DE2041967A1 - Photographic recording material - Google Patents

Description

Registration number. 122 573

Eastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Photographic recording material

The invention relates to a photographic recording material, consisting of a layer support and at least a photosensitive layer made of a photosensitive linear film-forming polymers with ethylenically unsaturated side chains on the linear main chains and optionally a sensitizer for the polymer.

It is known that images can be reproduced by photographic means by subjecting a photographic recording material to a light-sensitive layer whose physical properties are in the lit districts can be changed during exposure.

These are, in particular, photographic recording materials with photosensitive polymers become known, which in the Exposure to actinic radiation can become insoluble or hardened, the resulting differences in the physical properties of the exposed and non-exposed Districts can be used to produce images or reproductions in various ways, e.g. B. by application

10Ö812 / U9

BAD ORIQINAt

mechanical pressure, exposure to heat, treatment with solvents, and the like. For example the exposed layer of such a recording material by de-treatment with a solvent for the not hardened polymeric areas, which in turn does not dissolve the hardened polymeric areas, by dissolving the uncured polymeric areas Districts and leaving the hardened polymeric districts to be developed. It is also possible to do such a Heat recording material to a temperature which is between the tack point of the unexposed areas and the stickiness point of the exposed areas, whereupon the areas with the lower melting point using a so-called toner or can be transferred to an image receiving layer. Such procedures are known for the production of planographic printing plates (lithographic printing plates), photoresists, stencils and the like applied.

Suitable for the production of photographic recording materials Compounds with light-sensitive residues are, for example, those known from German Patent 1,119,510 p-Phenylenbisacrylate, from the German patents 703 230 and 1 132 761 known cinnamylidene malonates, the polyamides known from US Pat. No. 3,023,100, the polyurethanes known from US Pat. No. 2,9 ^ 8,706 and the polycarbonates known from US Pat. No. 3,043,802.

Photosensitive ones are also of particular importance Polymers, the photosensitive residues in the polymer side chains have, e.g. Such as those disclosed in U.S. Patents 2,610,120; 2 670 2Ü5 and 2 801 233 known polyvinyl cinnamates, the polyvinylbenzalacetophenones known from US Patents 2,566,302 and 2,716,097, those from US Patents

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109812/1491 "**"

2,908,667 and 3,257,664 known polyvinylstyrylpyridines and the polyvinyl styryl acrylates known from US Pat. No. 3,257,664 with two or more conjugated chromophores in the side chains.

The disadvantage of the known polymers suitable per se for the production of photographic recording materials is that their own sensitivity to light still leaves much to be desired leaves and that they often do not like that on sensitizers respond strongly, as it would be desirable in itself.

The object of the invention is to provide a photographic recording

109812 / U99

tion material, consisting of a layer support and at least a photosensitive layer of a photosensitive linear film-forming polymer with ethylenic unsaturated side chains on the linear main chains as well as optionally to indicate a sensitizing agent for the polymer which comprises a photosensitive layer has a photosensitive polymer, which has a particularly high inherent sensitivity, by adding a sensitizer can be sensitized particularly easily and also easily in a variety of Can produce embodiments.

It has been found that they are excellent for the production of photographic recording materials of the type described photosensitive polymers are suitable, which are characterized are that the main chains of the polymer or the so-called polymeric backbone of the polymer are light-sensitive side chains each having two ethylenically unsaturated radicals conjugated by an arylene radical. Here you can these photosensitive side chains to the polymer backbones or be bound to the polymer backbone, for example via a carbonyl radical.

The subject matter of the invention is thus based on a photographic one Recording material, consisting of a layer support and at least one photosensitive layer made of a photosensitive linear film-forming polymer Ethylenically unsaturated side chains on the linear main chains (or on the Polyiuerr backbone) and optionally one Sensitizer for the polymer, and is characterized in that the photosensitive polymer of the following Formula corresponds to:

BATH ORIGINAL. 109812 / U99

-A-

CI!

CIl

CIl

where mean:

-A- a main chain of the polymer;

Y is a carbonyloxy, oxycarbonyl or Auiido radical;

] \ « An aryl radical or heterocyclic radical which is substituted, if necessary, with 5- or fi-Rinj'j ', I ieder;

!! -, a water pot atom or a cyano, alkyl or *

Al 1enylrost;

a lVas: i (; rstoffatOM, a "jitro or heterocyclic reads or an alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, Alkenyloxycarbonyl or aryloxycarbonyl radical, where > "ilt that the aryloxycarbonyl, \ rylcarbonyl, aryloxy and aryl groups jief.eheiHMifalls by mitro, azido, alkyl, Alkoxy, dialkylamino or diarylamino radicals can be substituted.

BATH ORIGINAL

100812/1490

For the production of a photographic recording material Photosensitive polymers used after the invention can be produced in an excellent manner by means of a of the commonly known sensitizers to the Sensitize the visible part of the spectrum. Furthermore, the recording materials according to the invention can be used in the Frame of the most diverse photographic, therir.ophotographic and use photomechanical production before driving. The polymers used according to the invention, which themselves have a high sensitivity and are easy to add by adding of a sensitizer can be easily sensitized under precise control of their physical Establish properties.

The photosensitive polymers used for the production of a recording material according to the invention leave can be produced in a simple manner that a connection with the light-sensitive residues, which the side chains form, is reacted with a suitable polymer that forms the polymeric main chains or the polymer backbone. For this it is necessary that the connection with the photosensitive Radical, has a radical which reads to react with one of the polymers forming the main polymer chain able, so that the light-sensitive side chains on the main chains of the polymer or on the so-called polymer backbone can be bound.

If the connection with the photosensitive radical having more than one moiety that is capable of reacting the backbone-forming polymer or the polymer backbone by, the reaction of the compound with the polymer would during take place (} uervernotzunj> what hut result, that ER- for don intended use unusable polymers

ORfQINAL

109812/1499

would hold. As a result, according to the invention, one of the Ethylenically unsaturated radicals bonded to the main chain of the polymer by a radical which is linked to a radical of the polymeric main chain is able to react, whereas the other ethylenically unsaturated radical, the one leading to the compound used in the side chains is terminated by a residue that is associated with "the reactive residues of the Polymer main chain is unable to react.

For the production of the photographic recording material ™ according to the invention, suitable photosensitive polymers leave easily by condensation of a carboxylic acid or a carboxylic acid halide with the corresponding photosensitive Prepare the remainder with a polymer which is suitable for condensation with the carboxylic acid or the carboxylic acid halide Has radicals, for example reactive amino or hydroxyl radicals. This way you become photosensitive Polymers are obtained which have side chains which are linked to the main chains via amido or carbonyloxy radicals.

No other way to make the photosensitive Polymers consists in containing an Ilydroxylrestc derivative Jer the photosensitive side chain forming compound nit a polymer to implement, which has reactive radicals that interact with the hydroxyl group of the introduction of the photosensitive radicals are able to implement the compound used, for example free anhydride radicals, carboxylic acid radicals or carboxylic acid halide residues, in which case the light-sensitive side chains via oxycarbonyl residues a71 the polymer backbones or are bound to the polymer backbone.

BAD ORlOiNAL 109812 / U99

In detail can represent in the specified structural formula :

] { an optionally substituted mono- or] -. olynuclear arylene radical, e.g. B. an optionally substituted riienylene, naphthylene or biplienylene, z. B. a Chlorophenylcn- or Nitrophenylenrest. If ".. represents a heterocyclic radical with 5- or 6-membered rings, this heterocyclic!" Radical have one or more heteroatoms, for example oxygen, sulfur or nitrogen atoms. In this case, R «can be, for example, an optionally substituted pyridylene, furylene, thiofurylene, thienylene or 1-alkyl-Z-pyrrolylene radical «An optionally substituted phenyl radical.

The radicals R ₂ and R ₃ must not with the latter in the implementation of the compound introducing the side chains with the polymer forming the main chains! react.

If R2 has the meaning of an alkyl radical, then this has preferably 1-10 carbon atoms and consists, for example from a methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t, -Butyl ™, n-amyl, neopentyl, n-hexyl, n-Iieptyl, n-octyl or a 2-Ätliylhexylrest. Does R2 mean of an alkenyl radical, this preferably has 2-6 carbon atoms and consists, for example, of one Vinyl or allyl radical.

If Rj has the meaning of an alkyl radical, this also preferably has 1 to 10 carbon atoms. If R, has the meaning of an alkenyl radical, it preferably has 2-6 carbon atoms. If R _{3 has} the meaning one

BATH ORIGINAL 108812 / U9I

Aryl radical, this preferably consists of an aryl radical the phenyl or naphthyl series, e.g. B. a phenyl, Naphthyl or biphenyl radical. Has R-, the meaning of a heterocyclic radical, 30 / whichever is preferably 5- or 6- Ring members and preferably contains at least one oxygen or nitrogen atom and consists, for example, of one Puryl or pyridyl radical.

