DE2545327A1 - LIGHT SENSITIVE IMAGE GENERATION ELEMENT - Google Patents

Description

PATENT ADVOCATE Λ. GRÜNECKER

DIPL-K ¹ JG

H. KINKELDEY

DR-ING

W. STOCKMAIR

DRING-AeE (CALTECH)

K. SCHUMANN

DR BER NAT ■ DIPL-PHYS

P. H. JAKOB

G. BEZOLD

DR PER NAT- DIPL-CHEM

MUNICH

E. K. WEIL

DR REFl OEC IMG

LINDAU

8 MUNICH 22

MAXIMILIANSTRASSE 43

October 9, 1975 P9664

Fuji Photo Film Co., Ltd.

No. 210, Nakanuma, Minami Ashigara-Shi, Kanagawa, Japan

! photosensitive imaging element

The invention relates to a photosensitive imaging element, it relates in particular to a photosensitive element of the positive type having a photosensitive layer, which has an azide compound having an alkali-soluble group in their molecular structure contains.

photosensitive coating compositions for the production of Positive type imaging materials (hereinafter referred to as Posi type denoted) ^ as they are commonly used are e.g. those based on an o-quinone diazi & compound, a reaction product between a photosensitive diazonium salt and a heteropoly acid and the like. However, only a few of them are of commercial importance.

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TELEPHONE (089) 2C 28 62 TELEX Ο5-2β38Ο TELEaRAMMEMONAPAT

is sufficient with the exception of those based on o-quinonediazides.

As is well known, an o-quinonediazide (which in its Molecular structure contains the unit indicated below as a light-sensitive functional group) when exposed to light becomes, with formation of an alkali-soluble group according to the following mechanism (cf. 0. Süs, "Liebigs Annalen der Chemistry ", Volume 556, Page 65 ())

H FC = O ι

Such o-quinonediazide can be used alone or in admixture with other alkali-soluble resin materials such as phenol-formaldehyde resins, styrene / maleic anhydride copolymers and the like., used to increase the durability of the image, the film image- manure properties of the coating composition and the like. To improve. This compound can be used more advantageously in a homogeneous coating composition in combination with other additives such as a Dye, a plasticizer, and the like can be used.

A resin material that is blended to increase durability (resistance) To improve the image, but must not only be compatible with the o-quinonediazide compound, but also in one aqueous alkaline developer solution. · Since these conditions limit the range of resin selection, whereby e.g. the latter precludes the use of resins such as polyamides which are insoluble in an alkaline solution limits the resin materials that can be used to improve the durability or durability of the image.

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Previously AzidverMndungen were used as a light cross-linking agent, which decomposes by the action of active radiation, thereby causing crosslinking or dimerization _i and they were, therefore, on a large scale for light-sensitive coating compositions of the negative type (hereinafter referred to as Nega-type) is used. On the other hand, there are only a few examples in which azide compounds have been used in Posi-type coatings. An example is described by J. Kosar in "Light Sensitive Systems", John Wiley & Sons Ine, page 333, in which one Azide compound having an alkoxy group which forms a photodecomposition product having greater solubility than the original compound in dilute alkali is used, which compound is used for a Posi-type printing plate.

The main object of the present invention is therefore to provide a photosensitive Imaging material, particularly one of the Posi-type, specify which an image with an excellent mechanical strength provides, in particular, a polyamide resin component contains, which results in a very tough layer. The aim of the invention is in particular to provide a photosensitive Specify element of the Posi type, which consists of a beam and a thereon applied photosensitive material, which contains a polyamide resin component, which is an extraordinary results in a tough layer and provides an image with excellent mechanical strength,

After extensive research it has now been found that the The above objects can be achieved according to the present invention by means of a photosensitive layer containing an azide compound having an alkali-soluble functional group and containing a polyamide compound and for making a photosensitive Posi-type materials can be used.

