds of the phenol type. The DT-AS 1 120 273 describes

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also light-sensitive, photographic recording layers, especially for the production of printing forms. These layers consist in whole or in part one or more naphthoquinone- (1,2) -diazide-sulfonic acid esters containing at least one free hydroxyl group of hydroxyl compounds of diphenyl, naphthalene or Dinaphthyls, it being possible for the hydroxyl groups to be substituted. Copy layers for printing forms made from naphthoquinone (l,?) Diazide sulfonic acid esters are known from DT-AS 1 124.

When using the coating mixtures according to GB-PS 1 1Γ3 759 and the two DT-AS 1 120 273 "and 1 124 8l7 these are applied directly in liquid form to a base, which is the carrier material of the Representing printing form, for example on pretreated aluminum or zinc plates or special paper. To be adequate Adhesion on this carrier material, which is obtained as such during exposure and all further processing remains to ensure, its special pretreatment is required before applying the mixture. This should also contain a solvent to improve adhesion. Recording layers from the three known Mixtures produce positive images; when exposed, the exposed areas of the layer become soluble, while the unexposed areas Areas remain insoluble.

The photosensitive layers described have the disadvantage that, taking special precautionary measures, they have to be applied as firmly as possible to a layer support on which they remain during the exposure and the entire further processing. The existing from suitable for printing forms metal plates, metal foils or specialty papers permanent support are access- with the applied layer at all packaging, shipping and follow-up possible damage \

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The GB PC ^; IÜ1 898 describes a negative-working process in which layers of a colloidal material such as gelatin are tanned directly in the exposed areas during exposure by means of incorporated diazo compounds and thus made insoluble in the exposed areas. Diazo compounds listed include those of the formula RXR- in which X can represent a —CHp group and the radicals R and R are aromatic or hydroaromatic radicals, at least one of which has a diazo group. Any indications of directly positive photosensitive photoresist layers cannot be inferred from this suggestion of the prior art. GB-PS 1 001 821 finally describes the production of lithographic positive images, the photosensitive material used being a mixture of a hydrophobic, resinous coupling component of high molecular weight with hundreds of coupling functions together with certain diazo complex salts which in particular have ether groups or sulfonamide groups. As resinous hydrophobic coupling components, in particular polyvinyl acetacetate, acetoacetate ester of hydroxyethyl cellulose, polyvinyl acetate acetacetate and the reaction product of a copolymer of vinyl methyl ether and maleic anhydride with an aromatic hydroxycarboxamide compound are mentioned. After exposure, the material layers are developed with moist ammonia vapor, the coupling reaction being triggered in the unexposed areas. These areas should then be used as ink-accepting positive printing blocks.

The invention is based on the object by selecting suitable ones Components to create a photosensitive material for making positive photoresist images directly. That The photosensitive material to be selected should be used as a dry layer be usable and transferable, with in particular a sufficient thermal stability for implementation the transfer process should be guaranteed.

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The invention is accordingly based on a flexible, thermoplastic, photosensitive, crosslinkable, positive Images providing, given rifalls on a layer support applied mass, consisting of

a) a crosslinkable polymeric synthetic or naturally occurring, essentially uncured compound with adhering, repeating hydroxyl groups or amino groups and

b) a photosensitive, bifunctional compound that has a crosslinking effect when treated with basic substances.

It is characteristic that the mass as component b) is a photosensitive Contains bis-diazonium salt, in which the cationic portion of the salt of the formula

⁺ li jj N - R - (XR) - N ^ N ⁺

corresponds to where q = O or 1 and R is an aromatic one Kohlwa.ssersto.ff, a polynuclear quinone or a heterocyclic ring of aromatic character and the bonds adhere to its cyclic carbon atoms, X is an alkylene radical having at least 2 carbon atoms or an arylene, azo or sulfone radical, but where q = 1, X is also one Alkylenedioxy or arylenedioxy and then ™

R stands for an aroyl or arylsulfonyl radical, where the anionic portion of the salts is an anion of an inorganic salt.