If R, has the meaning of an alkoxy radical, then this has preferably has 1-10 carbon atoms and consists for example from a methoxy, ethoxy, propoxy, butoxy, amyl, f Hexyloxy or heptyloxy radical.

If R, has the meaning of an aryloxy residue, this exists preferably from an aryloxy radical of the phenoxy or kaphthoxy series. If R, has the meaning of a Heterocycloxyreatas, then this / consists of a Puryloxyrest.

e.g.

If R .. has the meaning of an Alkyloarbonylrestee, then has this preferably has 2-11 carbon atoms and consists, for example, of a methylcarbonyl, xthyloarbonyl, pro « pyloarbonyl-, butylcarbonyl-, amyloarbonyl-, hexy! carbonyl-, Octy1carbonyl or 2-Xthylhexyloarbonylrest. Owns R- the Meaning of an aryloarbonyl radical, this consists, for example, of a benzoyl or naphthoxyreat.

If R, has the meaning of an alkoxycarbonyl radical, then has which preferably has 2-11 carbon atoms and consists beiepielsweiee from a methoxycarbonyl ethoxycarbonyl, Propoxycarbonyl, butoxycarbonyl, amyloxycarbonyl, hexyloxyoarbonyl, heptyloxja carbonyl, octyloxycarbonyl or nonyloxycarbonylreat.

Has IX, the meaning of an Alkenyloxycarbonylreatea, so

10 * 012/1491

this preferably has 3-7 carbon atoms and ordered for example from an allyloxycarbonyl or Methacryloylcarhonylrest,

If R- has the meaning of an aryloxycarbonyl radical, then

ti

this preferably consists of a Pheiioxycarbonylrest.

In the aryloxycarbonyl, arylcarbonyl and aryloxy radicals can the aryl radicals may be substituted, in particular in the para position, for example with nitro, azido or alkyl radicals with preferably 1 - 10 carbon atoms, Alkoxy radicals with preferably 1 - 10 carbon atoms, dialkylamino or diarylamino residues.

For the production of the photosensitive polymers i'.ceignete Compounds for the introduction of the light-sensitive side chains are for example:

p-vinylcinnamoyl chloride, ζ. Γ>.

p-vinylcinnamoylchloritol,

p- (2-nitrovinyl) cinnainoyl chloride,

p ™ (2-propylvinyl) cinnajaoyl chloride »

p ~ (2-phenylvinyl) cinnanioyl chloride,

P- / 2- (p-Mitrophenyl) viiiyl / ciiinanioylchlorid, p- (2, 2-l) (ethylvinyl) cinnainoyl chloride, ρ- (2-amyloxyvinyl) cinnainoyl ciloride,

p- (2-EthoxyvLnyl) cinnamoyl chloride,

p- / 2- (2- "Uhylhcxyloxy) ν i ny 17c innainoyl chi or id, ρ- (2-propoxy-2-cyanovinyl) cinnamoyl chloride, p- (2-naphthoxyvinyl) cinnamoyl chloride _> p- (2-methylcarbonylvinyl) cinnamoyl chloride , p- (2-Ethylcarboiiylvinyl) cinnamoylchloride,

109812/149 " ^B "> OR | Q _INAL

p - (2-Ethyl-2-benzoylvinyl) cinnainoyl chloride, p- / 2-r.utyl-2-Cn-r; ethoxybcnzoyl) vinyl7cir! nan! oyl chloride, ρ- (2 - '\ thQxycarbonylvinyl) cinnamoyl chloride, p- / 2-Ethylhexyloxycarbonyl) vinyl7cinnamoyl chloride, p- (2-hexyloxycarbonylvinyl) cinnamoyl chloride, p- (2-ethyl-2-ethoxycarbonylvinyl) cinmmoyl chloride, p- (2-yinyl-2-ethoxycarbonylvinyl) cinnamoyl chloride, p- (2-allyl vinyl) cinnamoyl chloride -2-propoxycarbonylvinyl) cinnamoyl chloride, p- ( ₁ 2-ethoxycarbonyl-2-cyanovinyl) cinjiamoyl chloride,

p ~ / 2- (2-A "thylhexyloxycarbonyl) ^ -cyanovinyl ^ ciiinainoylchloride, f

p- (2-AlIy] oxycarbonylvinyl) cinnaTiioylchlori <i, p- (2-vinyl-2-allyloxycarbonylvinyl) cinnamoyl chloride and p- (2-phenoxycarbonylvinyl) cinnamoyl chloride; 4-vinyl chalcones, e.g. B.

4- (2-chlorocarbonylvinyl) chalcone, 4- (2-chlorocarbonylvinyl) -4'-methoxychalcone, 4- (2-chlorocarbonylvinyl) -4'-amyloxychalcone, 4- (2-chlorocarbonylvinyl) -4 '- C2-ätliylhexyloxy) chalcon, 4- (2-chlorocarbonylvinyl) -4'-PrOPyIcUaIcOn, 4- (2-chlorocarbonylvinyl) -4'-octylchalcone, 4- (2-chlorocarbonylvinyl) -4'-dimethylaminochalcone and

4- (2-A'thoxycarbonylvinyl) -4 '- (2-hydroxyethoxy) chalcon *

as well as ζ. Γ ». the following reaction components:

2-styryl-S- (2-chlorocarbonylvinyl) furan, 2- (2-anyloxyvinyl) -5- (2-chlorocarbonylvinyl) furan, 2- [1- (p-K5ethoxyphenyl) vinyl7-rj- (2-chlorocarbonylvinyl) furan , 2- [2- (2-ethylhexyl) vinyl7-5- (2-chlorocarbonylvinyl) thiofuran and 2- (2-ethoxycarbonylvinyl) -6- (2-chlorocarbonylvinylpyridine.

Suitable for the production of the photosensitive polymers Polymers that make up the main chains or what is known as the backbone of the photosensitive polymers and in which the

1Ö9812 / U99 BADORlGtNAL

V.

light-sensitive side chains can be introduced, can consist of natural and synthetic polymers that have hydroxyl or amino radicals.

For the production of the photosensitive polymers suitable starting polymers or starting resins with Ilydroxylresten are, for example, polyvinyl alcohols, partially hydrolyzed polyvinyl esters, z. B. PolyCvinyl alcohol-co-vinyl acetates), poly (vinyl alcohol-co-vinyl benzoates), poly (vinyl alcohol-co-vinyl acetate-co-vinyl benzoates), also partially hydrolyzed polyvinyl acetate, e.g. B. partially hydrolyzed polyvinyl butyral, partially hydrolyzed polyvinyl benzal, teilx \ ^T EISC hydrolyzed Polyvinylcinnamal, as well as mixtures of such teilx ^ else hydrolyze en acetal, further polyethers, z. B. epoxy and phenoxy polymers, e.g. B. the condensation products of an ice phenol, e.g. B. Diphenylolpropane irit Kpichlorhydrin, also naturally occurring Polyriere, z. 1-. Cellulose, starch, guar, alginic acid and its partially esterified or etherified derivatives, e.g. B. ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, as well as also Po lyest he. 3DEraXXHpi $ XK3 ^^

Starting polymers with reactive amino radicals which are suitable for the production of the Jichtenpfint ¹ lichen polymers used according to the invention are, for example, polyvinylamines, polyaminostyrenes, polyvinylanthranilates and the like.

Finally, are suitable for the establishment of the invention; Polymers used also those starting polymers that react

BATHROOM ORIQiNAL 109812 / U9Ö

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tionsOhii; e have anhydride residues, ζ. ',>. Mixed polymers or copolymers of maleic anhydride with ethylene or styrene.

Twiddles allow the photo-sensitive polymers required for the preparation of a Aufzeichnun & smarerials according to the invention, as already stated, easily by reaction of the hydroxy- or Aninoreste of the polymers with an acyl halide of a compound r.iit est lichteinnfindlichen the ^p-described or to V by reaction of a hydroxyl group%: iron derivative of a compound with the photosensitive radical described with a polymer with reactive anhydride, carboxylic acid or carboxylic acid halide groups.

The side chain is expediently introduced into the starting polymer using a suitable solvent, e.g. B. a tertiary amine, e.g. F>. Pyridine, picoline, lutidine or triethylamine. The reaction can take place at a wide variety of temperatures, e.g. Ii. at temperatures from room temperature to about 100 ° C,

A polyvinyl alcohol is advantageously used to produce the light-sensitive polymers used in accordance with the invention. In this case, the light-sensitive polymers used according to the invention can advantageously be made according to the method from BKK of German patent application P 20 12 389

known processes are produced. Hei this procedure the polyvinyl alcohol used is first swollen in a solvent consisting of a tertiary amine,

BATH ORIGINAL

1QI812 / U99

whereupon he by means of an aroyl chloride, z. B. benzoyl chloride, is partially esterified. The partially aroylated polyvinyl alcohol is then photosensitive or light-sensitive Esterified acid chloride, whereupon the remaining hydroxyl residues are esterified with further aroyl chloride, if necessary, can be.