The invention relates to a photosensitive image generator

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supply element, in particular one of the positive type (Posi type), which is characterized in that it consists of or contains a support and a photosensitive layer which is rendered alkali-soluble by exposure and (i) one Azide compound having at least one alkali-soluble group, such as a sulfonic acid, carboxylic acid or hydroxyl group, in their molecular structure and (ii) contains a polyamide.

According to a further aspect of the invention, the photosensitive Imaging element of the above construction has two photosensitive layers, the first having the photosensitive layer applied to the support is an o-quinonediazide compound and the second photosensitive layer applied to this first photosensitive layer Exposure is made alkali-soluble and contains the above azide compound and a polyamide.

In particular, the invention relates to a photosensitive imaging material from Posi-Tyj) which comprises an azide with a alkali-soluble group, for example a sulfonic acid, carboxylic acid or hydroxyl group. Although the mechanism according to which such a system functions as a photosensitive material of the Posi type, has not yet been fully clarified, it is assumed that alkali-soluble groups are introduced into the polyamide by the photodecomposition of the azide, whereby the polyamide is made receptive to the alkali. This is an essential point of the present invention, which means that the polyamides used in the invention do not have any particular restrictions are subject to so long as the system containing a polyamide is one which becomes alkali-soluble upon exposure to light. The different alkali solubility of the exposed and non-exposed areas enables the use of the areas according to the invention Elements as positive working elements.

According to the invention, a photosensitive coating which contains an azide and a polyamide as stated above can be

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if desired to another photosensitive coating containing an o-quinonediazide compound, whereby it is possible to improve the developability as well as the To further improve the quality of the image ·. At the same time can thereby an extremely durable or permanent image can be obtained, which can be achieved by using only a conventional light-sensitive o-quinonediazide coating is not achievable.

Various carrier materials can be used according to the invention These include, for example, metal plates such as those made of zinc, aluminum (including aluminum alloys such as Alloys with a predominant proportion of aluminum with Si, Cu, Mn, Mg, Cr, Zn and the like) or copper, plastic films, such as those made from nitrocellulose, cellulose diacetate, cellulose triacetate, cellulose butyrate, cellulose acetobutyrate, polyethylene terephthalate, Polystyrene, polycarbonate, polyethylene, polypropylene, Polyvinyl acetate and the like, paper, paper coated with polyethylene or polystyrene and the like, glass and the like. Regarding The carrier usable in the present invention is not particularly limited and the carrier may vary depending of ^ the requirements for the end use of the product to be manufactured Materials can be practically freely selected from those commonly used. The criteria used in the Selection of a suitable carrier used are known to those skilled in the art.

Examples of preferred aluminum alloys as mentioned above are (using the Aluminum Association of America nomenclature standards) the following alloys: 2S, which contains 0.4 wt% Si, 0.6 wt% Mg contains, AA1100, 3S, which contains 1.2 wt% Mn, and AA3OO3, 24-S, which contains 4.5 wt% Cu, 0.6 wt% Mn and 1.5 wt% Mg contains, 52 S containing 2.5 wt% Mg and 0.25 wt% Cr, 61 S containing 0.6 wt% Si, 0.25 wt% Cu, 1, 0 wt% Mg and 1.25 wt% Cr, and 75 S which contains 1.60 wt% C _u , 2.50 wt% Mg, 0.30 wt% Cr and Contains 5.60% by weight Zn, the remainder each consisting of aluminum.

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In the special case where the photosensitive imaging material of the invention is used as a photosensitive lithographic printing plate, the surface of the support should be hydrophilic, in which case the most preferred support is an aluminum plate. Such an aluminum plate is preferably a surface-treated aluminum plate, for example one whose surface has been mechanically treated by glass bead roughening (graining), ball roughening (graining), sandblasting treatment, brush roughening as described in Japanese Patent Application (OPI) No. 33411/73, or electrolytic roughening (Grain) or by chemical treatment with an aqueous solution of an alkali metal salt of phosphoric acid (followed by a 2 to 20 , aqueous solution of sodium tert-phosphate (Na, PO ^) at 50 to 85 ° C for a period of 30 seconds up to 5 minutes), a silicate or potassium fluorozirconate (e.g. with a he 0.3 to 10 ^ igen aqueous potassium fluorine zirconate solution at 65 ° C for a period of 1 to 3 minutes) and the like. Or by anodic oxidation using the aluminum plate as an anode (for example using a solution of an acid in water or a Solvents such as sulfuric acid, oxalic acid, boric acid, phosphoric acid. Sulphamic acid, chromic acid and the like _i in a concentration of