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Suitable aromatic rings are those of benzene. Naphthalene, acenaphthene, anthracene and phenanthrene. Suitable multi-ring quinones are anthraquinone and phenanthraquinone, suitable compounds containing heterocyclic rings are pyrazole and acridine. The rings can be substituted, for example by Cl, Br, an alkyl radical with 1-4 Carbon atoms and an alkoxy radical with 1 - 4 carbon atoms. Examples are: The methyl, ethyl, propyl and butyl radicals and the corresponding alkoxy radicals. To the Useful alkylene radicals with at least 2 carbon atoms include the ethylene radical, the isobutylene radical and the tetramethylene radical and polymethylene radicals with 5-8 carbon atoms, suitable arylenes are phenylene and naphthylene.

Photosensitive particularly suitable for the purposes of the invention bis-diazonium salts - i.e. as the aforementioned component b) particularly suitable bis-diazonium salts - are characterized in that the cationic part of the salt formula

U ^ NR '- Y - (CHp) _n -YR' -N = N!

! ι corresponds to where R 'is a substituted or unsubstituted Benzene, naphthalene, anthracene or phenanthrene radical stands, ;

Y is the -COO group or the -SO ^ group, where R 'is at Carbonato;

Group is liable,

Carbon atom or sulfur atom of -COO- or -SO, -

n is an integer of at least 4, preferably - 18,

The anionic part of the salt is an anion of an inorganic one Sa] ses is. Preferred salt-forming compounds are zinc chloride and acids or salts in which

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the anion is a fluoroborate residue, a sulfate residue, a fluorosulf onatresfc, an oxalate residue and a citrate residue isJ

The following bis-diazonium salts are for use Of particular importance in the context of the invention:

(1,4-butanediol) dibenzoate 4,4'-bis (diazonium zinc chloride), (1,5-pentanediol) -dinaphthoate-5,5'-bis (diazonium zinc chloride), (1,4-Butanediol) -dinaphthylsulfonate-4,4'-bis (diazonium-

fluoroborate),

(1,4-Butanediol) -dinaphthyl-6 ~ sulfonate-2,2'-bis / ~ metliyl_.7-1,1'-bis (diazonium fluoroborate),

Resorcinol dibenzoate 4,4'-bis (diazonium zinc chloride), (2,4-pyridinediol) -dibenzoate-4,4'-bis (diazonium zinc chloride),

Benzene-l, ^ - bis (diazonium fluoroborate), Denzol-1, ^ - bis (diazonium fluoroborate), naphthalene-l ^ -bi ^ (diazonium fluoroborate), naphthalene-1,5-bis (diazonium fluoroborate) -7-sulfonic acid, anthracene -l, 6-bis (diazonium fluoroborate ), anthranes-1,5-bis (diazonium fluoroborate) -7-sulfonic acid, anthraquinone-1,6-bis (diazonium fluoroborate), phenanthrene-1,5-bis (diazonium fluoroborate), fluorene-2 , 7-bis (diazonium fluoroborate), acenaphthene-4,6-bis (diazonium fluoroborate), 2, e-dimethoxypyridine - ^, 5-bis (diazonium fluoroborate), pyrazole-3,5-bis (diazonium fluoroborate), acridine-3,6 -bis (diazonium fluoroborate ), biphenyl-Ί, 4'-bis (diazonium fluoroborate), biphenyl-'i, 4 '-bis (diazonium fluoroborate) -2., 2' -bis-sulfonic acid, 2,2'-dimethyl- biphenyl-4,4'-bis (diazonium fluoroborate), 1,2-diphenyl ^: ithan-4,4'-bis (diazonium fluoroborate), 1,3-diphenylisobutane-4,4'-bis (diazonium fluoroborate), p-terphenyl -4,4'-bis (diazonium fluoroborate), diphenylsulfone-4,4'-bis (diazonium fluoroborate), azobenzene-4,4'-bis (diazonium fluoroborate).

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One suitable method for preparing the salts is in diazotizing the corresponding bis-amines; special examples for the production of the salts and for their use are described below. The bis-diazonium salts used according to the invention are thermally stable and can therefore with advantage in the crosslinkable photosensitive Masses and materials are used.

The colloids to be used in the context of the invention are more synthetic or natural and have repeating hydroxyl groups or amino groups. Examples are polymeric polyhydric alcohols, natural colloids such as gelatin, glue, shellac; also obtained by addition polymerization Polyesters such as polyesters of acrylic acid and methacrylic acid; furthermore polyvinyl alcohol, poly-p-aminostyrene.

The crosslinkable photosensitive layer preferably has a thickness of 1 to 75 / U or more; a support or a protective film to be applied if necessary lies in one Thickness from 6 to 125 / u before.