Apart from the photosensitive side chains described the polymers used according to the invention can be different Have side chains, e.g. B. side chains consisting of carboxylic acid residues exist. Such other side chains can advantageously be used to modify the physical Properties of the polymers, e.g. B. to modify the Solubility properties, adhesive properties, melting point, the ink absorption capacity, the resistance to chemical etchants and the like as well as to modify the sensitometric properties of the Polymers are introduced. To modify the polymers by introducing a side chain !! suitable compounds can consist of aliphatic or aromatic carboxylic acids, z. B. acetic acid, haloacetic acids, propionic acid, butyric acid, Isovaleric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 2-ethylhexanoic acid, uecanoic acid, Benzoic acid, ilalobenzoic acids, nitrobenzoic acids, toluene acids, p-ethylbenzoic acid, p-octylbenzoic acid, p-methoxybenzoic acid, p-; Uhoxybenzoes; lure, p -. \ my Ioxybenzoesiiure, p-Lauryloxybonr.ee-Silure, 2-naphthoic acid and the like. Are also suitable those carboxylic acids which are used for the production of light! pt "iiuilichen Polymers are suitable, ζ. Γ>. Acids n <it the: vinyl ketone residue, z. B. Cinnamic acid, llalocinnamic acid and Cinnamylidenesägsüure and the same.

BAD OBiGlNAt 10Ö812 / U6Ö

$ 4

Such modifying side chains can be introduced into the polymers by treating the latter with an acyl halide the modifying compound are implemented. the Modifying site chains or residues can be introduced into the polymer forming the main chains before the introduction of the described photosensitive residues are introduced or thereafter.

The modifying side chains can contain up to 95 mol-56 of the residues that are attached to the polymer backbone or backbone. This means that z. B. only (j 5 M0I - / & of the side chain of the polymer from the described light-sensitive side chains need to exist.

Those polymers have proven to be particularly advantageous in which 5-50 mol% of the side chains or radicals attached to the polymer main chains or the polymer backbone are bound, consist of the photosensitive radicals described. Of the in the individual case the most advantageous percentage of the photosensitive side chains described naturally depends somewhat on the nature of the starting polymer used, its molecular weight and the like.

Used, for example, for the production of photosensitive polymers as the starting polymer, a polyvinyl alcohol from a lower one average molecular weight used, i.e. H. e.g. from about 25,000 to about 35,000, preferably 20,100 Μο1-5ί of the polymer backbone or the polymer chains bound side chains from the photosensitive side chains described.

Used to produce the photosensitive, according to the invention polymers used a polyvinyl alcohol of medium average molecular weight is used as the starting polymer, d. H. e.g. from about 120,000 to 150,000, there are preferred

10Ö812 / UÖ9

wise 10 - 60 mol ⁰ O of the side chains from the light-sensitive side chains described.

Used to manufacture photosensitive polymers High molecular weight polyvinyl alcohol as the starting polymer used, then preferably 5-50 M of the side chains or side residues consist of the photosensitive described Leftovers.

Coating compositions suitable for producing the recording materials can be in a conventional manner by dispersing or dissolving the photosensitive polymer in a suitable solvent or a combination of solvents produce. For the production of coating compounds suitable solvents are, for example, ketones, e.g. B. 2-butanone, 4-methyl-2-pentanone, cyclohexanone, 4-butyrolactone, 2,4-pentanedione, 2,5-hexanedione and the like, lister, e.g. B. 2-Ä'thoxyäthylacetat, 2-Methoxyäthylacetat, n-butyl acetate and the like, chlorinated hydrocarbons, e.g. B. chloroform, dichloroethane, trichloroethane and tetrachloroethane, as well as dimethylformamide and dimethyl sulfoxide and mixtures of these solvents.

It has proven to be expedient to use coating compounds for the production of the recording materials which contain about 1-20% by weight ^? ₀ , in particular 2-10 wt ^. _{0 of} the photosensitive polymer included.

The coating composition can also contain conventional photographic Additives are incorporated, e.g. B. Additives for modifying the flexibility of the substrate to be applied photosensitive layer, compounds for modifying the surface characteristics of the material to be produced

⁺ a ;. B, from about 170,000 to 250,000 on average

108812/1499

BATH ORIGINAL

photosensitive layer, dyes and pigments for Coloring of the photosensitive layer, compounds for "Iodify the adhesion of the photosensitive layer on the substrate, antioxidants, condoms and the same.

The photosensitive polymers used in accordance with the invention can be advantageously ζ. Π. with pyryliuw and Thiapyryl iunfarbstoffsalzen, thiazoles, benzothinzolinen, N'aphthotHazolines, quinolizones, \ cridonen, cyanine dyes, f IHthiolium salts, Michler's ketone, Michler's thioketone and raise awareness of the like.

. in! a Sensi-II to produce the recording materials 1 isierunj'.smittcl is used, this is preferred in concentrations of 0.1 to 10% by weight, based on .! as Tevviclit dos 1 ichteil <essential polymers, especially in ! Concentrate ionon from et v / a 0.2 to 3 weight percent, based on the Weight of the 1 ichteiij) is used in the fiefdom polymer.

If necessary, with the invention? used 1 ichtei! customary polymers further other polymers to the λ

Mod if ize. the physical i; i} other than the light-sensitive layer or as a thinning agent, ' . b. Thermoplastic novolak resins or ilesol resin which are soluble in risunj'.smittoln can be used to improve the resistance to residue of the sensitive layer over the layer if the light-sensitive layer serves as a so-called photoresist layer. In addition, hydrophilic polymers, for example, can be incorporated into the protective layer for the preparation of the layer. H. Cellulose or cellulose derivatives, polyalkylene

BATH ORIGINAL

101812/1460

2OA1967

if.

oxides, polyvinyl alcohol and polyvinyl alcohol derivatives to to improve the hydrophilic properties of the photosensitive layer if the recording material is used for production used by planographic printing forms (lithographic printing columns) shall be. These modifying polymers can optionally up to 25% by weight of the polymers used for production of the photosensitive layer are used.

For the production of the photographic recording materials according to the invention, the usual known support can be used, for. R. layer support made of fibrous material, z. B. made of paper, polyethylene coated paper, with polypropylene coated paper, parchment or cloth as well as layer carriers made of plates or foils made of metal, z. B. aluminum, copper ,, magnesium or zinc and also glass or coated with a metal such as chromium or a chromium alloy, steel, silver, gold or platinum: glass, furthermore Substrate made of synthetic polymeric materials, e.g. 15. polyalkyl methacrylates, z. B. polymethyl methacrylate, films made of polyesters, e.g. polyethylene terephthalate or polyvinyl acetals or polyamides, e.g. B. from hexamethylenediamine and adipic acid, also from cellulose esters, z. Ii. Cellulose nitrate, Cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate. This means that conventional known ones for the production of the photographic recording materials according to the invention Supports can be used, as are customarily used for the production of photographic recording materials whose photosensitive layer consists of a photosensitive Polymers is made.

The layer thickness of the light-sensitive layer can vary

10 * 812/14 * 9

i $

be divorced. The thickness of the layer depends on various factors, in particular the intended use, the the recording material is to be supplied, the light-sensitive polymer used in the individual case and the nature of any other components present in the photosensitive layer. Usually this is Layer thickness about 0.00254 to 0.254 mm.

never photographic recording materials of the invention can according to customary known processes for production ™

of reproductions on photomechanical IVe ge can be used. This means that the recording materials can be exposed to a light source in a conventional manner suitable for the picture, by means of which the exposed areas of the photosensitive polymer are hardened or made insoluble. The known light sources rich in visible light and the known light sources rich in ultraviolet light, e.g. Previous year Carbon arc lamp !!, mercury vapor lamps, fluorescent lamps, volfrarilawpen, xitrophot lamps and the like. The exposed recording materials can then be developed by treatment with a solvent. ä All solvents are suitable which dissolve the unexposed, non-crosslinked polymer areas, but do not attack the exposed hardened polymer areas. A wide variety of known customary solvents can be used for this purpose, for example those as mentioned above and which are suitable as solvents for the production of the coating compositions.