1 to 80% by weight, using an electrolyte temperature of 5 to 70 C, a current density of 0.5 to 60 A / dm, a voltage from 1 to 100 V and for a duration from 30 seconds to 50 minutes).

An aluminum plate covered with an aqueous sodium silicate solution has been treated (e.g. by immersion in a

2 to 5% strength by weight aqueous sodium silicate solution at 70 to 90 ° C for a period of 1 to 2 minutes) after graining (roughening) as described in US Pat. No. 2,714,066 is, or one that is anodically oxidized and then treated with an aqueous alkali metal silicate solution

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(for example, in the manner described above) as disclosed in Japanese Patent Publication No. ^ A 25/72 can also be used for these purposes in the present invention.

The azide compound used in the invention has in its Molecule has at least one alkali-soluble group and it preferably contains no more than 3 alkali-soluble groups in its molecule, although it is by no means restricted to it. One such alkali-soluble group is in usually a sulfonic acid, carboxylic acid or hydroxyl group, which may also be in the form of a salt thereof, e.g., in the form of an alkali metal salt (such as Na- ^ K-, Li ^ salt and the like). Among the azides, the aryl azides are the most stable and most preferred. Those used with preference according to the invention Aryl azides contain one or two aryl groups, e.g.

CH = CH - </ MN ₃

and

= CH

-Ι / Λ

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The maximum number of azide groups present is T0 by choice Further typical examples of preferred azide compounds are given below:

, 4-'-diazidostilbene-2,2-disulfonic acid

CH = CH-

SO ^ H SO ₃ H

-N,

'-Azidobenzalacetophenone' -2-

^N 3 "\ y ~ ^{CH = CH} ~ ^c -Y y- ^N

l \, A) -'- Diazidostuben- «- carboxylic acid

N, -

-C = CH COOH

B.i ~ (4-azido-2'-hydroxybenzal) acetone ι-2-sulfonic acid

OH

\\ - CH = CH-

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4-azidobenzalacetophenone. -2-sulfonic acid

and the Ua, E or Li salts thereof.

3If the azide is decomposed by light, it may be possible to use suitable sensitizers are used, such as acenaphthene, pyrene, acrydone, anthraquinone, naphthoquinone, derivatives of nitro compounds such as 1-Uitroanthraquinone, 1-Uitropyrene, 1-LIitroacrydon xxnd the like, or thiazoline derivatives, such as they are set forth in U.S. Patent 2 94-8,610. One suitable amount of sensitizer is 3 to 30% based on the weight of the azide compound. If arylazides are used, typical ^ zide-sensitizer combinations are e.g. the following:

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Arylazide

Sensitizer

not mandatory.

N ₃ - (Z ^N ) -COOH

2-Benzoinmethylene'-1-methyl-β-naphthothiazoline

2-Benzoinmethylene -1-methyl-β-naphthothiazoline

Pyrene.

The polyamides are preferably soluble in a customary solvent for the azide compounds and the solutions form a homogeneous film after drying; in other words, those polyamides which are highly compatible with the azides are preferred. Such polyamides include, for example _, those which are soluble in a lower alcohol such as methanol, ethanol, n-propanol, isopropanol, butanol and the like. Suitable examples are polymers or copolymers of caprolactam, the hexamethylenediamine salt of adipic acid, the hexamethylenediamine salt of sebacic acid and the like.