The crosslinkable, photosensitive ones used according to the invention Materials can be produced by adding a solution or a dispersion of the crosslinkable, light-sensitive organic mass applied to a thin, flexible, smooth support and the layer by removal or evaporation any volatile solvent or diluent still present dries. The carrier should preferably solid, transparent to actinic light, with temperature changes dimensionally stable and resistant to the action of common solvents. The carrier is supposed to do so be that there is only a moderate adhesion or tendency to stick between the coating and the carrier, so that it differs easily from the networkable, light-sensitive, organic layer can be peeled off.

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A protective film can be pressed on or laminated on attach, for example, by removing the film or the Runs the film and the coated, crosslinkable material through rollers. If a protective film is used, it should have a lower adhesive strength on the layer than ' the "support.

According to a preferred embodiment of the invention, the layer of the photo-crosslinkable, photosensitive composition is present on a transparent base film and is covered on the surface with a removable protective film. The crosslinkable, photosensitive mass is used with a dry thickness of the layer of about 13 / u, although the layer thickness is between 3 λχ or less and 127 / u. or more can vary.

Suitable carrier films can be made from many metals or high polymers consist, for example, of polyamides, polyolefins, polyesters, vinyl polymers and cellulose esters; the Carrier foils can have a thickness of G to 127 / U. If one exposes before the removal of the base film, so it must of course allow a substantial portion of the incident actinic radiation to pass through. This requirement not applicable if the carrier film is removed before exposure. Have transparent films made of polyethylene terephthalate It has proven particularly useful as a layer support; it is expedient to use it in a thickness of about 25 / U. If you are with Removable protective films works, so these can consist of the same materials as the layer carriers and from be of the same thickness. The protective film should preferably be less strongly attached to the crosslinkable, photosensitive layer adhere as the substrate. The substrate and protective film protect the light-crosslinkable compound.

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When the material is ready for use, the protective film is removed. The crosslinkable, photosensitive film is then on a solid support with a smooth surface, for example one made of metal or glass, with the aid of heated laminated on resilient pressure rollers. In this way receives a crosslinkable, photosensitive material that can now be exposed, but against harmful influences the environment through the original carrier film is protected.

These photosensitive crosslinkable compositions and materials used according to the invention differ from them of the prior art in that the exposed areas are desensitized on imagewise exposure. the Desensitized areas do not crosslink and remain soluble if the material is subsequently exposed to basic vapors or a basic solution. In this way it is possible to use the exposed areas during development wash off the material with an organic or aqueous solvent.

The processing of the material according to the invention takes place example as follows:

It is exposed imagewise, preferably through the support, this is then peeled off and the unexposed Areas treated with the fumes of ammonia or an organic amine. The vapors network the unexposed bis-diazonium salt with, for example, a pendant hydroxyl group, with a hardening of these areas takes place. Then the material is washed out by washing out the uncured, exposed areas with a solvent developed. You can develop with both aqueous and non-aqueous organic solvents work, depending on the type of colloid applied in the! crosslinkable, photosensitive mass. Represents the colloid

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represents a hydrophilic compound, so used nan. an aqueous solvent, while an organic solvent is used if the colloid is a hydrophobic, oleophilic compound.

The washed out material is as relief or as positive Resist image usable.

In the experiments and examples below, the preparation of particularly suitable tetrazonium salts (experiments A and B) and the structure and use of the invention photosensitive materials described.

Try Λ '..

A new. Tetrazonium salt was prepared as follows: 0.5 mole of p-mitrobenzoyl chloride and 0.2 mole of 1,4-butanediol were refluxed in benzene for 18 hours. As

detected by infrared spectra, was confirmed by the addition of ^!

η-hexane precipitated a diester. The white precipitation |

(20 g) was dissolved in 250 ml of ethanol with 1 g of palladium on charcoal

reduced. (Hydrogen pressure: 4 atm at room temperature). j

Infrared spectroscopy of the product demonstrated the disappearance of the peak at 7.45 / u (N0 _o band) and the appearance of a band at 5.1 / u (NH _? Band). 0.1 moles of the (1,4-butanediol) dibenzoate-4,4'-bis-amine was diazotized with sodium nitrite and zinc chloride in 25 ml of hydrochloric acid at 10 ° C. The product was identified as (1,4-butanediol) dibenzoate -4,4'-bis (diazonium zinc chloride).