Finally, the invention can be photographic Recording materials developed thereby, for example

10Ö812 / U99

-Vf-

ZO

that the exposed recording materials ^{are heated to temperatures of about 50-20O 0} C, ie to a temperature which lies between the stickiness point of the polymer in the unexposed areas and the polymer in the exposed areas, the polymeric areas of the unexposed areas Districts softened or made sticky. The softened or tackified polymer can then be developed with a toner or, with the application of pressure, transferred to an image-receiving layer and toned there. Finally, toning can be omitted if the photosensitive layer of the recording material already contains a pigment, a dye or a component which forms a dye.

In the following, the production of some according to the invention will begin usable polymers are described in more detail.

The sensitivity values described in the following examples were after the by L. M. Minsk and coworkers in the journal "Journal of Applied Polymer Science", Volume II, No. 6, pages 302-311 (1959) determined. The sensitivity value of a polymer is a measure of the relative sensitivity of the polymer, if the polymer is exposed to ultraviolet or visible light compared to the sensitivity of the non-sensitized Polyvinyl cinnamate as a comparison standard.

The spectral range given in the following examples denotes the lower and upper limiting wavelengths in mu, which lead to effective cross-linking of the polymers, XHMXK ^ XlKMXX & t ^^
which were previously applied to a paper support.

109812 / U99

20A1967

Example 1 Preparation of a polyvinyl ρ- (2-benzoylvinyl) cinnamates ^ method A

A suspension of one gram of a commercially available polyvinyl alcohol of medium molecular weight with 12 % acetate ^{residues +} (;; lvanol 52-22, manufacturer DuPont) in 25 ml of pyridine was heated on a steam bath overnight. After cooling to 30 ⁰ C 2 * 1 g (0.007 moles) of 4- (2-Chlorocarbonylvinyl) chalcone was added and the reaction mixture stirred for two hours at 50 ⁰ C for. 1.8 g (0.013 moles) of benzoyl chloride were then added, whereupon the reaction mixture was stirred for a further hour at 50 ° C. The reaction product was then poured out by pouring the reaction mixture in the form of a fine stream into cold water with stirring. After pilling three times with fresh water, the polymer was filtered off and dried in vacuo over calcium chloride, giving a total of 3.2 g of polymer.

The polymer had a sensitivity value of 17,000 and a spectral range of 260 - 425 inu.

For applying the polymer to a substrate and |

to Ln ti. ic moo ;; a recording material prepared using the polymer can be used as a solvent, for. B.:. ^: , .I-dimethylfornamide can be used.

lurch Sojisibilisieruir-, -! es polynors iit 2 , (, - ! '- is (p-nethoxyjj'ienyl) - 1- (pn-ainyluxyplicnyl) - tli iapyryliumiierclilorat e.g. Ί / if't a Πι j> f indliCukoi tswcrt of Γ · 3 700 and a ■ spectral range of ZG) - 57 (5 nn).

* 12 Μοί-Ϊ aoetate residues, based on the number of HydroxyIre a th

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- ν * -U

Example 2 Preparation of a poly (vinyl-p- (2-benzoylvinyl) -cinnamates7-Hethode R

This example illustrates a process for the production of polyvinyl esters with particularly good solubility properties, which is particularly suitable when acid chlorides of relatively high molecular weight are used to prepare the polymers be used.

A suspension of 4.4 g (0> 10 moles) of a commercially available, high molecular weight, fully hydrolyzed polyvinyl alcohol (I-lvanol 72-60, manufacturer DuPont) in 100 ml of pyridine was heated on the steam bath overnight in order to swell the polyvinyl alcohol. After cooling to 30 ⁰ C was added 4 ml (0.035 iole) of benzoyl chloride, and the reaction mixture one hour was warmed to 50 ⁰ C for. Now 7.4 g (0.025 moles) of 4- (2-Chlorocarbonylvinyl) chalcone was added and the reaction mixture was stirred for another two hours at ⁰ C SO. Finally, 4.6 ml (0.04 mol) of benzoyl chloride were added, whereupon the reaction mixture was ^{stirred at 50 °} C. for a further hour. The polymer was precipitated by pouring the reaction mixture into water / water, filtered off and purified by stirring with two portions of fresh water, filtered again and dried in vacuo. 18 g of polymer were obtained.

Results from the hats compiled in the following table that the sensitivity and the spectral Response of the polymer to the addition of certain sensitizers can be increased considerably, whereas the addition of other sensitizers increases the spectral response leads to a loss of sensitivity leads.

109812/1499 bad

-Vt-
Room Sensitive-
worth 000 Spectral range
(my.) Sensitizers 27 000 260-435 without 19th 000 260-490 2-benzoylmethylene-1-methyl-
ß-naphthothiazole 17th 000 260-490 Methyl-3-methyl-2-benzothia-
zolinylidenedithioacetate 38 500 260-475 1,2-benzanthraquinone 13th 500 260-460 Michler's ketone 13th 600 260-440 4H-quinolizin-4-one 7th 700 280-490 4II-quinolizine-4-thione 2 000 280-560 Jiosin Y 24 250 260-440 N-phenylacridone 4th 000 290-505 N-phenylthioacridone 38 500 260-540 2,6-bis (p-ethylphenyl) -4- (p-
n-amyloxyphenyl) thiapyrylium-
perchlorate 53 000 260-590 2,6-bis (p-ethoxyphenyl) -4- (pn-
amyloxyphenyl) thiapyrylium per-
chlorate 38 260-440 5,6-dihydro-2,4-diphenylnanhtho-

/ 1 ^ -b / pyrylium fluoborate

Example 3 Preparation of an epoxy p- (2-benzoylvinyl) cinnamate

A mixture of 5 g (0.025 equiv.) Of a fipoxy resin from Epichlorohydrin bisphenol A type (commercial product EPON 1009, manufacturer Shell) with an equivalent weight of 200 sov.'ie 5 grams (0.017 moles) of 4- (2-chlorocarbonylvinyl) chalcone in 50 grams of 1,2-dichloroethane was left on a steam bath for 5 hours heated to reflux temperature. The polymer obtained in the reaction was then poured into the reaction mixture Ethanol precipitated. After washing with fresh ethanol it was the polymer is filtered off, on the filter again with ethanol

109812 / U99

wash and finally ge dried in vacuo over calcium chloride. The yield of polymer was 9.5 g.

Using 1,2-dichloroethane as a coating solvent as well as development solvent resulted in a sensitivity value of the polymer of 35.5 and a spectral range of 370-410 mu.

By sensitizing the polymer with 2,6-bis (p-üthoxyphenyl) -4- (p-n-amyloxyphenyl) thiapyryl unperchlorate a sensitivity value of 25 was achieved, whereby the spectral range was expanded to 540 mu.

Example 4 Preparation of a cellulose p- (2-benzoylvinyl) cinnamate

A mixture of 4 g of a commercially available Ilydroxyäthylcellulose of medium molecular weight (commercial product Natrosol 250-J, manufacturer Hercules) and 3 g of 4- (2-chlorocarbonylvinyl) chalcone in 75 ml of pyridine was ^{stirred at 50 0} C for 2 hours. A clear solution was obtained after 15 minutes. After 2 hours, 5.7 g (0.01 mole) Eenzoylchlorid were added, and the reaction mixture a further two hours' stirring at 50 ⁰ C for. The obtained polymer was then precipitated by pouring the reaction mixture into water. It was filtered off, washed and dried as described in Example 1.

The sensitometric data obtained for this polymer (17 % p-2-benzoylvinyl) cinnamate and 83 l benzoate) are summarized in the following table. Dimethylformamide was used as a coating solvent and a developing solvent.

100812/1499

Sensitive-
worth Spectral range
(i ^ i) 5000 270-430 6300 270-440 6300 270-440 25,000 270-580

Sensitizers

without
Benzil

2-Benzoylnothylene ~ 1-methylß-naphthothiazole

2,6-His (4-a "thoxyphenyl) -4- (pn-aniyloxyphenyl) thiapyry
lium perchlorate

Example 5 Production of a polyvinyl-p - /? - (p-methoxybenzoyl) -vinyl / cinnamatesj

1 g (0.02 mol) of a commercially available polyvinyl alcohol of medium molecular weight (commercial product Elvanol 52-22, manufacturer OuPont) was swollen for eight hours by heating in 35 ml of pyridine. The mixture was then stirred for one hour at 50 ⁰ C, after which 1.4 g (0.01 ilole, 1.15 ml) were added Henzoylchlorid. Finally, 1.3 g (0.04 moles) of 4- (2-chlorocarbonylvinyl) -4'-methoxychalcone was added, followed by stirring for an additional 6 hours with heating. The mixture was then allowed to stand over power at room temperature, after which the resulting viscous mass was decanted off from a small amount of solids. The viscous mass obtained was then poured into 1 liter of water, the polymer precipitating out. The liquid was decanted off and the solid polymer was washed several times with cold water and then dried at room temperature. Hs was obtained in a yield of 2.2 f>.