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borrowed, colorless and transparent, flexible, abrasion-resistant and are weather-resistant and have the following physical properties:

Elvamide (trade name)

ASTM

Procedure 8061 8062 8063

Melting point after

Fischer-Jones D789 14-9-16O ⁰ C 141-14-9 ° C 157 C

Molecular weight 20,000 20,000 20

Density at 22.8 ° C

(730B ¹ ) D742 1.08 1.08 1.08

Moisture absorption (% in
24 hours) D57O 2.0 2.3 3.0

Rockwell hardness D785 R83 R4-5 R14

Tensile strength in D638 520 (74-00) 352 (5000) 218 (3100) ^ ()

g / m (psi) at
22.8 ° G (73 ° F)

Elongation in% at D638 300 300> 65Q 22.8 ⁰ C (73 ° F)

Other preferred polyamide compounds include nylon copolymers, in particular nylon 6 / nylon 6,10 / nylon 6,6 copolymers, which are generally alcohol soluble. Conventional copolymers of 6-caprolactam are also particularly preferred, Hexamethylene diamine, adipic acid and sebacic acid or 6-aminocaproic acid, hexamethylene diammonium adipate, hexamethylene diammonium sebacate; or N-alkoxymethyl modified nylons, the by reacting a nylon with formaldehyde and an alcohol replacing a hydrogen atom of the amide group of the nylon, as shown by the following reaction equation:

-NHCO ⁺ CHpO ⁺ ROH> -NCO- -NCO-

^ 'or

CIUDR

17/1215 r _: alcohol residue;

such as N-methoxymethyl-polyhexamethylene adipamide (hexamethylene diamine + Adipic acid paraformaldehyde). Also according to the invention The polyamides described in British Pat. No. 826,272 are particularly advantageous.

Although an imaging is possible if the amount of the azide compound about 3 to about 30 wt .-%, based on the used polyamide resin is, a preferable range is from 5 to 15 wt .-% _o If amounts of the azide compound to be used, the are significantly below about 3 % , no positive images can be obtained. On the other hand, if amounts of the azide compound are used which are substantially more than 30% by weight, both the exposed and the non-exposed areas become alkali-soluble. As already stated above, however, the most important criterion that the polyamides used according to the invention must meet is that they interact in a certain way with the azide compound during exposure, whereby the exposed areas are made alkali-soluble and the unexposed areas remain alkali-insoluble . Suitable polyamides can be selected using a relatively simple test, which consists in, for example, mixing a certain amount of the azide compound within the amount ranges given above with the polyamide, exposing the system to light and then carrying out an alkali development, for example with an aqueous sodium hydroxide solution or the like Preferred polyamides are able to remove sharply delimited areas in the exposed areas during the development of alkali.

Most of the polyamides used according to the invention preferred polyamides have a molecular weight of about 1000 to about 50,000, but the invention is not limited to because lower and higher molecular weight polyamides can also be used, though at lower molecular weights occasionally no sufficiently sharp image due to the development of alkali in the exposed areas

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is obtained and polyamides with a higher molecular weight in the exposed areas occasionally only with a relatively can be removed at a slow rate, which means that longer treatment or development times are required.

The photosensitive coating composition according to the invention is shown in a suitable solvent or solvent system for azides and polyamides and these include e.g. a lower alkanol, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, Butyl alcohol, dimethylformamide and the like. To the coating composition If desired, suitable amounts of a wide variety of organic or inorganic additives can be added will. Such additives include, for example, coloring substances such as oil-soluble dyes (e.g. crystal violet) and / or pigments (e.g. phthalocyanine), which color the resulting coating, fillers to increase the physical strength of the coating, such as titanium dioxide, clay or calcium carbonate, or plasticizers. Coloring substances are usually used in a large number from about 0.5 to about 10% by weight, based on the polyamide resin, Fillers generally in an amount of about 1 to about 10% by weight, based on the polyamide resin, and plasticizers (such as e.g. octyl p-oxybenzoate and U-butylbenzenesulfonamide) in one Amount of about 3 to about 30% by weight, based on the polyamide resin, admitted These additives fulfill their generally recognized functions and, as is readily apparent to the person skilled in the art, be replaced by other conventional additives of a similar nature