Example 1

0.5 g of the zinc chloride salt of 1,4-butylene (4,4'-tetrazonium) dibenzoate were dissolved in 25 ml of acetone containing:

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2.5 g of poly (methyl methacrylate / hydroxyethyl methacrylate) with an average molecular weight of about 30,000; (90 Mol.-Ji methyl methacrylate).

0.5 g p-toluenesulfonic acid,
1.0 g triethylene glycol diacetate, 2 cm "" ethanol,
1 ml of water.

The material was applied to a 25 / U thick polyethylene enterephthalate film applied to a thickness of I3 / U.

The coated material was allowed to dry at room temperature and then placed on a copper-clad epoxy fiberglass panel laminate with the help of heated rollers at 120 ° C, the photosensitive layer adhering directly to the copper. The polyester base film was peeled off and the crosslinkable, light-

sensitive layer then 2 min. through a process negative _:

while maintaining a distance of 6l cm with the help of a j

Carbon arc lamp (2500 watts; 14 amps) exposed. Now j

i · the layer was treated with ammonia vapors and the

keep image in the exposed areas with the help of 1

1,1,1-trichlorethylene washed out. After etching with Iron (III) chloride remained a positive copper image.

Example 2

A mixture was prepared according to Example 1 with the exception that 2.0 g of polyvinyl alcohol (99 to 100 % hydrolyzed; viscosity in H 90 aqueous solution = 55-65 centipoise) were used instead of the mixed polymer. This mass was coated and dried in the same way as in Example 1.

The coated material was then laminated onto a glass plate, exposed and, as explained in Example 1, further treated with the exception that for washing out the

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exposed areas hot water was used. The plate was suitable as a positive working relief image.

Be is pie I

Example ? was repeated except that a coated material was laminated on a steel plate and an aluminum plate each to a thickness of 0.102 mm. The plates obtained were suitable for use as positive-working relief images.

example H

According to the information given in the experiment, the following were suitable for obtaining crosslinkable, photosensitive compositions Salts prepared by adding 1,4-butanediol and p-iJitrobenzoyl chloride have been replaced by the corresponding dialcohols and mitroaroyl chlorides:

(1,5-Pentanediol) -dinaphtboat-5,5'-bis (diazoniumzinkchlorld), (I, j5-isobutanediol) -dibenzoate-4 , H'-bis (diazoniumzinkchlorld), resorcirioldibenzoate-4,4'-bis (diazoniumzinc chloride ).

Other useful salts can be prepared by "grounding" one other polymethylene glycols or aromatic dihydroxy compounds instead of the above diols and other nitroaroyl chlorides.

A mixture of each of these salts with foil (methyl methacrylate / hydroxyrithyl methacrylate) was, as described in Example 1, prepared, coated and laminated. After an analogous exposure and treatment with methylamine vapors, the image obtained could be used in the exposed Areas washed out with the help of 1,1,1-trichloroethane will. A'tzen was awake with ferric chloride a positive copper image.

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Example 5

A new sulfonate ester bis (diazonium salt) was prepared as follows: 0.1 mol of 1-nitro-2-methylnaphthalene-6-sulfonyl chloride in 100 ml of itenzene was refluxed for 24 hours with 0.04 mol of 1,4-p.utanic jiol . A disulfonate ester identified by infrared spectra was precipitated by adding 30 ml of n-FFexane. Then 0.02 moles of the bis-mitro-diester in 200 ml of ethanol were reduced with 10 Gevi.-7b of palladium on carbon under a pressure of 5 atm of hydrogen at 45 ° C. The bis-ΛπιΙη identified by infrared spectra was precipitated by adding water. The precipitate was dissolved in excess hydrochloric acid and diazotized with sodium nitrite. The hydrochloric acid salt was treated with '(0 ml of a 40% strength fluoroboric acid to give the fluoroborate salt, namely (1,4-butanediol) dinaphthyl-G-sulfonate-2,2'-bis- / methy1_ / -1.1 '-bis (diazonium fluoroborate) to form.

0.5 g of this bis-diazonium salt in a 5 g of water and A solution containing 1 g of methanol was mixed with the following substances:

5 g polyvinyl alcohol, which is 88.2 % to 89.2%

was hydrolyzed,
50 g v / ater,
0.2 g citric acid,
1.0 g of triethylene glycol diacetate.

This mass was then applied to a 25 M thick polyethylene terephthalate support to a thickness of 13 / U and, after drying at room temperature, laminated with a / U thick protective film made of polyethylene.