The sensitometric Hijjonschafton give diose polymer

BATH ORIGINAL

101112/1489

3800 270-420 2690 290-460 8500 260-560

from the following table, As a solvent for the preparation Cyclohexanone was used in the coating composition for development.

Sensitizers Sensitive - Spectral Range

value (inu)

without

2-Benzoylmethylene-t-methyl-ßnaphthothiazoline

2,6-bis (p ~ ethoxyphenyl) -4- (p-n-arayloxyphenyl) thiapyrylium- perchlorate

Example 6 Production of a Polyfvinyl-p- ^ 2- (p-ar.iyloxyhenzoyl) vinyl / cinnamatesX * ·

This polymer was prepared according to the procedure described in Example 5, except that each one gram (0.02 moles) of the polyvinyl alcohol, 25 nL pyridine, t, 13 g (0.02 mole, 0.003 moles) renzoylchloric! and 1.9 g {0.005 mole) of 4- (2-Chlorocarbonylvinyl) -4 arnyloxycl ^u »a3con were used IIIe Ausleute of polymer was 2.7 g. The unsensitized polymer had an immunity value of 1010 and a spectral range of 280-125 nvi. Cyclohexanone was used as the layer solvent and solvent for development.

The one with 2,6-1Hs (p-iUhoxyphenyl) -4- (p-n-amyloxypheny 1) t h lapyrylium perchlorate aensil.i lisicrtt «polymer possessed an inpfind · probability value of 1000 um! a spectral range of 2oü 560 rim.

BATH ORIGINAL

Example 7 Production of a poly / vinyl-3- (5-styrylfur- ^ 2-y3) acrylate?

A mixture of 1 g (0.02 hole) of commercially available medium molecular weight polyvinyl alcohol (Elvanol 52-22) and 25 ml of pyridine was heated over power on a steam bath. Then 0.8 ml of benzoyl chloride were added, whereupon the mixture was stirred at 50 ° C. for a further hour. Thereafter -2-styrylfuran added 1.8 3 5- (2-Chlorocarbonylvinyl), followed by stirring for further three hours at 50 ⁰ C. Finally, a further 1 millimeter of benzoyl chloride was added, whereupon the mixture was stirred again for two hours ^{while heating to SO 0 C.}

The polymer obtained was then described as in Example 5, isolated. It was obtained in a yield of 3. G g.

The sensitometric properties of this polymer, the using 1,2-dichloroethane as the coating solvent and developing solvents are shown in the table below;

Sensitizers

without

2-Benzoylmethylene-i-methylß-naphthothiazoline

2,6-bis (p-ethoxyphenyl) -4- (p-n-amyloxyphenyl) thiapyry · Lium perchlorate

Sensitive
worth Spectral range
(nm) 2500 260-460 3150 280-470 1580 300-550

BATH 109812 / U99

-aiii

Example 8 Preparation of a poly ^ vinyl-p .- (2-nitrovinyl) cinnamate7

A mixture of 2.1 g (0.042 moles) of a commercially available medium molecular weight polyvinyl alcohol (Elvanol 52-22) and 70 ml of pyridine was heated on the steam bath overnight. The mixture was then cooled to 50 ° C and 1 ml of benzoyl chloride was added. The mixture was stirred for one hour while heating to 5O ⁰ C. Then 2.5 g of p- (2-nitrovinyl) cinnamoyl chloride was added, and the mixture was stirred with heating for another two hours. Finally, 3 ml of benzoyl chloride were added, whereupon the reaction mixture was ^{stirred at 50 °} C. for another hour. The polymer obtained was then isolated as described in Example 5.

Are bifunctional compounds with the photosensitive radicals described for the preparation of the invention The photosensitive polymers used are used, so it is necessary, as already stated, to use a to block the functional residues of the bifunctional compounds. The following is intended to block one of the functional groups, a carboxyl group, a bifunctional reaction component, namely a dicarboxylic acid Formation of the half-acid half-ester or ITalbic acid chloride half-ester are described in more detail.

A Production of di (2-ethylhexyl) -p-phenylene diacrylate

250 g (0.91 moles) of diethyl p-phenylene diacrylate were with 500 ml of 2-ethyl-1-hexanol and 1 ml of titanium isopropoxide in a column with a distillation head for separation

BATH ORIGINAL 109812 / U99

an azeotropic mixture heated as long to return flulJtep'pera door, reaching to the top of the column a temperature of 18O ⁰ C. A mixture of ethanol and 2-ethyl-1-hexanol was gradually distilled off. After most of the alcohols had been removed, the reaction mixture was cooled to room temperature, with partial solidification occurring, never supernatant liquid was removed by filtration, whereupon the resulting crystalline mass of petroleum

ether recrystallized, washed with cold petroleum ether |

and dried over phosphorus pentoxide under reduced pressure.

The yield of pure di (2; lthylhexyl) -p-phenyiendiacrylat having a melting point of 62-64 ⁰ C was 356 · ■ or 8.1,5% of theory.

Anal, I. calculated for C. ,,, 1 '0 _r : C: 76.0 ""; I!: 0.5 %. Cn found: C: 75.8 \\ II: <>, 5 I.

h lierstellunj? of the f! ono-2.-flthylhoxyl ester of phenylenhis (acrylic acid)

356 j (0.8O ^ moles) di (2-Uthylhoxyl) -p-phenylenebisacrylate in 2500 ml;) ioxane were mixed with 32.5 g (0.81 mol) of sodium hydroxide Stirred in 75 i :: l water until the cation mixture solidified. Then enough water was added that all the solids fi'CStestandi Ic went into solution. The solution obtained was then strongly acidified by the addition of hydrogen chloride, whereby the Ilalbs'iure-Ilalbester precipitated. The crude reaction product was invented with water, washed, dried, and off Benzene crystallized. The yield of white Μοηο-2-.Ίtbylhexyl-p-phenylenbi s (acrylic acid) was 2ΠΟ>. or 75.7 "the

BATH ORIGINAL

10IIU / U90

Theory. The acid had a melting point of 170-172 ⁰ C.

Anal. Calculated for found:

: C: 72.5 %; H: 7.9 C: 72.3 t; II: 8.1

C Production of p moyl chloride

- (2-Ethylhexyloxycarbonyl) vinyl7cinna-

To 37 g (0.112 moles) of p- / 2- (2-ethylhexyloxycarbonyl) vinyl7cinnamic acid was added a 100 liter excess of thionyl chloride and the mixture was heated to reflux temperature for two hours. The excess thionyl chloride was then distilled off, whereupon the remaining Hl was distilled in a high vacuum. (Kp. 158 ⁰ CZSyU, NJ ^ ⁵ = 1.6205).

The yield of reaction product was 36.5 g or P3.7 g the theory.

Anal. Calculated for C ₂₀ II ₂₅ O ₃ Cl: C: 68.8%; H: 7.2 %; Cl: 10.2 %. Found: C: 6 [beta], 4 % ; II: 6.8 Z; Cl: 10.0

Example 9 Production of a Polyfvinyl-p- / 2- (2-ethylhexyl oxycarbonyl) vinyl / cinnamates} of the formula:

, Z 1

38- ^ ^CH 2-? ^H - ^ ö-, 50

0 0 0 I. I. I. C-O OO o-c I. I. cn, Ij CH
Il CII

BATH ORIGINAL

109812 / U99 I.

0-CU-CuJ-CH (CIl ₂ ) 3-ClI,

JV

2 g (0.0454 equiv.) Of a commercial polyvinyl alcohol-average molecular weight (DuPont Elvanol 52-22) was heated in 100 ml of dry pyridine for 8 hours at 80 ⁰ C. The swollen polyvinyl alcohol was then cooled to room temperature and 2 ml (3.2 g, 0.0227 moles) of benzoyl chloride was added. The reaction mixture was then heated for 2 1/2 hours at 50 ⁰ C, followed by 8.0 g (0.0228 moles) of p- / 2- (2-Äthylhexyloxycarbonyl) vinyl7cinnamoy! Were added chloride. The mixture was then heated with stirring for a further four hours. The polymer obtained in the reaction was then isolated by slowly pouring the reaction mixture into 98% methyl alcohol. Leached in 98% methyl alcohol and then in aqueous methanol, the polymer was dried over phosphoric anhydride under reduced pressure. The yield of the photosensitive polymer was 10.5 g, corresponding to 92

% of theory.