The photosensitive layer should be in the 1-layer embodiment of the invention preferably a thickness of 0.01 to 5.0,

in particular from 0.02 to 3 _} 0 g / m, based on the dry weight, have «. The o-quinonediazide compounds optionally used in the fiction, contemporary light-sensitive material must have at least one o-quinonediazide group and increased solubility to alkali when they are exposed to active radiation, for example radiation from a mercury,

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Xenon, carbon arc lamp or the like., Be irradiated. A wide variety of compounds can be used, such as those described in more detail in US Pat. No. 2,663,640 and by J. Kosar in "Light Sensitive Systems", John Wiley & Sons, Inc., pp. 339-352. Particularly preferred compounds are sulfonic acid esters derived from aromatic polyhydroxy compounds and o-quinonediazides, as are given in Example 2. Examples of suitable aromatic polyhydroxy compounds are hydroquinone, pyrocatechol, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4 ^I -dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'- Dihydroxydipheny1-methane, bisphenol A, 1,8-Dihydroxynaphthaiin, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2 '-dihydroxy-1, 1' -dinaphthylmethan, 4,4 '- Dihydroxybenzophenone, ß-bis (4-hydroxyphenyl) ethane, 1,4-dihydroxyanthraquinone, 2,7-dihydroxyfluorene, pyrogallol, methyl gallate, 2,2 ', 4,4'-Te ^ ahydroxybiphenyl, tetrahydroxybenzophenone and the like.

Specific examples of sulfonic acid esters derived from aromatic polyhydroxy compounds and o-quinonediazides are 2,2'-dihydroxy-diphenyl-bis (naphthoquinone-1,2-diazide-5-sulfenic acid ester), 2,3 ^ -trioxybenzophenone-bis -Naphthoquinone-1,2-diazide-5-sulfonic acid ester), 2,7-dihydroxynaphthalene-bis- (naphthoquinone-1 _i 2 -! - diazide-5-sulfonic acid ester), an ester of a phenol-formaldehyde resin and uaphthoquinone-1,2- diazide-5-sulfonic acid and the like. A particularly suitable compound is the naphthoquinone-1,2-diazide-5-sulfene acid ester of polyhydroxyphenol, which has been prepared by the polycondensation of acetone and pyrogallol, as described in US Pat. No. 3,635,709 .

An organic photosensitive layer can be prepared by using any of these o-quinonediazides alone or in combination with a resin material in the form of a layer

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applies to a carrier and dries. Examples of suitable resin materials include alkali-soluble resins such as a phenolic resin, a cresol resin, styrene / maleic anhydride copolymers, shellac and the like.

Since the thickness of the photosensitive organic coating of the imaging photosensitive material according to the second embodiment of the invention may be smaller than that In addition, among conventionally known materials of the 1-layer type, resins can be used which are difficult in alkalis are soluble, such as p-phenylphenol-formaldehyde resins, p-t-butylphenol-formaldehyde resins and other substituted phenolic resins, e.g. bisphenol A-formaldehyde resins or polyvinyl butyral. These components improve the mechanical strength of the image areas obtained. When an o-quinonediazide compound is mixed with such a resin, the content of the o-quinonediazide compound is preferably not less than 20 % By weight based on the total weight of o-quinonediazide and alkali-soluble resin. If the content of the o-quinonediazide is below 20% by weight, no acceptable photosensitivity will be obtained is achieved and a sharp image is not obtained.

The coating composition containing an o-quinonediazide compound from which a photosensitive organic coating is made is to be dissolved in one or more solvent (s) suitable for the production of a coating, whereby to Examples of suitable solvents include ethylene glycol monoalkyl ethers and their acetate esters, such as ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate and the like., Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like, butyl acetate, dioxane, pyridine, dimethylformamide and the like.