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After 15 days the protective polyethylene film was peeled off and laminated the crosslinkable, photosensitive material, exposed and further treated as described in Example 1 with the exception that for washing out the exposed Areas hot water was used. The plate was suitable for use as a positive working Ke ran picture.

Attempt B

Naphthalene-1,5-bis (diazonium fluoroborate), which is suitable for use in the process of the invention, was prepared as follows: 0.1 mol of 1,5-naphthylenediamine was mixed with 28 g of sodium nitrite in 250 ml of conc. Sulfuric acid at 10 ° C for 1 hour. Stirred and then poured into 1 liter of ice water. The obtained bis- (diazonium sulfate) dissolved in 2 liters of water) was transformed by addition of 70 ml of ^l \ 0 £ sodium Plucrborsäure in Maphthalin-1,5-bis- (diazoniumf luorborat).

The following bis (diazonium fluoroborate) salts which are suitable for the Suitable use in the process of the invention can be prepared from the corresponding diamines by the same procedure getting produced:

Benzene-1, H -bis (diazonium fluoroborate), berizol-1,3-bis (diazonium fluoroborate) , naphthalene-1,5-bis (diazonium fluoroborate) -7-sulfonic acid , anthracene-1,6-bis (diazonium fluoroborate ) _s anthracene -1,5-bis (diazonium fluoroborate) -7-sulfonic acid, anthraquinones, 6-bis (diazonium fluoroborate), phenanthrene-1,5-bis (diazonium fluoroborate), fluorene-2,7-bis (diazonium fluoroborate), acenaphthene-4, 6-bis (diazonium fluoroborate), 2,6-dimethoxypyridine-j5j5-kis (diazonium fluoroborate), pyrazole-3,5-bis (diazonium fluoroborate), bi phenyl-J, 4 '-bis (diazonium fluoroborate) -2, 2' -bis-sulfonic acid,

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2,2'-dimethyl-bisphenyl-4,4'-bis (diazonium fluoroborate), 1,2-diphenylethane-4,4'-bis (diazonium fluoroborate), 1,3-diphenylisobutane-4,4'-bis (diazonium fluoroborate), ρ-terphenyl-4,4'-bis (diazonium fluoroborate), Diphenylsulfone-4,4'-bis (diazonium fluoroborate).

Example 6

A 10 g of ethanol and 2 g of water-containing solution of 1 g 'iaphthalin-l, 5-bis (diazoniumf luorborat) was added to a well stirred solution of 2.5 g of polyvinyl butyral (HydroxylgehaIt: 18 to 20 ^r / and Dutyralgehalt 80%) with 0.3 ß citric acid α and 0.8 g of triethylene glycol diacetate in 50 g of ethanol are added. This solution was coated on a 19 / U support film made of polyethylene terephthalate to a thickness of 51 u is applied and, after drying at room temperature, a piece of it to a sheet of red, anodized aluminum sheet was laminated by the sheet j on the on the support lying crosslinkable, photosensitive mass slowly passed between two rollers heated to 110 ° C! became. The material was then ^{exposed through a process negative:} and the transparent polyester layer support for 1 min. With a 500 watt mercury arc lamp (PEK 500) at a distance of 40.64 cm. Then, the polyester film was removed and the coated sheet punched with ammonia vapors behan- W, the crosslinked, the unexposed areas of the photosensitive, crosslinkable layer. The non-crosslinked areas were washed out by spraying with 2- (2-ethoxy) ethanol. The plate was then rinsed with water and at | Treated at 70 ° C. with 5 strength sodium hydroxide solution with formation of a luminous aluminum image in the exposed areas. The resist was then removed with methylene chloride.

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Example 7

Dlphenylmethane-'ί, 4'-bis (diazonium fluoroborate) was prepared from the corresponding diamine according to the procedure of Experiment B. The process according to Example 6 was repeated with this salt with the exception that the polymeric binder was polyvinyl formal with a hydroxyl content of 7-9 ^ and 80% formal content.