Anal. Calculated for C ₁₁ - rH _ir .0_: Found:

C: 73.8 %; H: 7.1
C: 74.4 %; II: 7.2

The sensitometric data of this polymer produced using dichloroethane was tested as a coating solvent and dichloroethane as a developing solvent, are compiled in the following table:

Sensitizers

without

2,6-bis (4-ethoxyphenyl) -4 - (4-nainyl oxyphenyl) -th iapyryl iumper ■ chloret

2-Benzoyl'nethylen-1-ynethyl-fnaph ti ίο th ia zol in

4-H-quinolizine-4-thione

Sensitive spectral sensitivity rich (rough)

2000 2 70-380 8000 2 70-520 20000 270-400 2 EOO 27Q-4SO

109812 / U99

BATH ORIGINAL

Example 10 Production of an epoxy-p- / 2- (2-äthylhexyloxycarbonyl) -vinyl / cinnamates of the Γοπηοΐ:

cn, -cr-ci -, - 0

Cn = CH-CO-CII ₉ -CC ₁ H _n II 2.49

0 C ₀ Il ₁ -

25 g (0.08 equivalents) of a polyether, produced by condensation of 2,2-bis (p-hydroxyphynyl) propane iuit \ l \ ichlorohydrin (manufacturer Union Carbide, Phenoxy P.'DA Resin) were made in 800 μl of a mixture Pyridine and dichloroethane dissolved in a ratio of 50:50. To the resulting solution then 31 g (0.089 equivalents) of p ^ 2- (2 ^ thylhexyloxycarbonyl) vinyl7-cinnamoyl chloride were added, was heated vvorauf the mixture in total darkness under ßelegentlichem shaking the reaction mixture for 4 hours at 50 ⁰ C.

The cooled solution was then slowly added in 4 1 of a 1 98 methanol solution. After leaching the polymer in the 98% methanol and then in anhydrous ethanol, it was dried over phosphoric anhydride under reduced pressure. All measures were carried out in the absence of white light.

BAD OftlQiNAL

109812 / U99

The yield of photosensitive poly {_2-jp- / 2- (2-ethylhexyloxycarbonyl) vinyl7cinnamoyloxyltririethylen-2,2-bis- (4-oxyphenyl) propane was 45 g, corresponding to 86.5 % of theory.

Anal. Calculated for C ₃₃ ¹ J ₄₄ O ₅ : C: 76.5 % ; H: 7.3 I. Found: C: 76.7 %; I !: 7.3 %,

The sensitometric data of the polymer, which were determined using dichloroethane as a coating solvent and as a developing solvent, are summarized in the following table:

Sensitizers Sensitive- Spectral-

value rich (mu)

without

2,6- »is (W! Thoxyphenyl} -4-

(4-n-amyloxyphenyl) -thiapy-

rylium perchlorate

2-Benzoylmethylene-i-methylß-napl »tnothiazoline

D Production of the monodethyl ester of p-phenylon bis (acrylic acid)

The compound was prepared according to the process described in B, but this time instead of dioxanethanol and, furthermore, diethyl-p-phenylcmllacrylate was used instead of di (2-ethylhexyl) ester. The reaction product was recrystallized from benzene. (Mp. 214-215 ° C; yield J) I ₁ O \ the Tlicorie).

• \ nal. i.frcchnct for C ^ i ₁₁ O ₄ : C: 6 «, 2 ',;H; 5, S 1, r; <> round: C: 6Γ,, 5 \\ W : 5.7 \.

BATH ORIGINAL

109812 / U99

1100 280-365 2300 280-360 4800 280-430

■ 704196 V

-SASH

M Production of a ρ- ( Z-itthoxycarbonylvin yljcinnainoylciil orides

The compound was prepared according to the process described in C, but this time the monoethyl ester of p-phenylenhis (acrylic acid) was used. The reaction product distilled at 160 ° C./10 η (melting point 125-126 ° C.; yield 80.5 % of theory).

Anal. Calculated for C ₁₄ II ₁₃ O 1 Cl: C: 63.5 I; H: 4.9 I; CI: 13.4 % Found: * C: 63.5 % ; II: 4.9%; Cl: 13.P ".

Example 11 Preparation of a Iipoxy-p- (Z-iithoxycarbonylvin; Ijcinnamates

CII.

ο - L ^w

J-CH-CH-

ο ο

34.08 g (0.12 equiv.) Of a polyether manufactured by Polycondensation of 2,2- "is (p-hydroxyphenyl) propane with lipichlorohydrin (manufactured by Union Carbide R-Co., commercial product Phenoxy PIU) A) were in POO ml of a mixture of dichloroethane and pyrhline by shaking under anhydrous conditions (The ratio of dishlorethane to pyrldine «11:10 parts by volume),

31.6K g (0.12 hole) of p- (2-Xthoxycarbony1vinyl) monoyl chloride in 300 ml of trocLencii P> ^r ri <lLn were then added to the resulting solution. The mixture obtained then became hotter

108812 / U99 bad original

Jf

Darkness with occasional shaking for six hours heated to 5 5 ° C.

The resulting solution was then slowly poured into 4 liters of a 98 ml • Lethanol poured. The polymer obtained thereby precipitated. To Leaching of the polymer in the 981 igen.! Ethanol and then in anhydrous methanol, it was dried over phosphoric anhydride under reduced pressure.

All process steps were carried out in the absence of light.

The yield of photosensitive polymer was 27 %, corresponding to 93% of theory.

Anal. Calculated for ^c - ₅₂ ^U 32 ° f> ^{: C: 75} »° * ' ^{Ii: 6} » ² *' Found: C: 74.5 % \ Yr. 6.2 %.

The determined sensitometric data of this polymer using dichloroethane as the layer solution liquid and developing solvents are in the following Table compiled:

Sensitizers

without ·

2,6-bis (4-ethoxyphenyl) -4- (4-n amyloxyphenyl) thiapyrylium perchlorate

2-Benzoylmethylene-i-methyl-ßnaphthothiazoline

4-H-quinolizine-4-thione

Recommended
no value Spectral range 1300 270-385 3000 270-560 8000 270-460 8000 270-485

10d8i2 / U99

2OA 1967

- 99 -

The following is the preparation of used according to the invention Described polymers similar to polymers of the type described in Example 41, but terminally unsaturated Have residues in the light-sensitive side chains.

F_ Production of diallyl-p-phenylene diacrylate.

274 g (1 mol) of diethyl p-phenylene diacrylate were heated to reflux temperature with 1250 ml of allyl alcohol and 5 ml of titanium isopropoxide in a flask with an attached column with a column head to collect an azeotropic distillation mixture until the temperature of the column head was 97 ⁰ C reached. A mixture of ethanol and excess allyl alcohol was slowly distilled off. After most of the alcohols had been removed, the mixture was cooled to room temperature, whereupon the reaction product crystallized out. The crystals were filtered off and recrystallized from hexane, washed with cold hexane and air dried. The yield of the reaction product was 2 50.8 g, corresponding to 83.8% of theory (mp. 60-62 ⁰ C).

Anal. Calculated for C ₁₈ H ₁₈ O ₄ : C: 72.4 % ; H: 6.0 %. Found: C: 72.3 % ; II: 6.4 %.

G Preparation of the mono-allyl ester of p-phenylenebis (acrylic acid)

A mixture of 258.8 g (0.84 moles) of the diallyl ester, prepared as described under F, in one liter of allyl alcohol and 33.3 g of sodium hydroxide in 100 ml of water was ^{stirred with heating to 50 °} C. until the reaction mixture had become solid. Then so much water was added that

109812 / U99

the solids were dissolved, and the resulting solution was made strongly acidic by adding hydrochloric acid. The ilealbic acid IIal ester precipitated out. The crude reaction product (218 g) was filtered off, washed thoroughly with water, dried and recrystallized from benzene. 160 ζ, corresponding to 65.5 % of theory, were obtained. (Mp 209-21O ⁰ C)

Anal, calculated for C ₁₅ II ₁₄ O ₅ : C: 69.8 %; II: 5.4 ^% .

Found: C: 70.1 %; II: 5.6 %.

i: Preparation of p- (2-allyloxycarbonylvinyl) cinnamic acid chloride

! - ° <i (O, 4f "6 moles) Jer 4- (2-Allyloxycarbonylvinyl) cinnaminsüurc, prepared as described in C were mixed with 63 g (0.5 Oil!) Of oxalyl chloride and ¹ drop of M, N Diinethylformamide was added, whereupon the reaction mixture was heated to the reflux temperature for 2 hours. 250 ml of zinc were then added, whereupon the mixture was allowed to run for another 30 minutes. was raised to the flow temperature. The excess oil was then removed by distillation, whereupon 250 ml. Of dry constituent were added , whereupon the lioal tion product: t was distilled. (Kp 1ΓΐΓ> ° (: / 3 u, Fp.

The yield of the reaction product was 99%, corresponding to 78 \ theory.

Anal,! Leruchnot for (; _{| r} JI ^ (: Li) ^; C: 65.3 ';;Ii; 1.7 I; CI: 12.7 I.