As stated above, the photosensitive materials contain according to the second embodiment of the invention, a first light

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Sensitive layer comprising an o-quinonediazide compound coated on a second photosensitive layer containing a polyamide resin and an azide compound having an alkali-soluble group (the second layer alone corresponds to the photosensitive layer of the photosensitive material according to the first embodiment of the invention). To increase the adhesion between these two coatings, a suitable silane coupler can be used, such as γ- glycidoxypropyltrimethoxysilane, ß- (3, ^ - epoxycyclohexyl) ethyltrimethoxysilane and the like., The silane coupler preferably in the coating mixture for the preparation of the Top coat is incorporated. A suitable proportion of this coupler is 1 to 100% by weight, based on the polyamide.

The manufacture of a two-layer structure according to the second embodiment of the photosensitive material of the invention takes place in the usual way by repeating the application of a layer and drying, but others can also be used if desired Process such as ζ, Ε coating by potting, by transfer or the simultaneous application of two coats. The production of the 1-layer structure according to the first embodiment of the photosensitive material of the invention is also carried out in the usual manner, in the cone through Dissolving the azide compound and the polyamide in a suitable conventional solvent and applying the resulting Solution in the form of a layer on a support and subsequent drying. Of course, others can too Methods other than those given above can be used which result in the formation of a 1-layer structure.

A suitable amount of each layer comprising the present invention photosensitive imaging material is at

the two-layer embodiment about 0.01 to about 5 »0 g / m 2 and the layer containing the polyamide and the azide compound

is preferably used in an amount of about 0.02 to about 4.0 g / m 2 applied while containing the o-quinonediazide compound

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Layer preferably in an amount of less than 3.0 g / m 2 is applied, the total coating amount for all organic layers on the carrier being below 7.0 g / m 2 should·.

A photosensitive imaging material according to the invention is usually made using a mercury, xenon or Carbon arc lamp imagewise exposed and then developed. Such developer solutions can be used as they are usually used for developing light-sensitive layers with o-quinonediazide compounds, such as aqueous solutions containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, tertiary sodium phosphate, tertiary potassium phosphate, sodium carbonate, Potassium carbonate and the like, and basic organic solvents such as ethanolamine. One used in the present invention a typical developer solution is a 7% strength by weight aqueous sodium silicate solution. To promote the penetration of the aqueous alkaline developer into the areas with the active radiation about 0.1% to about 10% by weight of an organic solvent such as n-propyl alcohol can be added to the developer and / or from about 0.1 to about 5.0 percent by weight of a surfactant Agents, such as sodium lauryl sulfate, sodium isopropyl naphthalene sulfonate, Sodium dodecylbenzenesulfonate and the like. ^ Be added in a suitable concentration. The inventive Photosensitive material can not only be used for the production of artwork, but for other purposes, For example, for the production of Hamensplatten, slides for overhead projectors and the like. Used.

The invention is illustrated by the following examples, in which preferred embodiments of the invention are described, explained in more detail, but without being limited thereto.

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Example 1 '-

5 parts by weight of an alcohol-soluble nylon resin ("Elvamide Hr .-. 8061 "from E.I. du Pont Co.) were in 100 parts by weight dissolved a solvent mixture, which consisted of equal parts by weight of n-propyl alcohol and methyl alcohol and had been heated to about 70 ° C. The resulting solution was cooled to about 25 G and then 0.5 part by weight of the sodium salt of 4,4'-diazide-2,2'-disulfonic acid and 0.2 Parts by weight of a dye (Oil Blue from Orient Chemical Co. (CI. No. 74-35O)) was added, the mixture was in the form a layer applied to a 0.3 mm thick aluminum plate, which is roughened (grain) and then anodic Oxidation (current density 1.6 A / dm, duration 2 minutes, electrolysis bath: 15% strength by weight sulfuric acid) had been subjected to Formation of a dry coating weight of 1.5 g / m ^.