Example 8

1 g of biphenyl-4, 4 '-bis (diazonium fluoroborate), dissolved in a mixture of 10 g of ethanol and 1 g of water / water, - which had been prepared from the corresponding diamine as described in Experiment B, was a solution of 2, 5 g flydroxypropyl cellulose, 0.5 g propylene glycol and 0.5 g citric acid in 50 g ethanol were added. The crosslinkable, photosensitive composition obtained was applied as indicated in Example 6 and dried. The material was then laminated with a 6 / U thick polyethylene protective film at 50 ° C. 2 days later the protective. film is peeled off and the crosslinkable, photosensitive material using V / a 1 ze η heated to 130 ° C. is laminated onto a glass plate cleaned with acid, so that the crosslinkable, photosensitive layer adhered to the glass. Then the polyester base film was peeled off and the plafc- 'te exposed to a process negative for 1.5 minutes at a distance of 40.64 cm with a 1000 W xenon arc lamp. Mach J Min. Treatment with ammonia vapors, the exposed areas were washed out by spraying 2-Mothoxyethanol. The Uber-coated plate was heated for 10 min. At I5O ⁰ C and then with an aqueous, 25 $ strength hydrofluoric acid 1 etched to form a positive image after removal of the remaining resist.

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Example 9

Azobenzene-Ή, 4'-bis (diazonium fluoroborate), which is suitable for use in the crosslinkable, photosensitive compositions of the invention, was prepared as follows: p-i'iitroaniline (2J, ^ g) was acetylated with excess acetic anhydride and reducing the nitro groups of the resulting p-mitroacetanilide according to Example 5 to the amine. Then 0.2 mole of p-aminoacetanilide in hydrochloric acid was diazotized with sodium nitrite and coupled with 0.2 mole of p-aminoacetanilide to form a symmetrical azoacetanilide. This azo compound was hydrolyzed in acid and further diazotized using the procedure described above to produce azobenzene- '1, H ' -bis (diazonium hydrochloride) which was converted to the fluoroborate salt by treatment with 70 ml of a 40 5% fluoroboric acid.

Example 10

A 10 g ethanol and 0.5 g V / ater containing solution of 1 g of azobenzene-4, k '-bis (diazonium) was added to a well stirred solution of 25 g cellulose acetate butyrate (50% butyrate), 0.5 g of p- Toluenesulfonic acid and 0.5 g of triethylene glycol diacetate in 30 g of acetone.

The crosslinkable, photosensitive composition was drawn onto a 25 / U thick carrier film made of polyethylene terephthalate with a thickness of 51 / U and laminated onto a copper-coated epoxy resin fiberglass plate with the aid of rollers heated to 1 ^ 0 C, the crosslinkable, photosensitive Layer adhered to the copper. The colored layer was exposed for 30 seconds through a process negative at a distance of 40.64 cm from a 1000 watt quartz iodine lamp, a visible image being obtained by bleaching the exposed areas. The polyester base film was "peeled off, the exposed layer

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adhered to the copper and was treated with ammonia vapors which enhanced the visible image. Then the exposed areas washed out with the help of 2- (2-ethoxy) -ethanol, I laugh at the etching in iron (III) chloride at 65 ° C and subsequent removal of the crosslinked, unexposed areas with methylene chloride, a copper image remained on the Fiberglass sheet that can be used as a card for printed circuits let use.

Example 11

1.5 g of acridine-J>, 6-bis- (diazonium fluoroborate) were in a Mixture of 15 g of ethanol dissolved with 1 g of water. That Fluoroborate was from the diamine according to the procedure -des Experiment B has been prepared, the solution described was partially acetylated from a well-stirred solution of 15 g Polyvinyl alcohols (viscosity: 900 to 1200 centipoise) added, which also contained 1 g of triethylene glycol diacetate and 0.5 g of citric acid in 33 g of water.

The crosslinkable, photosensitive composition was applied and laminated with a protective film as indicated in Example 6. Later the protective cover sheet was peeled off and the coated substrate laminated to a magnesium metal plate, heated to 80 ° C with Rolling was worked. The base film made of polyester was peeled off, and that on the magnesium sheet Adhesive, crosslinkable, photosensitive layer exposed for 2.5 minutes through a halftone negative, with a Distance of 60.96 cm from a 2500 watt carbon arc lamp (.14 amps) was worked. The exposed layer was treated with methylamine and the exposed, uncrosslinked areas with a mixture of 50 parts by weight of 2- (2-ethoxy) ethanol and 50 parts by weight of water washed out. The magnesium sheet was rinsed with water and the exposed parts were etched for 5 months with 10% nitric acid solution. Mach removal of the remaining, cross-linked layer is the sheet metal equipped with the etched image can be used for prints. 60985 3/085 1