'■ (■ found: C: fi5,. ·;?; Γ: 5.0 \; Cl: 13.1

BATH 101812/1499

204196V

Example 12 Preparation of a Iipoxy-p- (2-allyloxycarbonyl vinyl) -cinnainate of the following Tornel:

C = Q

cn

CII = CI! -C-0-CI! _o -CH = CfL · | 2 2

6 g of a polyether, prepared by polycondensation of 2,2-bis (p-hydroxyphenyl) propa ι wit Tpichlorohydrin rut an intrinsic viscosity of 0.87 (manufacturer Shell Chemical Co., retail product Upon 55P-40 Üesin) were in 200 vil a solution mixture of dry pyridine and dry egg :; 1,2-nichiorethane in a ratio of 1: 1 «elust. The 'was erwürmt to 70 ⁰ C iischung, after which 6.9 of, i> emäß Il prepared Sfiiireclilorides g were added with stirring under substantially anhydrous conditions.

Do four hours! The mixture was heated and stirred, cooled and by adding an equivalent volume of 1,2-dichlorotthane pre-thinned and filtered. The polymer obtained was then isolated in that. » the FiItrat very slowly in four times the volume of 95% methanol with stirring was poured. Do a thorough leach with fresh methanol the polymer was air dried. The yield of polymer was 10 g, never sensed by Italian standards

BATH ORIGINAL

of the polymer result from the following table:

Sensitizers Sensitivity Spectral Value Range (mu)

without 1500 280-390

2-benzoylmethylene-1-me thy 1 -

β-naphthothiazoline 5500 280-480

2,6-bis (p-ethoxyphenyl) -4-

(p-n-amyloxyphenyl) -thiapy-

rylium perchlorate 7000 280-580

Example 13 Preparation of a poly / vinyl p- (2-ethoxycarbonyl-2-cyanovinyl) cinnamate 7

This polymer was made according to the procedure described in Example 5 using one gram (0.02 moles) of the commercially available medium molecular weight polyvinyl alcohol, 25 ml pyridine, 1.2 ml benzoyl chloride and 1.16 g (0.04 moles) of p- (2-ethoxycarbonyl-2-cyanovinyl) cinnamoylchlorides. 2.2 g of polymer were obtained.

The unsensitized polymer had a sensitivity value of 1000 and a spectral range of 290 - 404 mu. As a coating solvent and a development solvent Cyclohexanone was used.

By sensitizing the polymer with 2,6-bis (p-ethoxyphenyl) -4- (p-n-amyloxyphenyl) thiapyrylium perchlorate a sensitivity value of 2200 and a spectral range of 290 - 565 became rough achieved. '

109812 / U99

HO

Example 14 Preparation of a Polyfvinyl-p- ^ 2 "- (2-ethyl · iiexyloxy-carbonyl-Z-cyanovinyl / cinnamatesj

This polymer was prepared according to the procedure described in Example 5 using one gram (O _f O2 moles) of the medium molecular weight polyvinyl alcohols, 25 ml pyridine, 1.2 ml benzoyl chloride and 1> 9 g p- / 2- ( 2-Ethylhexyloxycarbonyl) -2-cyanovinyl "7cinnainoyl chloride. 3.2 g of polymer were obtained.

The unsensitized polymer had a sensitivity value of 500 and a spectral range of 290-400 ir.u using a mixture of cyclohexanone and methylethyl keto n in a ratio of 50:50 as a coating solvent and developing solvents.

Was the polymer with 2,6-bis (p-ethoxyphenyl) -4- (p-n-anyloxy- ' phenyl) thiapyrylium perchlorate, a Sensitivity ranges from 1780 and a spectral range of 290-550 mi received.

Example 15 Preparation of a photosensitive polymer from a styrene-maleic anhydride copolymer

4 g 0.02 Hole) of a styrene-Maleinsäureanhydridmischpolymeren of high molecular weight with a Molvedältnis of styrene to Maleinsäureanliydrideinheiten of about 1: 1 (Ilandelsprodukt Lustrcx 810, Monsanto Chemical Co.) and 100 ml of pyridine was heated for one hour on the steam bath. After cooling to room temperature 3.8 g (0.01 mole) of 4 'was - (ß-IIydroxyifthoxy) -4- (2-äthoxycarbonylvinyl) chalcone was added and the mixture for four hours with stirring to 50 ⁰ C.

109812/1499

Hi

was heated. The mixture was then placed in a dilute hydrogen chloride solution, causing the polymer to precipitate. The aqueous phase was removed, whereupon the polymer was washed 3 times in 3 liters of cold water each time. Ice, 5.5 g of polymer were obtained.

Example 16 Preparation of a polyivinyl-p- / 2- (2-ethylhexyl oxycarbonyl) vinyl / cinnanate-co-vinylbutyralsj

30 g of a carefully, dried, partially hydrolyze ™ polyvinyl butyral (commercial product Butvar 72-Λ, manufacturer Shawinigan Itcsins Corporation, Springfield, Massachusetts) with an average molecular weight of 180,000 to 270,000 and a hydroxyl group content, expressed in weight! . Dissolved 1: polyvinyl alcohol 17.5 to 21.0 wt -X, were dissolved in 400 ml of a mixture of dry pyridine and 1,2-Dichloroiithan in the volume ratio 1.

Under practically anhydrous conditions, 43 g of p- ^ 2- (2-ethylhexyloxycarbonyl) vinyl7cinnamoyl chloride were then added over a period of 5.5 minutes. The flischung was heated under P. (your four-hours at 70 ⁰ C, then cooled to room temperature and {with an equal volume of 1,2-Uichloroüthan diluted, after which it was filtered. The polymer was then precipitated from the solution by that the piltrate was poured into 6 times the volume of 95 liter methanol. The precipitated polymer was filtered off, cut into very small strips and then thoroughly leached with methanol, then water and finally again with methanol. The filtered solid polymer was then over Phosphoric anhydride dried under reduced pressure. There was obtained 66.5 »of a thermoplastic polymer. The sensitometric data of this polymer obtained using

BAD LOCATION

of 1,2-dichloroethane as a coating solvent and Developing solvents are identified in the compiled in the following table:

Sensitizers

E rap f ind 1 i ch- Spe ktra Ibe ■ value rich (mu)

without 1000 28C - 38O 2-benzoylmethylene-i-methyl- ß-naphthothiazoline 7000 2 80-4SH 2,6-bis (4-ethoxyphenyl) -4- (4- n-amyloxyphenyl) -thiapyrylium- perchlorate 15000 280-580 4H-quinolizine-4-thione 5000 280-5OO

Example 17 Preparation of Copolyistyrol-4- _i ([p- (2-benzoylvinyL) ·

cinnamido / styrene ~ 4-ben2ar _i jiidostyrol | _i the form;

- (- CH ₉ -CH

C-O

CH-CH

^C 6 ^f! 5

ClI-CIl-CC, i! _
6 5

To. 7.3 g (0.03 mol) of a 45% batch of a copolymer from styrene and 4-amiaostyrene in a molar ratio from 1.7: 1) in Oioxan were 75 nl dry pyridine and 3.6 β (0.012 moles) 4- (2-chloroacarbonylviiiyl) chalccn against

BATH ORIGINAL

HS

ben. The mixture was then stirred at 50 ° C. for two hours during which time complete dissolution occurred. 2.2 μl of benzoyl chloride were then added to the mixture and the mixture was again heated with stirring for two hours. Shortly after the addition of the benzoyl chloride, a solid precipitate began to separate out. The leaction mixture was then poured into 3 liters of water, whereupon the precipitate was filtered off and laughed over in fresh; ! 'what has been soaked. Thereafter, the precipitate was filtered off, washed with water and dried in a Iixsi-% cator over calcium chloride. A total of 7 g of poly was obtained.

The polymer had a sensitivity value of 22 and one Spectral range from 230 - 380.

Use of the polymers Usage example 1:

Production of a planographic printing form (lithographic printing plate) using a poly / vinyl-p- (2-benzoylvinyl) cinnamate7. j

A 4 celled solution of poly / vinyl benzoate-vinyl-p- (2-benzoylvinyl) cinnamat7 prepared as described in Example 2, 25 I p- (2-benzoylvinyl) cinnamatresten in 2-butanone and cyclohexanone in a ratio of 3: 1 as Solvent, was after the. Fluidized coating process applied to a layer support made from a roughened aluminum plate and also onto a layer carrier made from a coarse-grained zinc plate.

The recording materials obtained were then each

BATH ORIGINAL

109812/1499

-Jf-HH

for two seconds with a standard lamp (General Electric RS Sunlamp) placed about 10 inches away was exposed through a transparent line and line negative.

The plates were then developed by buffing with cyclohexanone and 2-butanone. Then one became desensihilizing effective etchant applied, whereupon the plates finally colored with a bold lithographic ink.