A positive slide was brought into contact with it and the photosensitive plate produced in this way was exposed to a PS light (generated with a 3 KW light source from Toshiba, a metal halide lamp of the JU 2000- type) at a distance of 1 m for 20 seconds. 2-0L, sold by Fuji Photo Film Co., Ltd.). Then, development was carried out by immersing the exposed plate in an aqueous solution containing 7 wt .-% of sodium silicate and 2.5 wt -.% N-propyl alcohol contained, for a period of 2 minutes at room temperature and then brushing the plate with a Nylon brush, which removed the exposed areas. The resultant positive image-bearing plate, which was used as a printing pattern (printing master), exhibited both superior abrasion resistance and remarkable resistance to organic solvents.

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Example 2

4 parts by weight of an ester of a polyhydroxypheny3 (a Condensation product of acetone and pyrogallol, as described in Example 1 of US Pat. No. 3,635,709) and the Uaphthoquinone-1,2-diazide-5-sulfonic acid and 4 parts by weight of one Novolak type exesol-formaldehyde resin was used in 100 parts by weight of an ethylene glycol monomethyl ether dissolved. The solution thus prepared was applied in the form of a layer on an aluminum plate applied, which had been roughened and anodized as in Example 1. The coating amount was after Drying 1.5 g / m · The photosensitive described in Example 1 The coating mixture was based on the o-quinonediazide coating prepared above applied to form a dry layer

thickness of 1.2 g / m.

The photosensitive plate thus prepared was made using of PS light as described in Example 1 at a distance of 1 ι 50 seconds through a positive slide exposed. The plate was then immersed in the aqueous alkaline solution described in Example 1. For 1 minute at room temperature immersed. After the immersion, the plate was lightly rubbed with a brush in the horizontal position. The exposed areas of the coating were easily removed, leaving a clear and sharp positive rendition of the original image was obtained. The image formed in this way was superior because of the polyamide resin used Abrasion resistance and scratch resistance in continuous lithographic printing for more than 200,000 passes, high quality prints were obtained. If the top coat according to the invention is omitted (i.e. if only the photosensitive coating of the o-quinonediazide layer was used) were the image areas after 100,000 passes worn.

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Example 3

5 parts by weight of an alcohol-soluble nylon resin (trade name "Amilan CM4000" made by Toray Co.) was dissolved in 80 parts by weight of methanol while heating the methanol to the boiling point. After cooling, 0.4 part by weight of the sodium salt of 4,4 -'-Diazidstilbene-2,2 ¹ ^ iSuIfOnSaUTe and 0.3 part by weight of a dye (Oil Blue from Orient Chemical Co. ) added and dissolved therein. The resulting solution was applied in the form of a layer to a polyethylene terephthalate film with a matt surface and a thickness of 0.1 mm to form a dry coating

Weight of about 1.5 'g / m · If this light-sensitive Film treated as described in Example 1, i.e. exposed and developed, a transparent film was obtained, which carried a blue colored image and could be used as a photographic original.

Example 4

Similar results as in Example 3 were obtained when the nylon resin "Amilan CTvM-OOO" used in Example 3 by the alcohol-soluble nylon "Zytel" (from E.I. du Pont Co.) was replaced.

Example 5

5 parts by weight of an alcohol-soluble nylon resin ("Amilan CM4000" from Toray Co.) were mixed in 100 parts by weight of a 1: 1 mixture of propyl alcohol and methyl alcohol dissolved by heating the solvent mixture to the boiling point. After cooling down were 0.4 parts by weight of the phenylhydrazine salt of 4-diazidbenzenesulfonic acid, 0.04 part by weight of i-methyl-2-benzoylmethyleneß-naphthothiazoline, 0.2 part by weight of a dye (Oil Blue from Orient Chemical Co.) was added and dissolved therein.

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An aluminum plate treated as in Example 1 "was made with this coating mixture "coated to achieve a

ο Dry coating quantity of 1.5 g / m. After treatment as in the above examples, a very useful (permanent) positive image was obtained.