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20659H

Deisplel 12

A solution of 7 g of (1,4-butanediol) -dibenzoate-4,4'-bis (diazonium zinc chloride), 1 g of citric acid in 20 ml of ethanol and 30 ml of v / ater was kept at 27 C solution of 30 g of gelatin in 300 ml of deionized water and 1 ml of 10% aqueous saponin were added. After stirring for 30 minutes, the solution was applied with wiping to a 25 / U thick, flame-pretreated polyethylene terephthalate film. The resulting layer was cooled, dried and then laminated to a copper-clad epoxy resin fiberglass plate using rollers heated to 50 ° C., and the crosslinkable, photosensitive layer was adhered to the copper. 2 hours later, the layer was exposed, the carrier film peeled off and, as described in Example 1, a treatment with ammonia vapors was carried out. The image obtained was carefully washed out with water at 60 ° C. After etching in ferric chloride, a positive copper image remained.

Example 13

5 g of naphthalene-1,5-bis (diazonium fluoroborate) in a mixture of 10 g of ethanol and 10 g of water were added to a solution containing 20 g of poly-p-aminostyrene, 5 g of polymethyl-, W methacrylate (average molecular weight: 60,000 ), 7 g of triethyl glycol diacetate and 0.7 g of p-toluenesulphonic acid in 50 g of acetone and 10 g of ethanol. This crosslinkable, light-sensitive composition was prepared according to Example 1

ο '

brought and laminated to a zinc metal sheet at 120 C, j

that had been cleaned with pumice stone. The material was then processed through a negative and the transparent Polyester support through 10 seconds with a 500 watt mercury lamp (PEK 500) at a distance of 40.64 cm exposed. The carrier film was peeled off and the layer treated with ammonia vapors. The image obtained was washed out with methyl chloroform and the positive image produced is etched using 5 ^ nitric acid.

609853/0851

BAD ORfGJWAL

Claims (1)

20659U Claims 1.Flexible, thermoplastic, photosensitive, crosslinkable, positive images, if necessary on a layer carrier applied mass, consisting of a) a crosslinkable, polymeric, synthetic or natural occurring, essentially uncured compound with adhering, repeating hydroxyl groups or amino groups and b) a light-sensitive, bifunctional compound that has a crosslinking effect when treated with basic substances, characterized in that the mass as component b) contains a photosensitive bis-diazonium salt in which the cationic portion of the salt of the formula ⁺ N = N -R- (XR) -N 5 N ⁺ corresponds to where q = 0 or 1 and R is an aromatic one Hydrocarbon, a polynuclear quinone or a heterocyclic ring of aromatic character and the bonds adhere to its cyclic carbon atoms, in which, in addition, X is an alkylene radical having at least 2 carbon atoms or an arylene, azo or sulfone radical, but where q = 1, X also corresponds to an alkylenedioxy or arylenedioxy radical can and then R for an aroyl or arylsulfonyl radical stands, the anionic portion of the salts being an anion of an inorganic salt. : 2. Photosensitive composition according to claim 1, characterized ! net that the cationic portion of the salt of the formula "N ⁺ "N ₁ N - R ¹ - Y - (CHp) _n -YR ¹ - N ₁ corresponds to where R 'is a substituted or unsubstituted 609853/0851 _ ₂₂ _ 20659U ter benzene, naphthalene, anthracene or phenanthrene radical, while Y stands for -COO- or -SO, - and R ^{f is} attached to the carbon atom or the sulfur atom of these groups, η stands for an integer of at least 4 and the anionic portion of the salt is an anion from an inorganic salt. j5. Photosensitive composition according to Claims 1 and 2, characterized in that that the photosensitive bis-diazonium salt is a zinc chloride salt or a fluoroborate salt. 4. The photosensitive composition according to claims 1 to 3> characterized Wr, that the photosensitive bis-diazonium salt (1,4-butanediol) dibenzoate-4,4'-bis (diazonium zinc chloride), (1,5-pentanediol) -dinaphthoate-5> 5'-bis- (diazonium zinc chloride) or (L, 4-butanediol) -dinaphthylsulfonate-4,4 '-Ms- (diazonium fluoroborate) is. 5 · Photosensitive composition according to claim 1, characterized in that that the polymeric, crosslinkable compound is gelatin or polyvinyl alcohol. 609853/0851