Using the printing plates obtained, positives of excellent quality were obtained. Furthermore, a 3-term solution of a corresponding vinyl p- (2-benzoylvinyl) cinnamate polymer from a mixture of dimethylformamide and 1,2-dichloroethane in a ratio of 3: 2 and primed Unprimed roughened aluminum plates applied.

The plates were then removed again through a halftone line negative with a distance of about 50.8 cm exposed xenon lamp. The exposure took place while in a commercially available printing form manufacturing device (Nu-Arc-Flip-Top Platemaker, manufacturer Nu-Are Corporation, Chicago, Illinois). After 10 units of exposure, the panels were cleaned by buffing with 4-butyrolactone developed. A desensitizing etching agent was applied to this, whereupon the plates were treated with fetter Ink were colored. In this way they were awarded get sharp positive printing forms.

Use example 2 ;

Production of a photoresist material from a polyvinylp- (2-benzoylvinyl) cinnamate§7

10I812 / U99

«R

A partially hydrolysed polyvinylacetate of medium molecular weight was esterified by the method described in Example 2, wherein a light-sensitive polymer with 12% acetate residues, 68 I p-Lauryloxybenzoatresten and 20% p- (2-benzoylvinyl) was obtained -cinnamatresten.

The polymer obtained had a sensitivity value of 5000 and a spectral range of 280-425 μm.

Line 4 wt -.% Solution of this polymer with 0.1 wt -%. *

2,6-r.is (p-ethoxyphenyl) -4- (p-n-amyloxyphenyl) thiapyrylium perchlorate in chlorobenzene, the powder coating method was used applied to a 0.5 mm thick copper plate, which was previously treated with a 5% hydrochloric acid treated, washed, and air dried. The coated plate was then lana at SOoC for 10 minutes dried in a circulating air oven.

The plate was then placed in a device for generating Printing forms, such as sio Lm use sh ei spit; I 1 described was exposed through an Ilalbton line negative.

The plate was then developed in trichloro'lthane and rinsed with acetone. After masking the back of the plate with adhesive tape, it was etched for 10 minutes in a ferric solution of 4 2 ° rooms at room temperature. After rinsing with diluted acid and water, the plate was dried. Phoephor-

I) The plate obtained shows excellent resilience properties Jos Poly- ^ vlnyl-p- (2-bonzoyivln> 'l) cinnamatea7 opposite dor Ferric chloride solution.

1QM12 / U9Ö

2041367

Uses log example 3

Manufacture of planographic printing plates and photoresist elements.

1. A solution of 5 % of the polymer produced according to Example 9 in 1,2-chloroethane was applied by the coating process to an anodized, roughened tin-coated aluminum plate provided with an adhesive layer.

2. EIa corresponding recording material with dignity nnter '.he application van 0.1% 2, 6-bis (4-ilthoxyphenyi) -4- (4-n-amy7 <: ^x>;:' thiapyryliuniperchlorat prepared.

The recording material 1 was produced using the in Example 1 of an exposure of 40 units and the recording material 2 of an exposure suspended by 30 units

The plates were then developed by desensitizing them in 4-butyrolactone, whereupon they were rinsed with water and treated with a desensitizing etchant. Then wurden- by rubbing a fat lithographic printing ink eingefitrbt - _t which neg & iv working Flachdruckforraeii excellent quality were obtained.

3. A 10% solution of the polymer prepared according to Example 9 was dissolved in chloroform. 0.1 % of 2,6-bis (4-ilthoxyphenyl) -4- (4-n-amyloxyphenyl) thiapyrylium perchlorate were also added to the solution obtained. The ßschlchtungsmassc v.-was then applied "after the vapor coating process on a MlEXIi: /" with an approximately 0.038 mm thick copper layer for the production of printed circuits, whereupon the applied layer was dried for ^{15 minutes at 43 0 C}

/ "Sohlohfetrlger, - W. aus mit G · is ^f t« e.wi v «rstttrfct« n

or tiIr ► »Ραβκ-ιϋι * ⁷ λ»

¹ , / | * \ t ' ^l ' ^vi BATH ORIGINAL

♦ 7

The resulting recording material was then imagewise
15 units exposed in a commercial copier (type 3M 107), developed in a vapor degreasing device with hot trichlorethylene, heated to 120 ° C for 5 minutes and etched by placing a ferric chloride solution of 42 ° Baume at 54 ° on the plate for 3 minutes C was sprayed on. In this way, an ink-drawn resist image was obtained which was excellently suited for applications in the field of printed circuit boards.

108812/1499

Claims (1)

Hi Claims Photographic recording material consisting of a Layer support and at least one light-sensitive layer made of a light-sensitive linear film-forming polymer with ethylenically unsaturated side chains on the linear Main chains and optionally a sensitizer for the polymer, characterized in that the photosensitive Polymer is composed of units of the following formula -A- Y I CH Il CH CH where mean: -A- a main chain of the polymer; Y is a carbonyloxy, oxycarbonyl or amido radical; R.J an optionally substituted arylene radical or heterocyclic radical with 5- or 6-ring members; Pv2 is a hydrogen atom or a cyano, alkyl or Alkenyl radical; 109812/1499 - Jr * - Κ, a Kasserstof fator.i, a .Vitro or heterocyclic Radical or an alkyl, alkenyl, aryl, alkoxy, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, Alkcnyloxycarbonyl or aryloxycarbonyl radical, v.'obci pilt that the aryloxycarbonyl, arylcarbonyl, Aryloxy and \ ryl radicals, optionally by nitro, Azido, alkyl, alkoxy, dialkylainino or diaryl · amino radicals can be substituted. 2. Photo ranhischos Aufzeichnunßsi.i.material according to claim 1, da-! Urcu /.ekmarks that it has a light-sensitive linear polymer of the ^{formula at T} o,: cboncn, in which: Y an orarbonyloxy residue, Rj is an optionally substituted phenylene radical, ! '., an i.'asscrstoffatoi.'i and P, an alkoxycarbonyl, all onyloxycarbonyl or ■ '* Aryl carbonyl radical. 3. Photographic recording material according to claims 1 and 2, thereby {jckennzeichnot, <let it be a light-sensitive linear Polymer of the prestigious Poriuel, whose main chain -A-itself of polyvinyl alcohol, a partially hydrolyzed polyvinyl monster, an egg. partially hydrolyzed polyvinyl acetal, cincii J'oiy.'lther, cellulose, a partially ver; lthcrten or esterified !! Cellulose, a free Ilydroxylreste having Polyester, a polyvinylamine, a polyaminostyrene or a polyvinyl anthranilate derived. 1. Photographer inches Aufzeichnuni'.iüitatcrial according to claim 1 to 3, dadurcli marked, daf. d; is 1 ichtcitipf indigenous polymer dor BATH - ¥ 9 light-sensitive layer from the reaction product of (a) Polyvinyl alcohol or the condensation product of a Bisphenol with lipichlorohydrin with (L) a p-vinylcinnainoyl chloride vein a 4- (2-chlorocarbonylvinyl) chalcone, 5, photographic recording material according to claim 4, characterized in that the light-sensitive polymer is the light-sensitive layer made of the reaction product of (a) Poiy ¥ iny! alcohol or the condensation product of a; To· phenol with Hpichlorhydrin with (b) p- (2-kthoxycarbonylvinyl) cinnamoyl chloride, p- £ 2 ~ {2-Xthylhexyloxycarbonyl) vinyl7cinnamoyl chloride, 4- (2-chlorocarbonylvinyl) chalcone or 4 ™ (Z-chlorocarbonyl vinyl) -4 '-roethoxychalcone consists. 6. Photographic recording material according to claim 1, characterized characterized in that the main chains of the photosensitive Polymers other than side chains of the formula: S.
Y Ϊ " CII CU wherein Y, R ₁ , R ₂ and It _{3 have} the meaning given, has side chains from the polymer modifying carboxylic acid residues. BATH ORIGINAL 1439 ram _ (Pi 7. Photographic recording material according to claim 6, characterized characterized in that the main chains of the photosensitive polymer other than side chains of the formula given Has side chains of acetic acid or benzoic acid residues. 8. Photographic recording material according to claim 1, characterized characterized in that the photosensitive layer contains as photosensitive polymer: a Poly / vinyl p- (2-benzoyl vinyl) cinnamate 7; a polyvinylp- / 2- (2-ethylhexyloxycarbonyl) vinyl7cinnamate \; a polyfvinyl-p - / ^ - (2-ethylhexyloxycarbonyl) vinyl7cinnamatco-vinylbutyralj or a Poly £ [2 ~ fp- / 2- (2-ethylhexyloxycarbonyl) vinyl7cinnamoyloxy ^ - trimethylene-2,2-bis (4-oxyphenyl) propane? \. 109812 / U99