Example 6

The coating mixture given in Example 5 was applied to the In Example 2 used photosensitive o-quinonediazide coating applied, as in Example 2 on a roughened (grained) and anodized aluminum plate had been applied., to give a dry coating weight of 1.0 g / m · The photosensitive plate thus obtained worked satisfactory as a cross-country offset printing master with a permanent or long-lasting image.

Example 7

Example 5 was repeated, this time using the phenylhydrazine salt the 4-azidbenzenesulfonic acid by the 4-azidbenzenecarboxylic acid · The plate obtained was better than a positive type photosensitive plate Performance than the composition according to Example 5.

The invention has been explained in more detail above with reference to preferred embodiments, but it is for the A person skilled in the art, of course, that it is by no means restricted to it, but that it is modified in many ways and can be modified without affecting the frame the present invention is departed from.

Patent claims:

609817 / 121B

Claims (1)

Claims 1. A photosensitive imaging element characterized by a support and a photosensitive layer which is rendered alcohol-soluble by exposure and (i) an azide compound having at least one alkali-soluble group in their molecular structure and (ii) contains a polyamide. 2. A photosensitive imaging element characterized by a support having a first photosensitive applied thereto Layer containing an o-quinonediazide compound and a second layer coated on the first photosensitive layer photosensitive layer which is rendered alcohol-soluble by exposure and (i) an azide compound with at least one alkali-soluble group in their molecular structure and (ii) a polyamide. 3. Imaging element according to claim 1 or 2, characterized in that that it contains an aryl azide as the azide compound. 4. imaging element according to claim 3 »characterized in that that it contains an aryl azide with 1 or 2 aryl groups. 5. Imaging element according to claim 4, characterized in that that the aryl azide has at most 2 azide groups. 6. Imaging element according to claim 5, characterized in that the alkali-soluble group is a sulfonic acid, Carboxylic acid, hydroxyl group and / or an alkali metal salt thereof. 7. Imaging element according to at least one of claims 1 to 6, characterized in that the azide is 4-azidbenzenesulfonic acid, 4-azidbenzenecarboxylic acid and / or sodium 4-, 4- ¹ - 6 0 9 8 17/1215 contains diazidstilbene-2,2'-disulfonate. 8. Imaging element according to at least one of the claims 1 to 7 »characterized in that the polyamide and the Azide compound are soluble in the same solvent. 9. Imaging element according to claim 8, characterized in that the solvent is a low solvent Alkanol. 10. Imaging element according to claim 8, characterized in that that the solvent is dimethylformamide. 11. Imaging element according to at least one of claims 1 to 10, characterized in that it comprises the azide compound in in an amount from about 3 to about 30 parts by weight per 100 parts by weight of the polyamide. 12. Photosensitive imaging element according to at least one of claims 2 to 10, characterized in that it contains the quinonediazide compound in the first layer in an amount of more than 20% by weight. 13. Imaging element according to claim 1, characterized in that that it the photosensitive coating in an amount of about 0.01 to about 5 »O g / m, based on the dry weight, contains. 14 ·. Imaging element according to claim 13 »characterized in that that it contains the photosensitive coating in an amount of 0.02 to 3.0 g / m 2 on a dry weight basis. The imaging member of claim 2 characterized in that it includes said first and second photosensitive members Layer in each case in an amount of about 0.01 to about 5 »0 g / m, G09817 / 1215 based on the dry weight. 16. The imaging element according to claim 15, characterized in that it contains the layer containing the polyamide and the azide compound in a coating amount "of about 0.02 to about 4.0 g / _m 2 and the layer containing the o-quinonediazide compound in a coating amount of less contains than 3.0 g / m. 17 · Imaging element according to at least one of Claims 1 to 16, characterized in that it is a polyamide with a Contains molecular weight from about 1,000 to about 50,000. 18; Method of generating positive images, thereby characterized in that a photosensitive imaging element according to at least one of claims 1 to 17 is imagewise exposed and then selectively dissolves the exposed areas in an alkaline medium. 609817/1215